机敏混凝土的压敏性及钢筋腐蚀与防护机理研究
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摘要
机敏混凝土作为一种水泥基本征复合材料,与混凝土结构具有天然的相容性和同寿命性,还具有造价低、可大规模布设等特点,可满足土木工程结构长期健康监测的需要,已成为该领域的热点和前沿研究方向。
水泥基导电复合材料应变自感知性能是基于其电阻与应变的对应关系,即压阻特性。本文针对目前机敏混凝土存在的问题,提出了在制备水泥基复合材料时内掺水泥基渗透结晶防水材料(CCCW)、以碳纤维和石墨为导电相的技术路线,并从制备工艺及组分优化、单向和多轴应变状态下的自感知特性及机理,以及含CCCW和碳纤维混凝土中钢筋的腐蚀与防护机理等方面进行了较深入系统的研究。论文主要成果与创新之处如下：
1.首次提出了在机敏混凝土的制备过程中使用CCCW材料,以改进机敏材料的电学性能及压敏性的稳定性,提高机敏材料的力学性能。通过改进碳纤维分散工艺、内掺CCCW和采用浓硝酸浸泡PAN基碳纤维制备了碳纤维水泥净浆和砂浆,并对其微观结构、电学特性、单向循环荷载下的压阻特性和力学性能进行了实验研究和理论分析。同时,研究了内掺CCCW的石墨水泥基机敏材料(GCC)的导电及压阻性能、力学性能。结果表明,经浓硝酸浸泡处理的碳纤维分散性得到了增强,碳纤维在水泥基体中分散较为均匀。CCCW对试样的微裂缝具有自修复作用,可以提高机敏混凝土的力学性能和电学性能的稳定性。
2.研究了内掺CCCW的碳纤维石墨水泥基复合材料(CFGCC)的电学性能和力学性能。通过复掺长程导电的碳纤维和短程导电的石墨,内掺CCCW以部分弥补加入石墨导致的复合材料力学性能的下降,制备了电学性能稳定、力学性能较好的新型机敏材料。研究结果表明,内掺4%(CCCW(占水泥质量分数,下同)、1%碳纤维的CFGCC渗滤阈值为20%左右；石墨掺量为20%-30%的CFGCC的压阻特性最好,碳纤维和石墨复掺工艺提高了机敏材料电学性能的稳定性。
3.提出了利用羟丙基甲基纤维素(HPMC)作为制备机敏混凝土时所加短切碳纤维的分散剂。结果表明,HPMC可以替代羧甲基纤维素(CMC)分散碳纤维,有效解决其容易起霉、耐水性差的问题。
4.研究了所制备的新型机敏材料的应变灵敏度系数K(单位应变的电阻变化率),探讨了多循环对CFGCC试块电学性能的影响,基于隧道效应理论,对多轴应变下的力电理论进行了初步分析,并进一步探索了嵌入式GCC、CFGCC试块对混凝土柱的自感知特性,研究了多轴应变条件下机敏材料作为传感器监测结构埋入试样部位的受力状态的可行性。结果表明,在压应力幅值6.25MPa循环荷载作用下,含石墨20%和50%的GCC试样的K值分别为37和22：含碳纤维1%、石墨20%和30%的CFGCC的K值分别为63和25,均远高于电阻应变片的2。嵌入式GCC、CFGCC试块的混凝土柱具有良好的压敏特性。在循环荷载的作用下,内嵌混凝土柱中心的机敏材料试块的电阻变化率与混凝土柱所受的压力呈现良好的对应关系,具有很好的同步性。在单调加载条件下,试块的电阻值可以清晰反映试块的弹性范围、塑性范围和破坏范围。
5.采用新拌砂浆法、硬化砂浆法和宏观电池技术,研究分析了掺CCCW、短切碳纤维及盐水浸泡和干湿循环对钢筋锈蚀的影响,探讨了混凝土结构钢筋腐蚀与防护的机理。结果表明,短切碳纤维促进钢筋锈蚀,其含量越大,促进钢筋锈蚀作用越明显。结构系统防护法可有效实施对钢筋的保护。
As a kind of cement-based composites, smart concrete presents many characteristics, such as high durability and excellent compatibility with concrete structures themselves, as well as cheap and large-scale-distributed embeded and so on. Therefore, it has been more and more attractive for structural health monitoring in civil infrastructures due to its promising performance in long-term service, and has become an attractive topic and cutting-edge research in this field.
Cement-based conductive composite materials with strain self-sensing performance is based on the corresponding relationship between electrical resistance and applied strain, that is, piezoresistivity. At the existing problems on the smart concrete, this thesis focuses on the research of cement-based composite materials containing cementitious capillary crystalline waterproofing materials (CCCW), the electrical conductive phase of carbon fiber and graphite. The detailed contents include fabrication method and optimization of proportion, piezoresistivity and its mechanism under one-way and multiaxial stress state, and the effects of CCCW and short-cut carbon fiber on the corrosion and protection of reinforcement in concrete. The following conclusions and innovation can be obtained:
(1) Adding CCCW material in the preparation of smart concrete was proposed for improving the stability of electrical, pressure-sensing and mechanical properties of smart concrete for the first time. By improving the dispersion technology of carbon fiber, carbon fiber cement paste and mortar with CCCW were prepared, in which PAN-based carbon fibers were dipped by concentrated nitric acid. And their microstructure, electrical properties, the piezoresistivity under one-way cyclic loading and mechanical properties were carried out experimental research and theoretical analysis. At the same time, the above properties of graphite cement-based composites (GCC) have also investigated. The results have shown that the dispersion of carbon fiber after treatment by concentrated nitric acid in the block of cement paste has been enhanced. Carbon fibers were dispersed uniformly in the matrix. The active chemical material in CCCW has a kind of ability of self-repairing to micro-cracks in concrete, that may improve the stability of electrical properties and mechanical properties of smart concrete.
(2) The electrical and mechanical properties of carbon fiber graphite cement-based composites (CFGCC) with CCCW were studied. By coplexing long-range conductive carbon fiber and short-range conductive graphite, and adding CCCW to partially offset the decline in mechanical properties of CFGCC caused by graphite, the new-type smart materials were prepared. The results show that the percolation threshold of CFGCC with 4%(mass fraction of cement, the same below) CCCW and 1% carbon fiber is about 20%. The piezoresitivity of CFGCC with 20% to 30% graphite is the best. Mixing carbon fiber and graphite in smart materials improves the stability of electrical performance.
(3) The use of hydroxypropyl methyl cellulose (HPMC) as a dispersant of chopped carbon fiber in the preparation of smart concrete was proposed. The result shows that HPMC can replace carboxymethyl cellulose (CMC) in order to avoid its easy to moldy and non-water.
(4) The strain gage factor K (defined as the fractional change in resistance per unit strain) of smart materials GCC and CFGCC were studied. And the effect of multi-cycle on the electrical properties of CFGCC test pieces were discussed.Based on the theory of tunneling effect, the electric-mechanical theory was analyzed under multiaxial strain. The results show that, the blocks of GCC and CFGCC present a good piezoresistive effect. Under the action of 6.25MPa compressive stress amplitude cyclic loading, the measured gage factor of GCC with graphite content of 20% and 50% are 37 and 22 respectively, and the measured gage factor of CFGCC with 1% carbon fiber and 20% and 30% graphite are 37 and 22 respectively, which are higher than gage factor 2 of resistance-strain gauge. The self-sensing properties of GCC and CFGCC block embedded in concrete columns were also studied under the conditions of multiaxial stress. In the monotonic loading conditions, the resistance value of the block embedded in concrete column can clearly reflect its elastic range, plastic scope and failure.
(5) By the use of fresh mortar method, hardened mortar method and macro-cell technology, the effects of adding CCCW and carbon fiber, dipped in salt solution and wet-dry cycle on reinforcement corrosion in concrete were analyzed. And the mechanism of steel bar corrosion and protection was discussed. The results show that, the chopped carbon fiber is to promote steel bar corrosion, and the greater the content, the more obvious role in the promotion of steel bar corrosion. Structural system protection methods can be effectively implemented on the reinforcement of protection.
v
水泥基导电复合材料应变自感知性能是基于其电阻与应变的对应关系,即压阻特性。本文针对目前机敏混凝土存在的问题,提出了在制备水泥基复合材料时内掺水泥基渗透结晶防水材料(CCCW)、以碳纤维和石墨为导电相的技术路线,并从制备工艺及组分优化、单向和多轴应变状态下的自感知特性及机理,以及含CCCW和碳纤维混凝土中钢筋的腐蚀与防护机理等方面进行了较深入系统的研究。论文主要成果与创新之处如下：
1.首次提出了在机敏混凝土的制备过程中使用CCCW材料,以改进机敏材料的电学性能及压敏性的稳定性,提高机敏材料的力学性能。通过改进碳纤维分散工艺、内掺CCCW和采用浓硝酸浸泡PAN基碳纤维制备了碳纤维水泥净浆和砂浆,并对其微观结构、电学特性、单向循环荷载下的压阻特性和力学性能进行了实验研究和理论分析。同时,研究了内掺CCCW的石墨水泥基机敏材料(GCC)的导电及压阻性能、力学性能。结果表明,经浓硝酸浸泡处理的碳纤维分散性得到了增强,碳纤维在水泥基体中分散较为均匀。CCCW对试样的微裂缝具有自修复作用,可以提高机敏混凝土的力学性能和电学性能的稳定性。
2.研究了内掺CCCW的碳纤维石墨水泥基复合材料(CFGCC)的电学性能和力学性能。通过复掺长程导电的碳纤维和短程导电的石墨,内掺CCCW以部分弥补加入石墨导致的复合材料力学性能的下降,制备了电学性能稳定、力学性能较好的新型机敏材料。研究结果表明,内掺4%(CCCW(占水泥质量分数,下同)、1%碳纤维的CFGCC渗滤阈值为20%左右；石墨掺量为20%-30%的CFGCC的压阻特性最好,碳纤维和石墨复掺工艺提高了机敏材料电学性能的稳定性。
3.提出了利用羟丙基甲基纤维素(HPMC)作为制备机敏混凝土时所加短切碳纤维的分散剂。结果表明,HPMC可以替代羧甲基纤维素(CMC)分散碳纤维,有效解决其容易起霉、耐水性差的问题。
4.研究了所制备的新型机敏材料的应变灵敏度系数K(单位应变的电阻变化率),探讨了多循环对CFGCC试块电学性能的影响,基于隧道效应理论,对多轴应变下的力电理论进行了初步分析,并进一步探索了嵌入式GCC、CFGCC试块对混凝土柱的自感知特性,研究了多轴应变条件下机敏材料作为传感器监测结构埋入试样部位的受力状态的可行性。结果表明,在压应力幅值6.25MPa循环荷载作用下,含石墨20%和50%的GCC试样的K值分别为37和22：含碳纤维1%、石墨20%和30%的CFGCC的K值分别为63和25,均远高于电阻应变片的2。嵌入式GCC、CFGCC试块的混凝土柱具有良好的压敏特性。在循环荷载的作用下,内嵌混凝土柱中心的机敏材料试块的电阻变化率与混凝土柱所受的压力呈现良好的对应关系,具有很好的同步性。在单调加载条件下,试块的电阻值可以清晰反映试块的弹性范围、塑性范围和破坏范围。
5.采用新拌砂浆法、硬化砂浆法和宏观电池技术,研究分析了掺CCCW、短切碳纤维及盐水浸泡和干湿循环对钢筋锈蚀的影响,探讨了混凝土结构钢筋腐蚀与防护的机理。结果表明,短切碳纤维促进钢筋锈蚀,其含量越大,促进钢筋锈蚀作用越明显。结构系统防护法可有效实施对钢筋的保护。
As a kind of cement-based composites, smart concrete presents many characteristics, such as high durability and excellent compatibility with concrete structures themselves, as well as cheap and large-scale-distributed embeded and so on. Therefore, it has been more and more attractive for structural health monitoring in civil infrastructures due to its promising performance in long-term service, and has become an attractive topic and cutting-edge research in this field.
Cement-based conductive composite materials with strain self-sensing performance is based on the corresponding relationship between electrical resistance and applied strain, that is, piezoresistivity. At the existing problems on the smart concrete, this thesis focuses on the research of cement-based composite materials containing cementitious capillary crystalline waterproofing materials (CCCW), the electrical conductive phase of carbon fiber and graphite. The detailed contents include fabrication method and optimization of proportion, piezoresistivity and its mechanism under one-way and multiaxial stress state, and the effects of CCCW and short-cut carbon fiber on the corrosion and protection of reinforcement in concrete. The following conclusions and innovation can be obtained:
(1) Adding CCCW material in the preparation of smart concrete was proposed for improving the stability of electrical, pressure-sensing and mechanical properties of smart concrete for the first time. By improving the dispersion technology of carbon fiber, carbon fiber cement paste and mortar with CCCW were prepared, in which PAN-based carbon fibers were dipped by concentrated nitric acid. And their microstructure, electrical properties, the piezoresistivity under one-way cyclic loading and mechanical properties were carried out experimental research and theoretical analysis. At the same time, the above properties of graphite cement-based composites (GCC) have also investigated. The results have shown that the dispersion of carbon fiber after treatment by concentrated nitric acid in the block of cement paste has been enhanced. Carbon fibers were dispersed uniformly in the matrix. The active chemical material in CCCW has a kind of ability of self-repairing to micro-cracks in concrete, that may improve the stability of electrical properties and mechanical properties of smart concrete.
(2) The electrical and mechanical properties of carbon fiber graphite cement-based composites (CFGCC) with CCCW were studied. By coplexing long-range conductive carbon fiber and short-range conductive graphite, and adding CCCW to partially offset the decline in mechanical properties of CFGCC caused by graphite, the new-type smart materials were prepared. The results show that the percolation threshold of CFGCC with 4%(mass fraction of cement, the same below) CCCW and 1% carbon fiber is about 20%. The piezoresitivity of CFGCC with 20% to 30% graphite is the best. Mixing carbon fiber and graphite in smart materials improves the stability of electrical performance.
(3) The use of hydroxypropyl methyl cellulose (HPMC) as a dispersant of chopped carbon fiber in the preparation of smart concrete was proposed. The result shows that HPMC can replace carboxymethyl cellulose (CMC) in order to avoid its easy to moldy and non-water.
(4) The strain gage factor K (defined as the fractional change in resistance per unit strain) of smart materials GCC and CFGCC were studied. And the effect of multi-cycle on the electrical properties of CFGCC test pieces were discussed.Based on the theory of tunneling effect, the electric-mechanical theory was analyzed under multiaxial strain. The results show that, the blocks of GCC and CFGCC present a good piezoresistive effect. Under the action of 6.25MPa compressive stress amplitude cyclic loading, the measured gage factor of GCC with graphite content of 20% and 50% are 37 and 22 respectively, and the measured gage factor of CFGCC with 1% carbon fiber and 20% and 30% graphite are 37 and 22 respectively, which are higher than gage factor 2 of resistance-strain gauge. The self-sensing properties of GCC and CFGCC block embedded in concrete columns were also studied under the conditions of multiaxial stress. In the monotonic loading conditions, the resistance value of the block embedded in concrete column can clearly reflect its elastic range, plastic scope and failure.
(5) By the use of fresh mortar method, hardened mortar method and macro-cell technology, the effects of adding CCCW and carbon fiber, dipped in salt solution and wet-dry cycle on reinforcement corrosion in concrete were analyzed. And the mechanism of steel bar corrosion and protection was discussed. The results show that, the chopped carbon fiber is to promote steel bar corrosion, and the greater the content, the more obvious role in the promotion of steel bar corrosion. Structural system protection methods can be effectively implemented on the reinforcement of protection.
v
引文
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