矿渣-水泥复合胶凝体系低温水化动力学研究

研究了低温下矿渣-水泥复合胶凝体系的水化反应特性和水化反应动力学.研究表明:低温下,复合胶凝体系的水化放热速率随着矿渣掺量的增加和环境温度的降低而下降;非蒸发水含量随着矿渣掺量的增加呈现降低的趋势;对已有水泥水化动力学方程进行计算,得到了低温条件下复合胶凝体系的动力学参数以及不同阶段反应速率和水化度间的关系,通过计算获得的动力学参数,可以对低温条件下复合胶凝体系不同反应阶段水化反应程度进行预测;在水化早期,复合胶凝体系中矿渣水化程度较低,消耗少量Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较少.在水化后期,复合胶凝体系中矿渣水化消耗较多的Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较多.矿渣掺量为50％时,硬化浆体C-S-H凝胶的Ca/Si远小于纯水泥体系.     

水泥-矿渣复合胶凝材料硬化浆体的微观结构

利用压汞法、扫描电子显微镜和透射电子显微镜研究了两种不同养护条件下水泥-矿渣复合胶凝材料硬化浆体的微观结构.结果表明:常温养护3d龄期时,随着矿渣的掺入和掺量的增加,硬化浆体的孔隙率越大,大孔含量越多;硬化浆体微观形貌显示,掺矿渣试样的反应程度比纯水泥试样更低,密实程度较差.水化后期,复合胶凝材料的水化程度虽然比纯水泥试样低,但复合试样的孔隙率更低,孔径细化.纯水泥试样中水化硅酸钙(C-S-H)凝胶的微观形貌呈单向分布的纤维状,而复合胶凝材料试样中矿渣反应生成的C-S-H凝胶呈三维分布的箔片状,能更有效的隔断和填充连通的孔隙.在高温养护条件下,掺矿渣复合胶凝材料硬化浆体早期和后期孔隙率均较低,高温激发了矿渣早期的活性.     

水泥-矿渣复合胶凝材料硬化浆体的微观结构（英文）

利用压汞法、扫描电子显微镜和透射电子显微镜研究了两种不同养护条件下水泥-矿渣复合胶凝材料硬化浆体的微观结构。结果表明:常温养护3 d龄期时,随着矿渣的掺入和掺量的增加,硬化浆体的孔隙率越大,大孔含量越多;硬化浆体微观形貌显示,掺矿渣试样的反应程度比纯水泥试样更低,密实程度较差。水化后期,复合胶凝材料的水化程度虽然比纯水泥试样低,但复合试样的孔隙率更低,孔径细化。纯水泥试样中水化硅酸钙(C-S-H)凝胶的微观形貌呈单向分布的纤维状,而复合胶凝材料试样中矿渣反应生成的C-S-H凝胶呈三维分布的箔片状,能更有效的隔断和填充连通的孔隙。在高温养护条件下,掺矿渣复合胶凝材料硬化浆体早期和后期孔隙率均较低,高温激发了矿渣早期的活性。     

等28d抗压强度条件下粉煤灰和矿渣对C50混凝土后期性能的影响

在28 d抗压强度相近的前提下,制备了纯水泥混凝土、大掺量粉煤灰混凝土、大掺量矿渣混凝土,测定了不同混凝土的后期抗压强度、抗氯离子渗透性,以及胶凝材料的化学结合水、硬化浆体中的Ca(OH)2含量.结果表明:含大掺量矿物掺合料的混凝土的后期强度和抗氯离子渗透性均明显高于纯水泥混凝土;大掺量矿渣混凝土的后期强度高于同掺量的大掺量粉煤灰混凝土;复合胶凝材料的后期水化程度增长率明显高于纯水泥;复合胶凝材料硬化浆体中后期Ca(OH)2含量明显低于纯水泥硬化浆体.     

高炉镍铁渣粉在水泥基复合胶凝材料中的水化特性研究

通过对不同高炉镍铁渣掺量的水泥-高炉镍铁渣粉复合胶凝材料水化放热速率、高炉镍铁渣粉的反应程度、硬化浆体化学结合水含量以及水化产物中C-S-H凝胶Ca/Si的测定,分别研究了水泥-高炉镍铁渣粉复合胶凝材料的早期、中长期水化进程、浆体微观形貌以及水化产物特点等水化特性.研究结果表明:高炉镍铁渣的掺入会降低水化放热速率,并推迟水化加速期放热峰的出现时间;在复合胶凝体系中,随着高炉镍铁渣粉掺量的增大,其反应程度和硬化浆体中化学结合水含量将降低.复合胶凝材料水化生成的C-S-H凝胶的Ca/Si低于水泥,且随着水化的进行呈降低趋势;高炉镍铁渣粉中的Al,在水化过程中会取代部分Si进入C-S-H凝胶中,形成C-A-S-H凝胶.     

高温养护下粉煤灰在大体积混凝土中效应机理研究

以大掺量粉煤灰胶凝材料硬化浆体为研究对象,结合XRD、FTIR、NMR等仪器进行测试分析,研究高养护制度下粉煤灰掺量对其水化相C—S—H凝胶硅氧四面体聚合程度的影响规律。结果表明：高温养护的硬化浆体,其水化相C—S—H凝胶硅氧四面体聚合程度和Al原子取代Si原子的程度,在各个养护龄期始终高于常温养护的硬化浆体。     

温度对水泥-矿渣复合胶凝材料水化的影响（英文）

研究了温度对水泥-矿渣复合胶凝材料硬化浆体微观结构及净浆和砂浆后期强度的影响。利用背散射图像分析法测定了硬化浆体中水泥和矿渣各自的反应程度。探讨了水泥-矿渣复合胶凝材料水化程度、微观结构和力学性能之间的关系。结果表明:温度对纯水泥的水化程度影响很小,但高温(60℃)降低了纯水泥净浆的后期抗压强度。高温阻碍了复合胶凝材料浆体中水泥的后期水化,但促进了矿渣的水化,提高了矿渣的后期反应程度。高温下矿渣持续反应使硬化浆体的孔结构细化,使复合胶凝材料净浆的后期抗压强度与常温养护时相近。高温对水泥-矿渣复合胶凝材料砂浆后期抗压强度的不利影响大于净浆后期抗压强度。高温养护并不导致水泥-矿渣复合胶凝材料的后期水化程度降低。复合胶凝材料的水化程度与强度不呈线性相关。     

稻壳灰在丁苯聚合物/水泥复合胶凝材料凝结硬化过程中的作用

聚合物/水泥复合胶凝材料在解决普通水泥基材料脆性大、易开裂、抗拉抗折强度低等问题的同时还可使水泥基材料具有了更好的防水性和耐久性,但聚合物/水泥复合胶凝材料凝结硬化较为缓慢。针对此,采用稻壳灰作为调凝组分,研究稻壳灰对丁苯聚合物/水泥复合胶凝材料凝结硬化过程以及水化进程和水化产物的影响,探讨稻壳灰调节凝结硬化过程的机理。结果表明:稻壳灰能加快丁苯聚合物/水泥复合胶凝材料的水化进程,缩短水化诱导期、加速期,并提高早期水化程度,从而缩短凝结时间,提高早期强度。凝结硬化过程中,稻壳灰促进了C_3S的水化,并与部分水化产物Ca(OH)_2发生二次反应生成C–S–H凝胶。     

水泥—钢渣—矿渣复合胶凝材料的水化特性

通过测定水泥--钢渣--矿渣复合胶凝材料的水化热、砂浆的抗压强度、硬化浆体孔溶液的碱度、钢渣和矿渣的水化程度,探讨了复合胶凝材料的水化特性。结果表明:钢渣在复合胶凝材料水化硬化过程中所起的化学作用小于矿渣;随着复合胶凝材料中钢渣含量的增大和矿渣含量的减小,复合胶凝材料的早期和后期胶凝性能均降低;随着复合胶凝材料中矿渣的含量增大,硬化浆体孔溶液的碱度降低,矿渣的反应程度也随之降低,矿渣含量为10%~40%时,孔溶液的pH值为12.6~13.3;钢渣的反应程度受复合胶凝材料组成的影响很小;钢渣和矿渣在后期的反应程度提高明显,尤其矿渣所起的化学作用显著,矿渣在360d龄期的反应程度超过50%,甚至60%,使复合胶凝材料砂浆的后期强度与水泥砂浆的差距明显缩小。     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

Stoichiometry of Slag Hydration with Calcium Hydroxide

The stoichiometry of the reaction between ground granulated blast furnace slag (GGBFS) having an empirical formula of C_7.88S_7.39M₃A and calcium hydroxide (CH) was investigated. Scanning electron microscopy (SEM) was used to determine the slag consumption as well as the Ca/Si ratio in calcium silicate hydrate gel (C-S-H) products. A tentative stoichiometric ratio of 2.6 mol of CH consumed per mole of slag reacted was determined using two methods. By combining consumption data determined separately for slag and CH a molar stoichiometry of 2.79 was found. Similarly, by directly determining the Ca/Si ratio in the C-S-H gel product, a range for the molar stoichiometry between 1.65 and 3.42 was found. Finally, a comparison of the stoichiometry of the slag/CH reaction was made with slag/portland cement hydration. The basic features of both appear similar. In the C-S-H gel around slag grains, a calcium-to-silica ratio of 1.3 to 1.4 was found for both slag/CH and slag/cement systems.     

Highly Reactive β-Dicalcium Silicate: IV, Ball-Milling and Static Hydration at Room Temperature

The ball-milling hydration of highly reactive β-Ca₂SiO₄ synthesized from hillebrandite, Ca₂(SiO₃)(OH)₂, was investigated and compared with its static hydration under a water/solid ratio of 10. In static hydration, the hydration is completed in 8 d to yield C-S-H with a Ca/Si ratio of 1.81 and Ca(OH)₂. There is no major change after this period. In the case of ball milling, the hydration is completed in 2 d to yield C-S-H with Ca/Si = 1.81 and Ca(OH)₂. After this, the two products react to form a C-S-H(II)-like monophase hydrate having a Ca/Si ratio of 1.98. The morphology and structure of this hydrate are different from those of the earlier hydrate, and afwillite is not formed. ²⁹Si MAS NMR measurements indicated the C-S-H to be a mixture of dimers and single-chain structures. Dimeric species are the main species up to completion of the reaction, but polymerization progresses very rapidly after the completion.     

粉煤灰-水泥水化的核磁共振定量分析

利用高分辨固体核磁共振仪结合去卷积技术,定量分析了粉煤灰水泥浆体中水泥和粉煤灰的水化程度以及C-S-H凝胶中硅氧-铝氧链平均长度,同时研究了粉煤灰火山灰反应对C-S-H结构的影响。结果表明:水化3 d时,系统中约47%的水泥和14%的粉煤灰参与了水化反应,C-S-H平均链长为3.2;水化120d时,水泥和粉煤灰的水化程度分别为89%和33%,C-S-H平均链长约为3.8,远大于纯水泥浆体中C-S-H的平均链长(为2.7)。水化3 d时粉煤灰玻璃相结构中的Si—O—Si,Si—O—和Al—Al共价键断裂,形成了单体硅酸根和单体铝酸根,这些单体结构桥连体系中的二聚体单元进而提高了C-S-H平均链长。粉煤灰掺入并不会因为C-S-H聚合度提高以及ACL增加就能促进粉煤灰水泥浆体强度。     

Highly Reactive β-Dicalcium Silicate: II, Hydration Behavior at 25°C Followed by 29Si Nuclear Magnetic Resonance

The hydration behavior at 25°C of highly reactive β-dicalcium silicate synthesized from hillebrandite (Ca₂(SiO₃)(OH)₂) was studied over a period of 7 to 224 d using ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR). The hydration product, C-S-H, contains Q² and Q¹ silicate tetrahedra, the chemical shifts of which are independent of the water/solid (w/s) ratio and curing time. Until the reaction is completed, the amounts of Q¹ and Q² formed are independent of the w/s ratio, being determined only by the degree of reaction. The ratio Q²/Q¹ increases as the reaction progresses and as the curing time becomes longer. From the values of Q²/Q¹, it appears that the hydrate is a mixture of dimers and short single-chain polymers. The Ca/Si ratio of the hydrate is high, taking values close to 2.0, but the Ca/Si ratio does not influence the Q²/Q¹ ratio. It was also found that the NMR peak intensities allow quantitative assessment similar to XRD.     

Hydration products of alkali-activated slag-red mud cementitious material

A new kind of alkali-slag-red mud cementitious material, abbreviated as ASRC, with both high early and ultimate strength and excellent resistance against chemical attacks has been developed by the application of composite solid alkali activator into slag-red mud mixture system. The hydration products of this cement at ambient temperature have been investigated by means of XRD, IR, TG-DTA, TEM, EDXA, etc. The results showed that the hardened cement paste was mostly consisted of C-S-H gel, being very low in Ca/Si ratio, very fine in size and extremely irregular in its shape. Neither Ca(OH)₂ and AFt, which are usually present in the hardened Portland cement paste, nor zeolite-like products have been detected. These characteristics are considered to be the chemical reasons for the high early and ultimate strength and good resistance against chemical attacks of the hardened ASRC cement paste.     

Initial hydration of tricalcium silicate as studied by secondary neutrals mass spectrometry: II. Results and discussion

The hydration of tricalcium silicate (C₃S) was studied by secondary neutrals mass spectrometry (SNMS), a method that enables determination of the Ca/Si ratio of the formed calcium silicate hydrate (C-S-H) phase with an extremely low information depth. It was found that the magnitude of this parameter within the hydrate layer formed at the surface of the nonhydrated C₃S is not constant and increases with increasing distance from the liquid-solid interface. It was also found that, at a constant distance from the surface, the Ca/Si ratio declines with hydration time. The kinetics of the hydration process is characterized by a very fast initial reaction, followed by a dormant period and a subsequent period of renewed hydration. The rate of hydration becomes distinctly accelerated by elevated temperature and retarded by the presence of sucrose, while NaCl affects the initial hydration kinetics only to a small degree.     

协同水化制备水硬性材料及其水化产物的研究

按钢渣、矿渣和粉煤灰以5∶3∶2的比例组成复合废渣,在改性水玻璃等激发剂的协同作用下,制备得到的浆体28 d抗压强度高达53.56 MPa,凝结时间及安定性均合格。通过X射线衍射(XRD)分析、电子扫描电镜(SEM)形貌观察等对浆体中的水化产物进行分析,结果表明,在协同水化作用下,水化产物中存在网络状的水化硅酸钙(C-S-H)。     

Formation of ASR gel and the roles of C-S-H and portlandite

Experimental investigations of the reactions between silica, alkali hydroxide solution, and calcium hydroxide show that alkali-silicate-hydrate gel (A-S-H) comparable to that formed by the alkali-silica reaction (ASR) in concrete does not form when portlandite or the Ca-rich, Si-poor C-S-H of ordinary portland cement (OPC) paste is available to react with the silica. Under these conditions, we observe either the formation of additional C-S-H by reaction of Ca(OH)₂ with the dissolving silica or the progressive polymerization of C-S-H. The A-S-H dominated by Q³ polymerization forms only after portlandite has been consumed and the C-S-H polymerized. These conclusions are consistent with previously published results and indicate that the ASR gel of concrete forms only in chemical environments in which the pore solution is much lower in Ca and higher in Si than bulk pore solution of OPC paste. These results highlight the similarity between ASR and the pozzolanic reaction and are supported by data for mortar bar specimens.