超细CaCO3增强硫铝酸盐水泥强度的研究

在硫铝酸盐水泥硬化体中,钙矾石主要以柱状、棒状而存在,这对水泥的性能产生了不利影响。探讨了超细CaCO3对硫铝酸盐水泥进行改性的研究。试验结果表明,超细CaCO3掺量为3%时,明显改善了硫铝酸盐水泥的强度,其28 d净浆与砂浆抗压强度分别达到100.6 MPa和94.1 MPa,且水泥的28 d砂浆抗折强度高达12.5 MPa。SEM显示掺超细CaCO3硫铝酸盐水泥硬化体中难以发现大颗粒状的水化硫铝酸钙晶体,结构较致密、均匀。     

海工水泥抗硫酸盐侵蚀机理

采用浸泡抗蚀性能试验方法 （K法）,对比研究了海工水泥和普通硅酸盐水泥的抗硫酸盐侵蚀性能。使用X射线衍射（XRD）、热重分析（TGA）、电子扫描（SEM）和电子计算机断层扫描（Computed tomography, CT）分析了两种水泥硫酸盐侵蚀前后矿物成分和微观结构的变化,进行了机理分析。结果表明：海工水泥抗硫酸盐侵蚀性能优于普通硅酸盐水泥,海工水泥在3%硫酸钠溶液中浸泡11个月后侵蚀系数为1.03,而普通硅酸盐水泥为0.22。海工水泥主要水化产物为水化硅酸钙、钙矾石和较少的氢氧化钙,其在3%硫酸钠溶液中浸泡后生成微量二水石膏,不会对基体产生破坏。除水化硅酸钙和钙矾石外,普通硅酸盐水泥的水化产物中有较多的氢氧化钙和单硫型水化硫铝酸钙,其在3%硫酸钠溶液中会生成大量的二水石膏和钙矾石,两者的结晶膨胀会引起基体开裂。     

高含硼废液对硫铝酸盐水泥水化过程影响机理

研究了高含硼模拟液条件下硫铝酸盐水泥的水化反应特征、缓凝机理和使用氢氧化钙作为促凝剂的可行性。通过采用XRD、TG-DTG、微量热仪、SEM-EDS、EPMA等微观测试分析手段,表征了氢氧化钙对含硼模拟液条件下硫铝酸盐水泥水化过程和反应产物的影响。结果表明,在含硼模拟液中,硫铝酸盐水泥颗粒的表面会生成具有层状特征的硼化物,包裹水泥颗粒,阻碍其进一步溶解,延缓硫铝酸盐水泥水化。氢氧化钙的掺入能诱导硫铝酸盐水泥在含硼模拟液中优先生成含硼钙矾石,缓解硼酸根离子的缓凝效果,有效促进水泥水化反应;随着水化反应进行,含硼钙矾石会逐渐转变为钙矾石。     

早期养护条件对水泥石碳硫硅钙石型硫酸盐腐蚀的影响

研究了早期高湿度空气养护、水中标准养护及密封养护对水泥石碳硫硅钙石型硫酸盐腐蚀的影响。采用X射线衍射（XRD）、傅立叶转换红外光谱（FTIR）和扫描电子显微镜（SEM）等方法分析了水泥石经180 d硫酸盐侵蚀后的腐蚀产物。结果表明,早期高湿度空气养护,水泥石碳化生成的CaCO3填充于孔隙中,使表层结构更加致密,阻碍了SO4^2-等有害离子侵入,延缓了水泥石碳硫硅钙石型硫酸盐腐蚀过程。比较而言,早期密封养护,水泥水化不充分,水泥石内部缺陷相对较多,SO4^2-等有害离子容易侵入,水泥石碳硫硅钙石型硫酸盐腐蚀最为严重。     

应用量子化学方法研究钙矾石的强度特性

钙矾石相是许多水泥品种的主要水化相之一，对水泥石的强度起着重要作用。本文用量子化学ＳＣＣ－ＤＶ－Ｘａ方法对钙矾石和含锶钙矾石相进行了研究。研究结果表明：两者结构中Ａｌ的键级和Ａｌ—Ｏ键共价键级大致相同。含锶钙矾石中Ｓｒ的键级和Ｓｒ—Ｏ共价键级大于钙矾石中的Ｃａ和Ｃａ—Ｏ键．由此可以认为这是含锶硫铝酸钙水化强度高于硫铝酸酸钙的主要原因之一。     

钙矾石纤维的生长与形貌

采用硫铝酸盐水泥熟料-石膏-氧化钙三元体系、硫酸铝-氧化钙二元体系和硫酸铁-氧化钙二元体系制备钙矾石纤维,研究钙矾石纤维生长过程,分析不同铝质原材料、反应温度和水固比对钙矾石纤维生长速度和形貌的影响。结果表明：不同铝制原材料制备的钙矾石纤维形貌差异较大,由硫铝酸盐水泥熟料制备的钙矾石纤维尺寸最大,为类木质形貌,由硫酸铝制备的钙矾石纤维尺寸最小且形貌多样,由硫酸铁制备的钙矾石纤维为层状结构;提高反应温度和加大反应水固比均促进反应进行,增大钙矾石纤维尺寸,其中反应温度的影响更为显著。将钙矾石作为一种纤维材料进行研究,突破了钙矾石单纯为水泥水化产物的局限,为调控钙矾石纤维在纤维增韧复合材料中的应用提供了理论基础。     

石灰石粉铝酸盐水泥复合体系的水化反应

石灰石粉具有水化活性,能与硅酸盐水泥中的C₃A、铝酸盐水泥中的CA、CA₂等铝酸盐矿物发生反应,水化产物为水化碳铝酸钙。利用微量热仪法、胶砂强度和X射线衍射（XRD）,研究不同比例的石灰石粉铝酸盐水泥复合体系的水化反应,结果表明：石灰石粉会加快铝酸盐水泥的水化进程,水化过程诱导期缩短,放热速率峰值下降;复合体系中石灰石粉占比越高,早期水化反应速率越快,但水化反应放热量越低;相对而言,复合体系中石灰石粉掺量为20%时石灰石粉参与反应程度最高,且掺量为20%时石灰石粉对复合体系强度有显著贡献。随复合体系中石灰石粉比例增加,铝酸盐水泥水化产物越来越不明显;石灰石粉掺量为20%~40%时,水化碳铝酸钙XRD特征峰相对最明显,复合体系中石灰石粉与铝酸盐水泥存在一个最佳的比例范围。研究表明,石灰石粉与铝酸盐水泥间会发生明显的水化反应,石灰石粉与铝酸盐水泥复合有望制得一种新型胶凝材料。     

含钡硫铝酸盐水泥的研究

含钡硫铝酸盐水泥的主要矿物组成为含钡硫铝酸钙(简写3CA·BaSO_4)、硅酸二钙(β-C_2S)以及少量的铁相。本文详细地研究了这种水泥的烧成制度和各项物理力学性能;使用x射线分析和扫描电镜分析探讨了水泥水化产物及水泥石结构。     

硅酸盐水泥熟料对硫铝酸盐水泥某些性能影响的研究

本文利用硫铝酸盐水泥熟料、二水石膏、硅酸盐水泥熟料配制了三组份硫铝酸盐水泥,研究了硅酸盐水泥熟料对硫铝酸盐水泥某些性能的影响。试验结果表明,掺入适量的硅酸盐水泥熟料,对硫铝酸盐水泥某些性能有明显影响:一、提高水泥早期的抗压强度;二、可以改变水泥的热稳定性;三、调整硅酸盐水泥熟料和石膏的加入量,可以调整水泥的凝结时间和自由膨胀率。作者利用X射线衍射分析、差热分析、电子显微镜观察、压汞测孔仪、热膨胀仪及光电比色计等方法和手段,研究了提高强度和热稳定性的原因。结果表明,加入硅酸盐水泥熟料后,减小了钙矾石结晶尺寸,降低了水泥石的孔隙率、增加了结构的密实度。作者根据实验结果,进一步讨论了减小钙矾石结晶尺寸、增加结构密实度的原因。加入硅酸盐水泥熟料后,提高了水化液相的碱度,使得钙矾石结晶尺寸减小。关于水泥石结构的密实度,主要从水泥浆体的凝聚结构方面进行了讨论。在实验条件下,测得钙矾石的表面电性为正、水化硅酸钙的表面电性为负。由于电性相反,范德华引力与电性引力一致,增加了形成凝聚结构的力,致使形成较为致密的凝聚结构。测定水泥浆悬浮体的透光率的结果进一步证实了此结论,未加硅酸盐水泥熟料的水泥悬浮体透光率小,而加后的透光率大。在此基础上,作者提出了在凝聚结构形成过程中,应创造条件使之产生相互匹配的异性水化物的看法。水泥热稳定性增加,作者认为与钙矾石的尺寸减小和均匀分布有密切关系。钙矾石结晶尺寸大而集中时,加热水泥石,开始受热膨胀,到达钙矾石脱水温度后,继而急剧收缩,造成较大的局部应力,破坏水泥石结构。测定水泥石热膨胀系数表明,未加硅酸盐水泥熟料的热膨胀系数大,而加后热膨胀系数减小。     

磷石膏/矿粉复合过硫胶凝材料的制备研究

通过研究磷石膏、硫铝酸盐水泥熟料、碱激发剂等组分掺量对过硫胶凝材料体系物理力学性能的影响,借助XRD、SEM等微观测试手段对水化产物及机理进行分析探讨,确定了过硫胶凝材料组成的最佳配合比。结果表明:5%的硫铝酸盐水泥熟料、30%的磷石膏、63%的矿粉、2%的碱激发剂制备出的磷石膏/矿粉复合过硫胶凝材料标准稠度用水量为30.8%,初凝时间为312min,终凝时间为514min,3d抗压强度可达13MPa,28d抗压强度超过48MPa。微观分析表明,在该配比下制备的过硫胶凝材料主要水化产物为钙矾石和C-S-H凝胶,水化28d时钙矾石生成量较大,结构较为致密,强度大幅度提高。     

Carbonation of sulphoaluminate cement with layered double hydroxides

The increasing importance of the ecologically minded production of building materials makes it necessary to develop reasonable alternatives to the CO2-intense production of ordinary Portland cement （OPC）. The development of new or modified concrete is an important part of existing strategies to improve performance and minimize life-cycle costs. Therefore, we investigated carbonation resistance properties of sulphoaluminate cement （SAC） concrete incorporating layered double hydroxides （LDHs）. X-ray diffraction （XRD） and IR-spectroscopy were employed to characterize the component and structural changes of LDHs and cement paste before and after carbonation test. Carbonation resistance of concrete was experimentally evaluated. Finally, carbonation of Portland cement and SAC concrete was compared. The experimental results show that carbonation depth decreases remarkably with the addition of LDHs, especially the calcinated LDHs. Carbonation depth of SAC concrete is smaller than that of PC concrete regardless of curing time.     

Carbonation resistance of sulphoaluminate cement-based high performance concrete

The influences of water/cement ratio and admixtures on carbonation resistance of sulphoaluminate cement-based high performance concrete (HPC) were investigated. The experimental results show that with the decreasing water/cement ratio, the carbonation depth of sulphoaluminate cement-based HPC is decreased remarkably, and the carbonation resistance capability is also improved with the adding admixtures. The morphologies and structure characteristics of sulphoaluminate cement hydration products before and after carbonation were analyzed using SEM and XRD. The analysis results reveal that the main hydration product of sulphoaluminate cement, that is ettringite (AFt), decomposes after carbonation. Funded by the National Natural Science Foundation of China (No.50872043)     

Carbonation of low heat portland cement paste precured in water for different time

The carbonation technique was applied to accelerate the hydration of low heat portland cement （LHC）. Before carbonation, the demoulded pastes were precured in water for 0, 2, 7, and 21 d, respectively. The results show that precuring time in water strongly influences the carbonation process. The phenolphthalein test indicates that the paste precured in water for a shorter time is more quickly carbonated than that for a longer time. The content of calcium hydroxide increases with increasing the precuring time in water, whereas, the amount of absorbed carbon dioxide changes contrarily. Scanning electron microscope （SEM） observation shows that portlandite always fills up big air bubbles in the paste during precuring in water, and the mercury intrusion porosimetry （MIP） results show that there are less large capillary pores in the paste precured in water for a longer time. It is found that the paste without precuring in water has more carbon dioxide absorption during curing in carbon dioxide atmosphere, and its total pore volume decreases remarkably with an increase in the carbonation time than that precured in water. X-ray diffraction （XRD） and Brunauer-Emmett-Teller （BET） surface area analyses indicate that the carbonate products are vaterite and calcite; CxSHy formed from carbonation has low BET surface area in comparison with that of C-S-H formed from curing in water.     

Carbonation of low heat portland cement paste procured in water for different time

The carbonation technique was applied to accelerate the hydration of low heat portland cement (LHC). Before carbonation, the demoulded pastes were precured in water for 0, 2, 7, and 21 d, respectively. The results show that procuring time in water strongly influences the carbonation process. The phenolphthalein test indicates that the paste precured in water for a shorter time is more quickly carbonated than that for a longer time. The content of calcium hydroxide increases with increasing the procuring time in water, whereas, the amount of absorbed carbon dioxide changes contrarily. Scanning electron microscope (SEM) observation shows that portlandite always fills up big air bubbles in the paste during precuring in water, and the mercury intrusion porosimetry (MIP) results show that there are less large capillary pores in the paste precured in water for a longer time. It is found that the paste without precuring in water has more carbon dioxide absorption during curing in carbon dioxide atmosphere, and its total pore volume decreases remarkably with an increase in the carbonation time than that precured in water. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) surface area analyses indicate that the carbonate products are vaterite and calcite; CxSHy,, formed from carbonation has low BET surface area in comparison with that of C-S-H formed from curing in water.     

Effects of LiAl-layered double hydroxides on early hydration of calcium sulphoaluminate cement paste

As a 3D micro-nano material, layered double hydroxides have been widely used in many fields, especially for reinforced composite materials. In this paper, LiAl-LDHs was obtained by a hydrothermal method. In order to investigate the effects of LiAl-LDHs on the early hydration of calcium sulphoaluminate (CSA) cement paste, compressive strength, setting time and hydration heat were tested while X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron microscopy (SEM) and differential scanning calorimetry (DSC) analysis were employed. The results indicated that LiAl-LDHs could significantly improve the early compressive strength and shorten the setting time of calcium sulphoaluminate cement paste with 3wt% concentration. Besides, the hydration exothermic rate within 5 h was accelerated with increasing LiAl-LDHs content. Moreover, the addition of LiAl-LDHs did not result in the formation of a new phase, but increased the quantity of hydration products providing higher compressive strength, shorter setting time and denser microstructure.     

Effects of Carbonation on Micro Structures of Hardened Cement Paste

In order to investigate the effects of carbonation on the microstructure of cement concrete,the carbonation depth and microstructure of cement paste with 0.3,0.4 and 0.5 water/cement ratio after 7,14,21 and 28 d accelerated carbonation were studied respectively.The results showed that with the increase of waterto-cement ratio and carbonation age,the carbonation depth was deepened with faster early carbonation speed and slower later carbonation rate.Carbonation densified the structure of hardened cement stone with refinement of pore structure and reduced porosity.Then,during the carbonation process from the surface to the inside of carbonation area,it was prone to form micro-cracks extending to the interior specimen,resulting in cement paste carbonation depth uneven.It is further illustrated that the color reaction method using phenolphthalein solution combined with X-CT and X-ray diffraction analysis is much more reasonable to evaluate the cement concrete carbonation degree.Moreover,during carbonation process sulfur element in cement paste migrated to the area un-carbonated and the concentrated shape of sulfur element is consistent with the coloring region in carbonation interface.Finally it was identified that carbonation not only reduced the p H value in cement concrete but also made prone to crack in carbonation zone,which increased the probability of reinforcement corrosion.     

煤矸石水泥混凝土水化物及其碳化性能的研究

本文研究了煤矸石水泥混凝土在不同养护条件下,碳化前后的水化物及其所形成的微结构特点,并与普通水泥混凝土进行对比,探讨了煤矸石水泥混凝土的碳化性能。     

Hydration mechanism of sulphoaluminate cement

The feasibility of sulphoaluminate cement (SAC) utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement (SAC) paste were examined, hydration kinetics behavior was determined through Isothermal Calorimeter, and hydration mechanism was investigated by X-Ray diffraction analysis (XRD) and field emission scanning electron microscopy analysis(FSEM). Results showed that as-received SAC contained 61% of anhydrous calcium sulfate (3CA·CaSO4) and dicalcium silicate (C2S). The strength after 1 day or 3 days grew to 68.6% or 85.7% of that after 28 days respectively, while most of hydration heat was released within 1 day. The emergency of three exothermic peaks at acceleration stage was found and hydration kinetics model was established choosing the terminal time of the first exothermic peak at accelerating stage as the beginning of accelerating stage. XRD analysis suggested that large amount of ettringite (AFt) was produced at early age and FSEM observation revealed that ettringite (AFt) formed in sulphoaluminate cement (SAC) paste was characterized of different morphology which was proved to be caused by different ion concentrations.     

Study on activity evaluation of activated coal-gangue and the hydration process

Chemical compositions,mineral compositions and the activated mechanism of the coal-gangue were analyzed. And pozzolana activities of the coal-gangue were evaluated after activated. Moreover,hydration heat and hydration compositions of activated coal-gangue-calcium oxide system,as well as hydration degree and hardened paste microstructures of activated coal-gangue-cement system were studied. Results show that pozzolana activities of the activated coal-gangue root in amorphous SiO2 and activated Al2O3. With the exciting of gypsum,the reaction of activated coal-gangue and Ca(OH)2 would produce hydration products as ettringite,calcium silicate hydrate,and calcium aluminate. The relationship between the curing age and the content of Ca(OH)2 in coal-gangue-cement system was ascertained. Unhydrated particles in the coal-gangue-cement paste were more than that in the neat cement paste at the same hydration periods,and even existed at the later stage of hydration. Furthermore,the activated coal-gangue could inhibit growth and gathering of the calcium oxide crystal,and improve the structure of hardened cement paste.