亚硝酸钙与富铝矿相协同调控碱矿渣氯离子固化能力研究

胶凝材料的氯离子固化能力是影响海工混凝土结构服役寿命的关键影响因素。选用亚硝酸钙作为额外钙相，偏高岭土或纳米氧化铝作为额外铝相，探究了钙相和铝相对碱矿渣胶凝材料水化产物、氯离子固化能力和宏观性能的影响。结果表明：亚硝酸钙和铝相的掺入有效促进了胶凝材料的化学反应和氯离子固化能力，胶凝材料的固氯量相较对照组提高了11.5%～34.8%;体系中的m(Ca)/m(Al)值对氯离子固化能力有重要影响，m(Ca)/m(Al)值的降低导致AFm相、C-(A)-S-H凝胶等产物生成量增加；亚硝酸钙的掺量存在极值，若掺量过高会对材料强度造成不利影响，但纳米氧化铝的加入可在一定程度上弥补这一缺陷。     

水泥-粉煤灰-矿粉-偏高岭土四元胶凝材料氯离子固化机理研究

本文在水泥、粉煤灰和矿粉组成的三元胶凝材料基础上掺入第四元矿物掺合料偏高岭土,利用X射线衍射(XRD)和热重分析(TGA/DTG)定性分析了四元胶凝材料水化产物与氯离子固化能力的关系,并在此基础上利用TGA/DTG和Rietveld外标法定量分析不同形态氯离子固化量。研究表明,掺入偏高岭土能够增加体系早期水化反应速率,促进粉煤灰和矿粉早龄期水化,增加了四元胶凝材料水化AFm相(单硫型水化硫铝酸钙)和C-S-H凝胶含量。同时也增加了体系中铝钙摩尔比,使得单硫型硫铝酸钙(Ms)在碳酸盐存在的条件下更加倾向于转化为半碳型碳铝酸钙(Hc)。氯离子等温吸附结果表明,AFm相含量与氯离子固化能力呈正相关。Rietveld外标法结果表明,掺入偏高岭土后四元体系的氯离子化学固化能力提高,物理吸附能力降低,与三元体系相比,氯离子化学固化量提高了94.16%,物理吸附量降低了7.62%,TGA/DTG定量结果表明Rietveld定量分析具有可行性。     

煤矸石质硅铝基胶凝材料固结氯离子性能研究

煤矸石是我国排放量最大的固体废弃物之一,近年来越来越多的应用于制备胶凝材料,氯离子是影响混凝土耐久性的重要因素之一,本文针对煤矸石质硅铝基胶凝材料的固结氯离子性能进行研究,研究了硅铝基胶凝材料组成、氯盐阳离子类型以及掺入其它阴离子对煤矸石质硅铝基胶凝材料固结氯离子性能的影响,研究结果表明:相同情况下,矿渣固结氯离子能力大于煤矸石,随着龄期的增长,固结氯离子的量增加,随着氯离子掺量的提高,固结氯离子的量也增加;当加入不同阳离子的氯盐的时候,固结的量按Ca2+、K+、Na+顺序递减,掺入其它阴离子不利于氯离子的固化,体系中加入SO2-4、SO2-3、CO2-3、OH-等阴离子后,固结氯离子的量减小,阴离子对固结氯离子的影响从高到低依次SO2-4、SO2-3、CO2-3、OH-.     

碳化作用对镁质胶凝材料微观结构演变过程的影响

为揭示碳化作用对镁质胶凝材料微观结构演变过程的影响,通过扫描电镜（SEM）、X射线衍射（XRD）和压力试验机,对室内养护5 a龄期的镁质胶凝材料净浆试样和30 a龄期的镁质胶凝材料房梁试样进行分析。结果表明,碳化作用对镁质胶凝材料的微观形貌和物相组成影响较大。空气中的二氧化碳由表及里渗入镁质胶凝材料中,在二氧化碳渗入的过程中引起镁质胶凝材料微观形貌和物相组成的变化。镁质胶凝材料的微观形貌主要由针棒状、多孔状向块状转变,物相由5·1·8［5Mg（OH）₂·MgCl₂·8H₂O］相经2·1·1·6［2MgCO₃·Mg（OH）₂·MgCl₂·6H₂O］相最终转化为稳定的水菱镁矿和菱镁矿。由于碳化作用,镁质胶凝材料5 a龄期的抗压强度相比1 a龄期下降了22.1 MPa。因此,需要采用隔离方法处理镁质胶凝材料,以减少其碳化作用,延长其使用年限。     

钙质促凝剂对固化高含水率工程废浆强度的影响

为明确钙质促凝剂添加对固化高含水率工程废浆强度性状的影响,对含钙质促凝剂的固化工程废浆开展一系列无侧限抗压试验,研究不同促凝剂性质及掺量下固化工程废浆强度性状的变化。结果表明:加入钙质促凝剂将显著增强固化工程废浆的无侧限抗压强度q_u,适宜的促凝剂掺量可将固化工程废浆的强度提高1倍左右;不同养护龄期下固化工程废浆的q_u随CaCl₂掺量的增加先增大后降低,随Ca(OH)₂掺量的增大则表现出先增大后减小再增大的变化趋势。和CaCl₂相比,添加Ca(OH)₂引起固化工程废浆强度的增加相对较小。此外,固化工程废浆的破坏应变ε_f和变形系数E50随促凝剂性质和掺量不同也是变化的。对于研究所用工程废浆和促凝剂,固化处理后土体的E50≈(30~100)q_u。     

KR脱硫渣碱激发矿渣的配比优化及水化特性

KR脱硫渣是铁水脱硫工序产生的废渣,多种固废协同制备胶凝材料是脱硫渣资源化的有效途径。本文利用KR脱硫渣、矿渣和脱硫石膏制备固废基胶凝材料,研究KR脱硫渣和矿渣掺量对胶凝材料力学性能的影响,优化原材料配比。通过XRD、TG-DSC、IR、SEM-EDS和水化热测试方法研究了固废基胶凝材料的水化产物及水化特性。结果表明,固废基胶凝材料优化配比为KR脱硫渣25%(质量分数,下同),矿渣60%,脱硫石膏15%,胶凝材料3 d、28 d、90 d抗压强度分别达到30.01 MPa、49.47 MPa和55.73 MPa。固废基胶凝材料的早期水化放热速率低,3 d累积放热量仅为普通硅酸盐水泥(OPC)的37.9%,其水化产物主要是针棒状钙矾石(AFt)和无定形水化硅酸钙(C-S-H)凝胶。KR脱硫渣中大量的Ca(OH)₂在水化早期可以碱激发矿渣,使玻璃相硅酸盐解体,同时与脱硫石膏反应促进AFt的生成。KR脱硫渣、矿渣和脱硫石膏协同反应使水化后期的水化产物持续增加,相互胶结形成致密结构,有利于强度的持续增长。     

高炉矿渣-粉煤灰地聚合物胶凝材料固化砷钙渣

以高炉矿渣、粉煤灰为地聚合物胶凝材料原料,配合复合化学激发剂固化砷钙渣,并采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)探究固砷机理。研究结果表明,固化体优选质量配比为高炉矿渣粉∶粉煤灰∶砷钙渣=4∶2∶4,配合1.5%~2.0%的NaOH和工业水玻璃复合化学激发剂,固化体砷浸出浓度0.5~0.9mg/L,低于危险废物浸出毒性鉴别标准限值(5mg/L)。XRD、FTIR和SEM结果表明,砷钙渣经高炉矿渣-粉煤灰地聚合物胶凝材料固化,反应体系液相环境pH13,促使砷钙渣中的含砷矿物CaHAsO_4·3H_2O向更加稳定的Ca_5(AsO_4)_3OH及类质同象物Ca_5(AsO_4)_3(OH,F)转变。同时地聚合物胶凝材料水化产生的网络状水化凝胶可把砷钙渣中的各组分胶结在一起有效抑制固化体中砷的溶出。可见,高炉矿渣-粉煤灰地聚合物胶凝材料可作为固化含砷渣的一种潜在固结剂。     

钙添加剂对Na2CO3催化高铝煤焦水蒸气气化反应性的影响

以孙家壕高铝煤为实验煤样,将煤样在800℃制成煤焦,采用热重分析仪(TGA)研究了钙添加剂对孙家壕煤焦Na₂CO₃催化水蒸气气化反应性的影响。结果表明：Ca(OH)₂对孙家壕煤焦水蒸气气化具有催化作用,在对孙家壕煤焦进行800℃Ca(OH)₂催化水蒸气气化时,Ca(OH)₂的负载量在15%(质量分数,下同)时达到饱和;通过比较Na₂CO₃和Ca(OH)₂对孙家壕煤焦800℃水蒸气气化的催化活性,发现Na₂CO₃的催化气化活性比Ca(OH)₂的催化气化活性大,负载5%Na₂CO₃和10%Ca(OH)₂的孙家壕焦的800℃水蒸气气化反应性相等;添加10%Ca(OH)₂添加剂可以使负载10%Na₂CO₃的孙家壕煤焦在700℃...     

纳米SiO2对钢渣水泥基胶凝材料的影响

钢渣和水泥具有相似的矿物组成,可以作为一种潜在的胶凝材料,然而钢渣掺量较高时并不利于混凝土早期性能的发展。以钢渣质量分数为30%的钢渣水泥基胶凝材料为研究对象,探讨纳米SiO₂对其早期性能的影响。主要通过测量流动度、凝结时间和抗压强度评估物理力学性能,并利用微量热分析、X射线衍射(XRD)、差热分析(DSC-TG)等方法对掺有纳米SiO₂的钢渣水泥基胶凝材料的水化过程和水化产物进行分析。结果表明,当纳米SiO₂掺入的质量分数为3%时,纳米SiO₂可充分发挥火山灰活性,消耗大量Ca(OH)₂,同时由于纳米SiO₂颗粒的结晶成核作用和微集料填充作用,促进了钢渣和水泥的水化,水化初期的放热速率有所提高,从而提高钢渣水泥基胶凝材料的力学性能,28 d的抗压强度提高了14.0%。     

电石渣-脱硫灰复掺对流态固化土基本性能及微观特性的影响

流态固化土基本性能指标包括湿密度、泌水率、流动值和抗压强度。为探究电石渣和脱硫灰复掺对流态固化土基本性能及微观特性的影响，使用同掺量的电石渣和脱硫灰单一替代以及同时替代Ca(OH)₂和CaSO₄(分析纯),测试其对流态固化土的流动值、泌水率、抗压强度等的影响，采用XRD及SEM对比分析两种分析纯试剂和两种固废制备的试件28 d的物相组成及微观形貌。结果表明，使用电石渣和脱硫灰单掺或复掺制备的流态固化土的流动性均优于使用Ca(OH)₂和CaSO₄复掺流态固化土，泌水率均满足要求，虽然其28 d抗压强度小于Ca(OH)₂和CaSO₄复掺试样，但是能满足大部分应用场景抗压强度要求。     

MgO源对纳米η-Al2O3制备镁铝尖晶石的影响

分别以轻烧氧化镁粉、碳酸镁、分析纯氢氧化镁为MgO源,纳米η-Al₂O₃为原料(其摩尔比为1∶1),采用固相反应法制备镁铝尖晶石。研究不同MgO源对纳米η-Al₂O₃制备镁铝尖晶石的显气孔率、体积密度、物相组成、晶胞参数以及微观结构的影响。结果表明,随着烧结温度升高,三种MgO源与纳米η-Al₂O₃制得镁铝尖晶石试样的致密性逐渐升高。在1 600 ℃下,以氢氧化镁为MgO源与纳米η-Al₂O₃制得尖晶石试样的体积密度最大为3.296 g/cm³,显气孔率最低为1.9%,晶粒发育最好,晶粒尺寸约为3~5 μm。1 300 ℃时,三种MgO源与纳米η-Al₂O₃全部生成镁铝尖晶石,与以α-Al₂O₃为Al₂O₃源制备镁铝尖晶石的传统固相法相比,镁铝尖晶石的合成温度降低了100 ℃,可以降低镁铝尖晶石的成本,对镁铝尖晶石的应用具有实际意义。     

聚乙二醇对聚合氯化铝制备γ-Al2O3的影响（英文）

A polyaluminium chloride solution with high Al 13 content self-prepared was used as material for preparing the spherical γ-Al 2 O 3 by the sol-gel and oil-drop method. Polyethylene glycol with different molecular mass was used as surfactant to investigate the effect on property of γ-Al 2 O 3 . The physical property was characterized by 27 Al NMR (nuclear magnetic resonance) spectra, X-ray diffraction, FT-IR (Fourier transform infrared spectroscopy) and TG-DTA (thermogravimetric-differential thermal analysis). The results showed that surface area, pore volume and pore size of γ-Al 2 O 3 all increased with the increase of polyethylene glycol molecular mass in the experimental research range, and polyethylene glycol 10000 was the most suitable pore forming additive. γ-Al 2 O 3 with surface area of 339 m 2 ·g 1 , pore volume of 0.59 cm 3 ·g 1 and pore diameter of 6.9 nm were obtained at 450 °C.     

Hydrothermal transformation of the calcium aluminum oxide hydrates CaAl2O4·10H2O and Ca2Al2O5·8H2O to Ca3Al2(OH)12 investigated by in situ synchrotron X-ray powder diffraction

The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 °C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl₂O₄·10H₂O converted to Ca₃Al₂(OH)₁₂ and amorphous aluminum hydroxide. Ca₂Al₂O₅·8H₂O transformed via the intermediate phase Ca₄Al₂O₇·13H₂O to Ca₃Al₂(OH)₁₂ and gibbsite, Al(OH)₃. The phase Ca₄Al₂O₇·19H₂O reacted via the same intermediate phase to Ca₃Al₂(OH)₁₂ and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.     

Preparation of new solid superacid catalyst, zirconium sulfate supported on γ-alumina and activity for acid catalysis

Zirconium sulfate supported on γ-Al₂O₃ catalysts were prepared by impregnation of powdered γ-Al₂O₃ with zirconium sulfate aqueous solution followed by calcining in air at high temperature. For Zr(SO₄)₂/γ-Al₂O₃ samples, no diffraction line of zirconium sulfate was observed up to 50 wt.%, indicating good dispersion of Zr(SO₄)₂ on the surface of γ-Al₂O₃. The acidity of catalysts increased in proportion to the zirconium sulfate content up to 40 wt.% of Zr(SO₄)₂. 40-Zr(SO₄)₂/γ-Al₂O₃ calcined at 400 °C exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for both reactions, 2-propanol dehydration and cumene dealkylation were correlated with the acidity of catalysts measured by ammonia chemisorption method.     

含钙镁废渣综合利用的现状及展望

钙镁型废渣可分为氢氧化钙型、碳酸钙型,根据其中镁含量高低,又可分为高镁型和低镁型,只有高镁型废渣才需要对镁元素进行分离回收;常见的钙镁型废渣有电石渣、碱渣、皂化废渣、磷尾矿等。对钙镁型废渣充分综合利用的现状总结归纳为：氢氧化钙型废渣需通过浸取、过滤分离、浸取液碳化等主要化学物理分离步骤;碳酸钙型废渣需要经过煅烧分解、消化浸取、过滤分离、浸取液碳化等化学物理分离步骤,就可实现将钙元素以轻质碳酸钙（PCC）的形式分离出来;如果是高镁型废渣,则需要增加残渣中氢氧化镁的二氧化碳碳化、过滤分离、氨水沉淀分离或碳酸氢镁热解等化学物理步骤来实现镁元素的分离回收。展望未来,钙镁型废渣充分综合利用是一类兼具环境效益、社会效益和经济效益的循环经济项目,值得关注、重视与推广。     

TiO2与SiO2掺杂对Al2O3相转变的研究

通过球磨混合法,制备TiO₂、SiO₂和TiO₂+SiO₂掺杂的Al₂O₃粉体,经不同温度煅烧后进行X射线衍射(XRD)测试,比较研究这三种掺杂对Al₂O₃粉体相转变温度的影响。研究结果表明,TiO₂、SiO₂掺杂对γ-Al₂O₃向α-Al₂O₃的相转变均有促进作用。在掺杂质量分数为0.5%的情况下,二者可分别使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低100 ℃和125 ℃。而TiO₂+SiO₂复合掺杂对γ-Al₂O₃向α-Al₂O₃相转变的促进作用优于TiO₂、SiO₂单独掺杂。TiO₂、SiO₂的质量分数均为0.3%时,复合掺杂可使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低150 ℃。此外,还对TiO₂、SiO₂和TiO₂+SiO₂掺杂促进Al₂O₃粉体相转变的机理作了简单分析。     

车用三效催化剂剖析

对两种国外公司车用三效催化剂进行全面剖析,采用XRF测定催化剂涂层中各组分含量,采用XRD、XPS、H_2-TPR和TEM对催化剂进行物化性能表征。结果表明,A公司的三效催化剂是将Pd和Rh贵金属分别负载到γ-Al_2O_3和Ce_(0.35)Zr_(0.65)O_2固溶体材料上,B公司的三效催化剂是将Pd和Rh贵金属负载到Ce_(0.35)Zr_(0.65)O_2和γ-Al_2O_3混合载体上。     

高Al_(13)含量聚合氯化铝制备γ-Al_2O_3及表征(英文)

In this paper a polyaluminum chloride solution with high Al13 content was prepared and used as raw material for preparation ofγ-Al2O3.The texture and crystalline phase of the prepared alumina samples were characterized by energy dispersive X-ray spectroscopy(EDX) ,X-ray diffraction,transmission electron microscope(TEM) and nuclear magnetic resonance(NMR) analyses.The effects of alkaline solution and calcination temperature were investigated.The results showed that alkaline solution including NH3·H2O and NaOH had little effect on the alumina sample formation.The impurities of NH4Cl and NaCl in solution can be removed through repeated washing by EDX analysis.Calcination temperature had a significant effect on alumina crystal phase.The alumina sample can transform completely toγ-Al2O3 in the subsequent heating from 600°C to 800°C.It is very interesting that Al13 can be existed inγ-Al2O3 phase even after calcinations.The results indicate that polyaluminum chloride with high Al13 content is an effective material to prepareγ-Al2O3.     

高温下改性钙基吸附剂固定床反应器从烟气中捕捉二氧化碳(英文)

Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors: calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299mg·g-1. The morphology of those sorbents was examined by scanning electron microscope (SEM), and the changes of composition before and after carbonation were also determined by X-ray diffraction (XRD). Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca(OH)2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area, larger pore volume and appropriate pore size distribution than that of CaO-CaO and Ca(OH)2-CaO.     

Study of interactions at water-soluble polymer/Ca(OH)2 or gibbsite interfaces by XPS

In an attempt to better understand interactions occuring at hydrated cement/organic polymer interfaces, the reaction mechanism and products formed at the interfaces between poly(acrylic acid), p(AA) or poly(acrylamide), p(AM), and Ca(OH)₂ or gibbsite, Al₂O₃·3H₂O, were explored using x-ray photoelectron spectroscopy (XPS). It was estimated that at p(AA)/Ca(OH)₂ interfaces, a Ca-complexed carboxylate interfacial reaction product was formed by an ionic reaction between the COOH in p(AA) and Ca²⁺ ions from Ca(OH)₂. A similar reaction product was formed at p(AM)/Ca(OH)₂ interfaces as a result of an inter-facial transformation of amide in p(AM) into carboxylic acid, caused by the alkali-catalyzed hydrolysis of the amide. The proton-accepting hydroxyl groups existing at the outermost surface sites of Al₂O₂·3H₂O react favorably with proton-donating COOH groups in p(AA). This acidbase interaction at the p(AA)/Al₂O₃·3H₂O joint formed hydrogen bonds. Whereas, when the p(AM) was applied on Al₂O₃·3H₂O surfaces, interfacial electrostatic bonds were formed through charge-transferring reaction mechanisms in which the charge density was transferred from the Al in Al₂O₃·3H₂O to the C=0 oxygen in p(AM).