变温下SO_2~(-4)对水泥硬化浆体中Al~(3+)配位分布的影响

基于大体积混凝土内部的温度变化,利用27 Al魔角旋转核磁共振(27 Al MAS NMR)结合去卷积技术,研究变温下SO2-4对水泥硬化浆体中Al 3+配位分布的影响。结果表明,变温的高温阶段促进AFt、TAH(third aluminum hydrate)和掺杂在C-S-H结构中(C-S-A-H)的四配位铝(Al[4])向AFm转化;降温阶段促进TAH生成,利于AFm和C-S-A-H中Al[4]向AFt转化;而变温后20℃常温不仅利于AFt向AFm转化,TAH向Al[4]转变,而且利于Al[4]进入高钙硅比(Ca/Si)C-S-H结构。在5%Na2SO4溶液中,SO2-4在侵蚀3d时首先对AFm侵蚀,对TAH和C-S-A-H中Al[4]侵蚀作用较小;变温过程的高温加快SO2-4对AFm和TAH的侵蚀,并且对C-S-A-H凝胶有脱铝作用;变温后20℃常温有利于C-S-H凝胶与硫酸根竞争Al[4],低Ca/Si的C-S-A-H凝胶具有较强的抗SO2-4脱铝能力。     

碳硫硅钙石型硫酸盐侵蚀

介绍了碳硫硅钙石型硫酸盐侵蚀(TSA)的形成机理、形成条件、侵蚀模型、影响因素、预防和处理措施。形成机理包括溶液反应机理和硅钙矾石转变机理;侵蚀模型可分为化学模型和物理模型;形成条件包括硫酸盐、硅酸盐、碳酸盐、水和低温;影响因素主要有水泥种类、C3A和Al2O3含量、矿物掺合料、pH值、侵蚀介质、水胶比等。     

聚丙烯酸类水凝胶的制备及其在碱性溶液中的pH敏感性

以（NH₄）₂S₂O₈和NaHSO₃为氧化-还原引发剂、N,N′-亚甲基双丙烯酰胺（MBA）为交联剂,采用自由基水溶液聚合方法,分别合成了聚丙烯酸（PAAc）、聚丙烯酰胺（PAAm）和系列丙烯酸（AAc）质量分数（fAAc）不同的聚（丙烯酸-co-丙烯酰胺）（P（AAc-co-AAm））水凝胶。进而分别对其在碱性缓冲溶液和NaOH溶液中的pH敏感行为进行了探讨。结果表明,PAAc和P（AAc-co-AAm）凝胶在2种溶液中均具有优良的pH响应行为,且在NaOH溶液中的溶胀比大于缓冲溶液中;而PAAm凝胶仅在NaOH溶液中具有pH敏感性。2种溶液中,随f（AAc）的增加,P（AAc-co-AAm）凝胶的平衡溶胀比（ESR）增大;但在缓冲溶液中,当f（AAc）≥20%时,P（AAc-co-AAm）凝胶的溶胀行为与PAAc相似,而当f（AAc）<20%时,其溶胀则同时表现出PAAc和PAAm凝胶的溶胀特性。溶胀机理分析表明,凝胶的溶胀主要受聚合物网络内静电排斥作用和离子屏蔽效应控制。     

硫酸盐环境下灌浆材料长龄期力学性能及微观结构分析

本文将抗硫酸盐水泥和中热水泥掺粉煤灰制备的水泥浆体浸泡在5%Na2SO4溶液至1110d,研究长龄期硫酸盐侵蚀下各试件的力学性能和微观结构。结果表明:限制空间中形成的细小钙矾石是引起基体开裂的主要原因,石膏的形成会引起水泥基材料剥落,抗硫酸盐水泥不能有效防止石膏型硫酸盐侵蚀;大掺量粉煤灰的二次水化反应能够消耗大量氢氧化钙,从而降低侵蚀过程中石膏相的形成且能有效改善浆体微结构;水电工程中采用中热水泥+50%粉煤灰制备的水泥基材料能够有效抑制钙矾石和石膏的形成,其抗硫酸盐侵蚀性能和经济性明显优于抗硫酸盐水泥制备的水泥基材料。     

复合盐类侵蚀对硅酸盐水泥固化氯离子影响研究

研究了硫酸盐、碳酸盐和硝酸盐与氯盐复合侵蚀下硅酸盐水泥固化氯离子性能,采用水溶法测定了水泥净浆中自由氯离子含量并计算得出其氯离子固化率,对试样进行了XRD物相分析以及其水溶液的pH值测定。结果表明,水泥浆体的氯离子固化率随水化龄期的增长而增加;随氯离子浓度增大,水泥浆体中F盐的生成量增加,其氯离子固化率先增大后减小。随硫酸盐和碳酸盐浓度增大,水泥浆体的氯离子固化率均降低,硫酸盐的降低程度稍微比碳酸盐大。硫酸盐和碳酸盐通过结合AFm分别生成钙矾石(3CaO·Al_2O_3·3CaSO_4·31H_2O)和单碳硫铝酸钙(3CaO·Al_2O_3·CaCO_3·12H_2O)提高了水泥浆体的pH值,减少了F盐的生成量。硝酸盐对水泥浆体的氯离子固化率和F盐的生成没有影响。     

聚环氧琥珀酸对水泥浆体铝离子配位结构的影响机理

采用XRD、29Si和27 Al NMR等测试手段,研究了聚环氧琥珀酸对水泥浆体铝离子配位结构的影响机理。结果表明,聚环氧琥珀酸能阻止硅酸盐矿物水化,抑制掺杂在Alite和Belite矿中的四配位铝(Al[4])参与水化,不利于铝氧四面体进入到C-S-H结构取代硅氧四面体,促使浆体中Al[4]向六配位铝(Al[6])转化。聚环氧琥珀酸掺量存在一个最佳值,掺量较小时,聚环氧琥珀酸与水泥浆体中Ca2+键合后带正电荷,极易与SO42-结合形成螯合物,促使AFt、AFm中Al[6]向TAH(Third aluminum hydrate)中Al[6]转化,达到抑制AFt、AFm结晶的作用;当掺量较大时,聚环氧琥珀酸通过Ca2+桥连另外的聚环氧琥珀酸形成环状结构,降低了聚环氧琥珀酸固化SO42-的程度,进而使大量TAH中Al[6]逐步向AFm、AFt中Al[6]转化,反而促进了AFt结晶形成。     

K~+和Na~+在C_3S-纳米SiO_2浆体上的存在形式

以拌合液为KOH和NaOH混合溶液的C_3S-纳米SiO_2浆体为对象,研究了液固比对浆体在去离子水中释放K~+和Na~+的影响以及浆体对K~+和Na~+的滞留能力;并采用29Si MAS NMR分析讨论了K~+和Na~+在C_3S-纳米SiO_2浆体上的存在形式。结果表明:随着液固比的增大,浆体释放的K~+和Na~+的百分数逐渐增大;经去离子水充分洗涤后仍有一部分K~+和Na~+存在于浆体中,且浆体对K~+和Na~+的滞留能力随着纳米SiO_2掺量的增加以及拌合液碱浓度的增大而增强。29Si MAS NMR分析证实了K~+和Na~+能够进入C-S-H凝胶层间形成不可逆的化学结合。K~+和Na~+通过取代C-S-H凝胶层间≡SiOCa+中的Ca2+,缩短了C-S-H凝胶中[SiO4]4-四面体链长,从而使凝胶中Q1和Q2峰向左移动。     

Fabrication of ZrO2/AI203 green body through gelcasting process using low-toxicity monomer DMAA

采用低毒的单体N,N-二甲基丙烯酰胺（DMAA）制备了氧化锆增韧氧化铝（ZrO2／A12O3）坯体。讨论了分散剂的用量、ZrO2／Al203浆料的pH值、粉体中Zr02含量、粉体所占浆料的固相体积分数、球磨时间、预混液中DMAA的浓度（质量分数）对ZrO2／Al203浆料黏度的影响。并研究了注凝成型ZrOz／Al203坯体的性能和显微结构。结果表明,当浆料pH值为9,分散剂的添加量为ZrO2／A1203粉体质量的0．6％,球磨时间为6h,ZrO2／Al203浆料具有最小的黏度。固相体积分数的提高和DMAA加入量的增大都会提高ZrO2／A12O3浆料的黏度,ZrOz的加入会降低浆料的黏度。用DMAA制备得到的ZrO2／Al203坯体结构均匀,抗弯强度达到25MPa。     

疏水性聚酰亚胺增强SiO2气凝胶复合材料的制备与表征

采用化学交联、溶胶-凝胶和表面改性的方法,制得疏水性聚酰亚胺（PI）增强SiO₂气凝胶复合材料。以均苯四甲酸二酐（PMDA）和4’,4’-二氨基二苯醚（ODA）为聚合单体,3-氨丙基-三己氧基硅烷（APTES）为封端剂,合成APTES封端的聚酰亚胺,与正硅酸乙酯（TEOS）混合形成前驱体。采用酸碱两步催化凝胶、湿凝胶依次进行表面疏水改性、溶液置换及CO₂超临界干燥,得到聚酰亚胺增强SiO₂气凝胶复合材料样品。利用FTIR、SEM、比表面积测试仪、万能材料试验机、接触角分析仪等表征样品的化学组成、微观形貌、孔结构、力学性能及疏水性能等。结果表明：PI质量分数为6wt%的样品密度为0.124 g/cm³,比表面积为724 m²/g,平均孔径尺寸为14 nm,接触角为134°,抗压强度为0.295 MPa。20wt%含量的PI增强SiO₂气凝胶样品抗压强度为0.556 MPa。     

J55钢在模拟CO2注入井环空环境中的关键性腐蚀因素

基于实际CO₂驱注井环空环境计算环空参数、测试电化学和进行相关性分析,研究了环境总压、CO₂分压、pH值以及温度对J55钢腐蚀电化学行为的影响。结果表明,CO₂分压和温度是影响J55钢腐蚀速度的关键因素。CO₂分压与电荷转移电阻(R_ct)显著相关,Spearman相关系数为-0.623;CO₂分压的升高使溶液的pH值降低从而促进析氢反应,使腐蚀速率提高。温度与R_ct的相关行显著,Spearman相关系数为-0.692;温度的降低抑制材料的电化学反应活性且阻碍腐蚀产物膜的形成,减缓了J55钢的腐蚀。溶液初始p H值的降低能促进J55钢的腐蚀,但是温度和CO₂分压的影响可将其覆盖。     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Al(H2PO2)3/聚氨酯弹性体复合材料的制备及阻燃性能

采用熔融共混技术,将Al（H₂PO₂）₃引入聚氨酯热塑性弹性体,制备了一系列次磷酸铝/聚氨酯弹性体复合材料（Al（H₂PO₂）₃/TPU）。采用极限氧指数（LOI）、垂直燃烧（UL-94）、锥形量热测试、TG和SEM研究了Al（H₂PO₂）₃对Al（H₂PO₂）₃/TPU复合材料阻燃性能及热稳定性的影响,采用力学测试研究Al（H₂PO₂）₃对其力学性能的影响。阻燃测试表明,Al（H₂PO₂）₃可以有效提高Al（H₂PO₂）₃/TPU复合材料的阻燃性能。当Al（H₂PO₂）₃添加量为20wt%时,Al（H₂PO₂）₃/TPU复合材料UL-94级别达到V-0级,LOI达到30.5vol%。热重测试表明,Al（H₂PO₂）₃的加入会导致复合材料热分解温度降低,但其残炭率有明显升高。锥形量热测试表明,Al（H₂PO₂）₃的加入有效降低复合材料热释放速率峰值（pHRR）和总热释放（THR）,并明显提高其火灾安全性能,其中20wt% Al（H₂PO₂）₃/TPU的pHRR和THR相对纯TPU分别下降65.7%和20.2%。SEM表明,Al（H₂PO₂）₃/TPU复合材料炭渣致密性有明显提高。在此基础上,采用TGA-FTIR联用分析Al（H₂PO₂）₃/TPU复合材料阻燃机制,研究发现,Al（H₂PO₂）₃在燃烧过程中可以有效促进TPU裂解产物成炭,降低可燃性气体生成量,从而提高复合材料阻燃性能。     

Sol–gel preparation of boron-containing cordierite Mg2(Al4−xBx)Si5O18 and its crystallization

Five cordierite-based powders were investigated regarding their thermal and crystallization behaviors. The powders were obtained from amorphous gels having nominal compositions of 2Mg : xAl : (4 − x)B : 5Si where x = 4 down to 0. Thermal gravimetry analysis of the dry gels showed some absorbed water and decomposition of organic ligands in addition to network condensation. Gradual substitution of B for Al in the dried gel powders showed a new band in their infrared spectra corresponding to triangular BO₃, whereas the bands corresponding to Al vanished. This also showed a noticeable effect on the crystallization trends, type and stability of cordierite. Cordierite crystallized in samples of B/Al ratio up to 1 while protoenstatite predominated in samples of higher B/Al ratios. In addition, some silica minerals, with little amorphous phase, were formed. Incorporation of boron and increase in temperature enhanced the transformation of γ cordierite to its form.     

杂多酸离子液体负载氨基化Fe3O4磁性复合材料的制备及其超声辅助催化脱硫性能

以N-甲基咪唑、溴代正丁烷、磷钨酸为原料制备了1-丁基-3-甲基咪唑磷钨酸离子液体[BMIM]₃PW₁₂O₄₀,将其通过超声浸渍法负载于氨基化Fe₃O₄（Fe₃O₄-NH₂）,得到枣糕型结构的[BMIM]₃PW₁₂O₄₀/Fe₃O₄-NH₂磁性复合材料,通过FTIR、XRD、XPS、TEM、振动样品磁强计（VSM）、SEM等对其组成、形貌等进行表征。以[BMIM]₃PW₁₂O₄₀/Fe₃O₄-NH₂磁性复合材料为催化剂,以H₂O₂为氧化剂,催化氧化以二苯并噻吩为硫源的正辛烷模拟油样,通过单因素法分别考察了超声时间、H₂O₂用量、反应温度和催化剂用量等因素对脱硫效果的影响,并初步探讨了[BMIM]₃PW₁₂O₄₀/Fe₃O₄-NH₂磁性复合材料催化脱硫机制。结果表明:0.5 g/L[BMIM]₃PW₁₂O₄₀/Fe₃O₄-NH₂磁性复合材料超声辅助催化氧化浓度为500 mg/g模拟油样,在323 K下H₂O₂与二苯并噻吩的摩尔比n（O）:n（S）为8:1经超声10 min时,催化脱硫率达到最佳,为88.13%;重复使用5次后,[BMIM]₃PW₁₂O₄₀/Fe₃O₄-NH₂磁性复合材料对模拟油样的催化降解率仅下降了2.51%。说明该材料具有良好的催化脱硫性能,并可重复使用。催化机制初步研究表明,活性中心可能为杂多酸阴离子、Fe₃O₄-NH₂和离子液体分别起到载体和协同增容作用。      

Synthesis and Characterisation of Some New Ferrocenyl- and Ferrocenylalkynyl-[60]Fullerene Compounds

We report the synthesis and characterisation of a series of ferrocenylfullerene compounds, and some new ferrocene derivatives required as intermediates. The new fullerene species are Fc-[60]fullerene, (8); Fc-C=C-[60]fullerene, (10); Fc-C=C-C=C-[60]fullerene, (12); and (η-C₅H₄SiBu₃)Fe(η-C₅H₄)-[60]fullerene, (14).     

Carburization performance of Incoloy 800HT in CH4/H2 gas mixtures

Carburization performance of Incoloy 800HT has been studied after cyclic and isothermal exposures to CH₄/H₂ carburizing gas mixtures at high temperatures for 500 h. At 800 °C in 2% CH₄/H₂, Incoloy 800HT suffered external oxidation and carburization, the external continuous layer of reaction products consists primarily of Cr₇C₃, Mn_1.5Cr_1.5O₄, and FeCr₂O₄ with Fe(Cr, Al)₂O₄ as a minor phase. At 1100 °C in 10% CH₄/H₂, external carburization did not occur likely due to high carbon dissolution in the alloy substrate at this temperature. A thermodynamic analysis indicated that 1000 °C was an approximate critical temperature, below which the environment should result in mixed oxidizing/carburizing behavior, while above this temperature reducing carburizing behavior should occur. The experimental results approximately agree with the thermodynamic analysis. Metal dusting was not observed under highly carburizing conditions (a_C>1). The size and morphology of Cr-rich phases (or Cr-carbides) are both temperature- and time-dependent, while the external continuity is more temperature-dependent rather than time-dependent.     

Formation of MgAl2O4 in Al2O3-(Al-4wt.%Mg) composites

The Al₂O₃ particles are introduced into the Al-4wt.%Mg melt by the “vortex” method. After being cast, Al₂O₃-(Al-4wt.%Mg) composites are remelted at 700, 750, 800 and 850°C for different residence times to investigate the formation of MgAl₂O₄ (spinel).

The results show that MgAl₂O₄ is the unique interface of the Al₂O₃-(Al---Mg) composites held at 700–850°C. Fine MgAl₂O₄ crystals grow on the surface of the Al₂O₃ particle but, as the holding temperature and the residence time increase, some spinels will form themselves into pyramidal shape. The MgAl₂O₄ grows not only at the matrix-particle interface but also on the surface of the composite specimens. The formation reactions of interfacial MgAl₂O₄ are as follows: Mg(1) + 2Al(1) + 2O₂(g) = MgAl₂O₄(s)3Mg(1) + 4Al₂O₃(s) = 3MgAl₂O₄(s) + 2Al(1) Both of them are equally important.     

RuO2–TiO2 mixed oxides prepared from the hydrolysis of the metal alkoxides

The hydrolysis of ruthenium alkoxide/titanium tetraethoxide mixtures to gels and powders containing 30–40 mol% Ru was investigated. Basic or neutral conditions led to powders consisting of 2–10 nm diameter crystalline RuO₂ nanoparticles embedded in a matrix of crystalline (anatase) and amorphous TiO₂. Acid hydrolysis conditions gave gels containing smaller, amorphous RuO₂ nanoparticles (1–3 nm). In all samples the RuO₂ nanoparticles tended to clump into aggregates up to 0.5 μm across. Acid or neutral hydrolysis of ruthenium ethoxide gave samples which displayed lower surface Ru:Ti ratios as measured by XPS compared to the bulk (XRF), and also contained more low-valent Ru (as measured by XRF), probably due to incomplete hydrolysis of the precursors. These samples also contained more Ru metal after calcination (XRD). Calcination (450 °C) was accompanied by Ru-promoted combustion of organic material and led to crystalline (anatase) TiO₂ and Ti_xRu_1−xO₂ solid solution (rutile phase).     

Measurement of the current transient in Ta2O5 films

Current vs. time (I−t) measurements were performed on Ta₂O₅-based devices. Charge build-up at the Ta₂O₅/SiO₂ interface was used to explain the transient. The interfacial charge density was calculated from the I−t curve and the maximum was found to be 398 nC cm^-2 and 317 nC cm^-2 for Al/Ta₂O₅/Si and Al/Ta₂O₅/SiO₂/Si capacitors respectively. The value for MTOS was comparable with the value obtained by quasi-static measurements.     

热轧高含量B4C颗粒增强Al基复合材料的成形性能

高含量B₄C (B₄C≥30wt%)颗粒增强Al基(B₄C_P/Al)复合材料具有优异的结构和功能特性,尤其是具有优异的中子吸收性能,在核防护领域被用做屏蔽材料使用。但由于高含量B₄C颗粒的加入,使B₄C_P/Al复合材料变形困难。采用ABAQUS数值模拟方法对不同变形量下B₄C_P/Al复合材料的热轧过程进行数值模拟分析,在480℃温度下对热压烧结的B₄C_P/Al复合材料坯料进行轧制,并对其微观组织和力学性能进行分析。数值模拟结果表明,热轧变形量达到60%以上时,B₄C_P/Al复合材料板材表面中间区域应力较小,侧面应力较大,在板材边缘容易产生残余应力。研究结果表明,随轧制下压量的增加,B₄C_P/Al复合材料中B₄C颗粒分布明显均匀,位错密度增加。当轧制变形量达到70%时,B₄C_P/Al复合材料的屈服强度提高至249.46 MPa,极限抗拉强度提高至299.56 MPa。在拉伸过程中,B₄C颗粒优先断裂,但并未与基体界面脱黏,B₄C颗粒承受了主要载荷,Al基体发生塑性流动,从而提高了B₄C_P/Al复合材料的强度。