氧化石墨烯增强水泥基复合材料的力学性能及微观结构

本文采用改进的Hummers法制备了氧化石墨烯（Graphene oxide,GO）悬浮液,通过FTIR、XRD和AFM等测试技术对GO晶体结构和尺寸形态进行了表征,考察了GO掺量和水灰比的变化对GO增强水泥基复合材料力学性能和微观结构的影响。结果表明：GO增强水泥基复合材料抗折抗压强度随GO掺量增加而先提高后降低,且对于抗折强度增强效果远超过抗压强度,当GO掺量为0.03%时,抗折强度达到最大值13.72 MPa;高水灰比条件下掺入GO对水泥胶砂强度的提高更显著;通过SEM对GO增强水泥基复合材料微观结构进行表征,发现GO能够优化水泥水化产物的微观结构形态,细化晶体尺寸,形成更加致密均匀的网络结构,从而改善水泥基复合材料的宏观性能。     

A novel approach of developing micro crystalline cellulose reinforced cementitious composites with enhanced microstructure and mechanical performance

This paper reports a novel approach of preparing aqueous suspensions of microcrystalline cellulose (MCC) for fabrication of cementitious composites. MCC was dispersed homogeneously in water using Pluronic F-127 as a surfactant with the help of ultrasonication process and the aqueous suspensions were added to cement/sand mixture to prepare cementitious composites. A commonly used stabilizing agent for MCC, carboxy methyl cellulose (CMC) was also used for the comparison purpose. The prepared suspensions were characterized through visual inspection, UV-Vis spectroscopy and optical microscopy. The developed composites were characterized for their bulk density, flexural and compressive properties as well as microstructure. The influence of Pluronic and CMC concentration, superplasticizer, dispersion technique and dispersion temperature on mortar's mechanical performance was thoroughly studied to find out the optimum conditions. Overall, Pluronic (with Pluronic: MCC ratio of 1:5) led to better MCC dispersion as well as dispersion stability as compared to CMC. The best mechanical performance was achieved with Pluronic in combination with superplasticizer using ultrasonication process, resulting in improvement of 106%, 31% and 66% in flexural modulus, flexural strength and compressive strengths, respectively (highest values reported till date). The bulk density and hydration of cementitious composites also improved significantly with the addition of MCC.     

混杂纤维增强水泥基复合材料的力学性能

研究了化学改性聚丙烯（PP）纤维以及掺加聚丙烯纤维和芳纶纤维混杂比例和混杂效应对水泥基复合材料力学性能的影响,并构建了纤维增强水泥砂浆界面层的物理模型,描述了纤维对水泥砂浆的增强机制。实验表明,聚丙烯纤维经改性后使水泥砂浆前期抗折强度明显提高,聚丙烯纤维和芳纶纤维的混杂使水泥砂浆的后期抗折强度显著提高。改性聚丙烯纤维掺加体积分数为0.56%,芳纶纤维的体积分数为0.24%时,混杂纤维增强水泥砂浆试样较空白试样,3天、28天抗折强度分别提高了18.48%、31.17%,3天、28天抗压强度分别提高了7.16%、5.19%。     

掺CWCPM的砂浆强度灰色关联分析及预测模型的建立

为提高建筑垃圾砖粉活性,将其与粉煤灰、矿粉、激发剂复合形成建筑垃圾复合粉体材料(Construction waste composite powder materials,以下简称CWCPM)。从宏观和微观两方面研究了CWCPM对砂浆力学性能的影响,并采用灰色关联分析及多元回归分析理论,研究了水灰比、CWCPM掺量与砂浆强度的关联性,建立了砂浆抗压强度与水灰比、CWCPM掺量、龄期之间的定量关系模型。结果表明,CWCPM降低了砂浆早期强度,而其合理的颗粒级配及二次水化反应提高了砂浆后期强度;其中CWCPM掺量为抗压强度的准优因素,抗折强度受水灰比的影响较大;多元回归模型对砂浆抗压强度的预测精度较高,为CWCPM的有效利用提供了理论依据。     

响应面方法优化碱激发矿渣-石粉水泥砂浆的研究

基于响应面中的中心复合试验法,选择碱含量和石灰石粉含量作为配合比变量,制备碱激发矿渣-石粉水泥砂浆,并研究其不同龄期的力学强度。通过数据处理得到各变量与抗折、抗压强度的响应曲面,分析了各变量对碱激发矿渣-石灰石粉水泥砂浆强度的影响规律,建立了各龄期强度的响应面模型,为现场不同龄期的砂浆强度预测提供了科学的方法。结果表明,当Na2O含量为8.27%(质量分数,下同)、石灰石粉含量为14.02%时,各组分能充分发挥协同作用,保证良好的力学性能,且响应面法是一种有效优化碱激发水泥砂浆组分的方法。     

Effect of shrinkage reducing admixture on flexural behaviors of fiber reinforced cementitious composites

The use of shrinkage reducing admixture (SRA) at various concentrations was investigated in fiber reinforced cementitious composites. Both mortar and high strength concrete (HSC) matrices were tested. Two types of fibers—steel and polypropylene—were assessed. The effect of SRA was measured on the fundamental properties such as surface tension of the bulk fluids and the contact angle developed between the fibers and the bulk fluids, on the fresh properties such as the air content and the density, and finally on the hardened mechanical properties, specially the flexural behaviors. It was noted that SRA enhances the wettability of fibers and reduces the air content of fiber reinforced cement mortars, while critical SRA concentrations are existing. SRA with critical concentration can significantly improve the flexural toughness and residual strength of steel fiber reinforced cement mortar. In the case of polypropylene fiber, SRA is not as effective in enhancing the flexural behaviors as it is in the case of steel fiber. SRA is generally ineffective in reducing the air content of HSC and the properties of steel fiber reinforced HSC with SRA are inferior to those without SRA.     

微胶囊-玄武岩纤维/水泥复合材料的力学性能

以水泥、玄武岩纤维和脲醛/环氧树脂微胶囊为主要材料,制备水泥基复合材料标准试样,研究纤维掺量、纤维长度、微胶囊质量分数、水灰质量比和养护龄期对复合材料抗折强度和抗压强度的影响,利用正交实验确定微胶囊-玄武岩纤维/水泥自修复复合材料力学性能的最优配比。实验结果表明：抗折强度随着纤维掺量的增加而增加,抗压强度随着纤维掺量增加而减小;随着纤维长度的增加,抗折强度略有增加,抗压强度略有降低;抗折强度随着微胶囊质量分数的增加呈现出先增加后减小的趋势,而抗压强度则呈现下降趋势;抗折强度与抗压强度随养护龄期的增加而呈增加的趋势;材料经损伤后修复,抗折强度修复率为117%,恢复率为103%,抗压强度修复率为71%,恢复率为97%。     

化学改性芳纶纤维增强水泥基复合材料的性能

采用化学改性法对芳纶纤维进行表面处理, 研究了改性前后芳纶纤维对水泥基复合材料强度及抗冲击性能的影响。结果表明: 芳纶纤维的掺入可以提高水泥砂浆的抗折强度和抗冲击性能, 经化学改性后的芳纶纤维增强效果更加明显。当掺杂纤维的体积分数为1.0%时, 化学改性前后芳纶纤维增强水泥砂浆试样与基准砂浆试样相比, 其28天抗折强度分别提高了15.18%和23.85%, 抗冲击韧性分别提高了276.74%和294.54%。采用SEM对芳纶纤维表面微观形貌及试样断口形貌进行了观察, 利用XPS对改性前后芳纶纤维表面元素变化进行了研究, 探讨了芳纶纤维对水泥砂浆的增强机制。      

Dispersion of multi-walled carbon nanotubes and its effects on the properties of cement composites

In this study, two types of multi-walled carbon nanotubes (pristine, p-CNT and functionalized, f-CNT) were dispersed in water by sonication and then added to cement mortar. The purpose of this study was to characterize the dispersion degree of the CNTs in aqueous suspension and to investigate whether achieving dispersion in water would also result in dispersion inside mortar. Dispersion of the CNTs in water was investigated by means of UV–vis spectroscopy, using different CNT concentrations and sonication durations. Dispersion of the CNTs in cement mortar was investigated by measuring the compressive and flexural strength and fracture toughness as well as the microstructural characterizations of scanning electron microscopy and mercury intrusion porosimetry. The effects of the CNT addition on drying shrinkage and cement hydration were also investigated for cement pastes. The results of UV–vis spectroscopy showed that by increasing the sonication time to 120 min, the dispersion degree of the f-CNT suspension increased progressively, while for p-CNT, a maximum was reached with 60 min of sonication. The compressive and flexural strength and fracture toughness of mortars containing f- and p-CNTs were not significantly improved either by increasing the amount of CNT or imposing sonication in mixing water. High CNT dispersion in cement matrix was not equally obtained by utilizing highly dispersed CNT suspension. Sonication of f- and p-CNT led to a remarkable deceleration of cement hydration in the first hour of hydration and drying shrinkage of the cement composites was found to be reduced by f- and p-CNT addition.     

Electrostatic self-assembled carbon nanotube/nano carbon black composite fillers reinforced cement-based materials with multifunctionality

Electrostatic self-assembled carbon nanotube (CNT)/nano carbon black (NCB) composite fillers are added into cement mortar to fabricate smart cement-based materials. The grape bunch structure of CNT/NCB composite fillers is beneficial for dispersing CNT/NCB in cement mortar matrix and achieving cooperative improvement effect. The mechanical, electrically conductive, and piezoresistive behaviors of the cement mortar are investigated. The CNT/NCB composite fillers can effectively enhance the flexural strength and electrical conductivity of cement mortars, and endow stable and sensitive piezoresistivity to cement mortar at a low filler content. However, they weaken the compressive strength of cement mortar to some extent. The percolation threshold zone of cement mortar with CNT/NCB composite fillers ranges in the amount of 0.39–1.52 vol.%. The optimal content of CNT/NCB composite fillers is 2.40 vol.% for piezoresistivity and the stress and strain sensitivities can reach 2.69% MPa⁻¹ and 704, respectively.     

Reinforcing graphene oxide/cement composite with NH<Subscript>2</Subscript> functionalizing group

In this study, pure and NH₂-functionalized graphene oxide (GO) nanosheets have been added to the cement mortar with different weight percents (0.05, 0.10, 0.15, 0.20 and 0.25 wt%). In addition, the effects of functionalizing GO on the microstructure and mechanical properties (flexural/compressive strengths) of cement composite have been investigated for the first time. Scanning electron microscopy (SEM) images showed that GO filled the pores and well dispersed in concrete matrix, whereas exceeding GO additive from 0.10 wt% caused the formation of agglomerates and microcracks. In addition, mercury intrusion porosimetry confirmed the significant effects of GO and functionalizing groups on filling the pores. NH₂-functionalizing helped to improve the cohesion between GO nanosheets and cement composite. Compressive strengths increased from 39 MPa for the sample without GO to 54.23 MPa for the cement composites containing 0.10 wt% of NH₂-functionalized GO. Moreover, the flexural strength increased to 23.4 and 38.4% by compositing the cement paste with 0.10 wt% of pure and NH₂-functionalized GO, compared to the sample without GO, respectively. It was shown that functionalizing considerably enhanced the mechanical properties of GO/cement composite due to the interfacial strength between calcium silicate hydrates (C-S-H) gel and functionalized GO nanosheets as observed in SEM images. The morphological results were in good agreement with the trend obtained in mechanical properties of GO/cement composites.     

石墨烯表面性质对水泥砂浆复合材料力学性能和微观结构的影响

近年来,利用石墨烯及其衍生物改善水泥基复合材料性能受到了广泛关注。但是,关于石墨烯表面性质对水泥基材料的性能影响却鲜有报道。为此,采用不同浓度的L-抗坏血酸(10wt%、20wt%、30wt%、50wt%和70wt%)和还原时间(15 min、30 min、45 min和60 min)将氧化石墨烯(GO)转化为还原氧化石墨烯(rGO),然后以相同剂量(水泥质量的0.05%)加入到水泥砂浆复合材料中,研究了不同还原程度的rGO对水泥砂浆力学性能的影响。测试结果表明,通过50wt%L-抗坏血酸还原30 min制备的rGO的加入使水泥砂浆28天抗压强度和抗折强度相比于普通试样分别提高了36.84%和43.24%。SEM等分析表明,GO和不同还原程度的rGO均可促进Ca(OH)₂的结晶和水化硅酸钙凝胶(C-S-H)中二氧化硅四面体的形成,形成致密的微观结构。但存在一个最佳阈值(即通过50wt%的L-抗坏血酸还原30 min),在该阈值下,有利于rGO表面官能团与水化产物的结合。      

Use of biochar as carbon sequestering additive in cement mortar

Biochar is widely considered as effective way of sequestering carbon dioxide. The possibility of using it to enhance the mechanical strength and reduce permeability of cement mortar is explored in this study. The effect of fresh biochar and biochar saturated with carbon dioxide a priori on the setting time, mechanical strength and permeability of cement mortar was evaluated. The biochar was prepared from mixed wood saw dust at 300 °C and added to mortar during mixing at 2% by weight of cement. It was found that addition of fresh biochar and saturated biochar reduce initial setting time and significantly improve early compressive strength of mortar. The experimental results suggested that biochar addition can impart ductility to mortar under flexure, although flexural strength was not significantly influenced. Water penetration and sorptivity of mortar was significantly reduced due to addition of biochar, which indicate higher impermeability in biochar added mortar. However, it is found that addition of fresh biochar offers significantly higher mechanical strength and improved permeability compared to biochar saturated with carbon dioxide. These results suggest that biochar has the potential to be successfully deployed as a carbon sequestering admixture in concrete constructions that also provides a way to waste recycling.     

亲水型功能化石墨烯的分散性及其对水泥基复合材料力学性能的影响

为了解决石墨烯纳米片在水泥基体中的分散问题,采用芳基重氮盐(F)对氧化石墨烯(GO)进行改性,制备了一种新型亲水型功能化石墨烯(FG)。结果表明,FG在水溶剂中最大的分散浓度能够达到2.1 mg/mL。FTIR、拉曼光谱和XPS结果表明F成功对石墨烯进行了表面改性。对比纯水泥基体材料,本文所制备的亲水型FG/水泥复合材料的28天抗折强度和抗压强度相对提高了95.3%和78.3%。F对GO进行改性,实现了石墨烯在水泥基材料中的均匀分散及对其力学性能的提升。      

Effect of gypsum type on properties of cementitious materials containing high range water reducing admixture

In this study, the effect of cement gypsum type on properties of the properties of cement paste, mortar and concrete mixtures containing high range water reducing admixture (HRWR) was investigated. Two different types of cement prepared from the same clinker but containing either calcium sulfate hemihydrate or dihydrate as retarder were used. The fresh and hardened (compressive strength and drying-shrinkage) properties as well as static and dynamic rheological behavior of the mixtures were investigated. Compared to the mixtures containing dihydtate, the fresh and rheological properties of mixtures were negatively affected when cement-containing hemihydrate was used. However, hemihydrate utilization had a positive influence on the early compressive strength. The adverse effects on fresh properties were more significant in paste mixtures. These negative effects decreased in the mortar and concrete mixtures. The presence of hemihydrate in cement was found to increase the drying-shrinkage.     

Flexural performance of fiber-reinforced ultra lightweight cement composites with low fiber content

This paper presents an experimental study on flexural performance of ultra lightweight cement composites (ULCC) with 0.5 vol% fibers. Low density of the ULCC is achieved by using cenospheres from coal-fired power plants as micro aggregates. Effects of shrinkage reducing admixture (SRA) and fiber types on compressive strength and flexural performance of the ULCC are investigated. ULCC with density of 1474 kg/m³, compressive strengths of 68.2 MPa, flexural strength of 8 MPa, and deflection hardening behavior can be produced. Such good performance could be attributed primarily to the SRA which reduced entrapped air in paste matrix and densified fiber–matrix interface. The improvement on the flexural performance of the ULCC depends on fibers used and bond between fibers and matrix. Improvement of the flexural performance of the steel fiber (coated with brass) reinforced ULCC due to the densification effect by SRA was more significant than that of the PE fiber reinforced ULCC.     

硫铝酸盐水泥基复合相变储能砂浆的制备及其性能

采用熔融共混法制备“低密度聚乙烯（LDPE）-石蜡-石墨”复合定形相变材料（SSPCM）,并以硫铝酸盐水泥作为胶凝材料,制备了硫铝酸盐水泥基复合相变储能砂浆（TESCCM）。利用SEM、激光扫描共聚焦显微镜（LSCM）、DSC和TGA分析了SSPCM和TESCCM的微观形貌、蓄热能力和热稳定性。通过测试TESCCM的抗压和抗折强度,分析了SSPCM含量对TESCCM力学性能的影响,并利用自制热性能测试箱评价了TESCCM的热调节性能。结果表明：LDPE能够形成多层次网状结构,可实现对相变石蜡的有效包裹,所制备的SSPCM热焓值可达88.02 J/g; SSPCM与水泥基体结合良好; TESCCM具有热稳定性好、强度增长快、早期强度高及调温性能显著等特点。SSPCM含量增加会使TESCCM的强度降低,但对材料的韧性却有所改善。对于SSPCM与水泥质量比为50%的TESCCM,1天和3天抗压强度分别为5.58 MPa和6.51 MPa,28天压折比为2.7。     

Function of styrene-acrylic ester copolymer latex in cement mortar

This paper focuses on the effect of the styrene-acrylic ester copolymer (SAE) latex on the performance of cement mortar, through studying on the water-reduction and water-retention effects of the SAE latex in the mortar, and the influence of the SAE latex on the air-content and the bulk density of the fresh mortar and the bulk density, compressive and flexural strengths, shrinkage rate, water capillary adsorption and anti-penetration capacity of the hardened mortar. The experimental results show that the SAE latex has good water-reduction and water-retention effects in mortar. The SAE latex has also air entrainment effect, increasing the air content and reducing the bulk density of the fresh mortar. The apparent bulk density and dry bulk density of the hardened mortars decrease with the increase of the SAE latex/cement-ratio (m_p/m_c) and the change is in accordance with that for the bulk density of the fresh mortar. The SAE latex influences the development of the compressive strength but slightly on the flexural strength, and improves the toughness, shrinkage property, waterproofing quality and anti-penetration capacity of the mortar significantly.     

稻壳纤维粒径和掺量分数对水泥复合材料性能的影响

以稻壳纤维（Rice husk fiber,RHF）为增强材料,以水泥为基体,制备了RHF/水泥基复合材料。研究了粒径对RHF在水泥基体中分散性能的影响;并以RHF粒径和掺入质量比为考察因素,采用响应曲面法,以RHF/水泥基复合材料的密度、抗折强度、含水率、吸水率和导热系数为响应值,建立数学模型,对RHF/水泥基复合材料的成型工艺进行优化设计。结果表明：RHF的粒径越小,在水泥基体中分散性能越好,粒径为150 μm的RHF分散系数达到最大值,为0.981;响应曲面模型分析表明RHF的粒径为150 μm、掺入质量为水泥质量的3%时,RHF/水泥基复合材料的性能达到最优,此时RHF/水泥基复合材料的密度为1 559.26 kg/m³,抗折强度为9.38 MPa,含水率为7.05%,吸水率为16.71%,导热系数为0.50 W/（m·K）,达到了建筑行业标准JC/T 411-2007的要求。     

环境湿度对玻璃纤维增强水泥力学性能的影响

通过开展在不同龄期、不同环境湿度下玻璃纤维增强水泥(GRC)试件的抗折强度、抗压强度试验和基体pH值测定,研究了环境湿度对掺加粉煤灰和硅灰等活性矿物掺合料的GRC试件力学性能的影响。结果表明:环境湿度对GRC试件的抗折强度有重要影响,相对湿度越大,随着龄期增加, GRC试件抗折强度降低越严重;在温度60℃、相对湿度95%条件下,经过56 d龄期后,掺有40%粉煤灰和10%硅灰的GRC试件抗折强度比未掺加粉煤灰和硅灰的GRC试件的抗折强度提高48.5%、抗压强度提高23.6%, GRC基体pH值降低6%。在相同的湿度条件下,掺有粉煤灰和硅灰试件的pH值在各个龄期都低于普通硅酸盐水泥试件,说明粉煤灰和硅灰的掺入能降低水泥水化液相的碱度,进而延缓了纤维受侵蚀的速度,显著改善了GRC试件的力学及耐久性能。通过对试验结果进行分析,利用MATLAB软件建立了GRC试件抗折强度和抗压强度与水泥砂浆基体pH值及时间的关系式。