WO2023272905A1 - 一种可调控颜色的修复剂及制法和含有该修复剂的混凝土 - Google Patents

一种可调控颜色的修复剂及制法和含有该修复剂的混凝土 Download PDF

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WO2023272905A1
WO2023272905A1 PCT/CN2021/113384 CN2021113384W WO2023272905A1 WO 2023272905 A1 WO2023272905 A1 WO 2023272905A1 CN 2021113384 W CN2021113384 W CN 2021113384W WO 2023272905 A1 WO2023272905 A1 WO 2023272905A1
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agent
powder
dopamine
color
microbial
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PCT/CN2021/113384
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English (en)
French (fr)
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钱春香
任新涠
陈沁文
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东南大学
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Priority to US18/276,065 priority Critical patent/US20240132403A1/en
Publication of WO2023272905A1 publication Critical patent/WO2023272905A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0001—Living organisms, e.g. microorganisms, or enzymes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to a cement-based material and a preparation method, in particular to a repairing agent for microbial self-repairing concrete cracks, a preparation method thereof, and microbial self-repairing concrete using the repairing agent.
  • Self-healing concrete refers to the composite method of repairing adhesive and concrete material, which has the function of self-repairing and regeneration for material damage and damage, and restores or even improves the performance of the concrete material.
  • Self-healing concrete can solve difficult problems such as untimely repair and difficult construction in traditional passive repair methods. It has great potential in timely repair of major civil infrastructure and in reducing the impact of typhoons and earthquakes. Material safety and durability are of paramount importance.
  • Microbial self-healing concrete belongs to the category of self-healing concrete. This type of concrete is based on the microbial-induced calcium carbonate precipitation technology, and the cracks generated during the use of concrete are repaired by the way of microbial-induced mineralization and deposition of calcium carbonate to fill the cracks. Compared with self-repair methods based on chemical principles or physical principles, the microbial self-repair process is greener and gentler. Under the guidance of the current green development direction, microbial-induced calcium carbonate precipitation technology has attracted widespread attention and has been applied in many projects.
  • the purpose of the present invention is to provide a repairing agent that can regulate the color of microbial mineralization products and reduce the color difference between the repairing product and the concrete matrix;
  • the second purpose of the present invention is to provide a preparation method for the above-mentioned repairing agent;
  • the third object of the invention is to provide a microbial self-healing concrete containing the above-mentioned repairing agent.
  • a color-controllable repairing agent of the present invention is a mixture of cement-immobilized microbial powder, dopamine and calcium source, wherein, based on the total mass of the mixture, the mass percentage of microbial powder is 44 ⁇ 54%, the mass percentage of dopamine is 1 ⁇ 5%, the mass percentage of calcium source is 44 ⁇ 54%
  • a mixture powder of cement-loaded dopamine, microbial powder and calcium source is used to obtain a repair agent with adjustable color.
  • the microbial powder is selected from colloidal bacillus, alkalophilic bacillus, etc. Purchased from China Industrial Microbial Strain Preservation Management Center, can produce spores, can induce the formation of mineralization products, is harmless to the human body and has good ecology;
  • the calcium source includes one or more solid powders of calcium formate and calcium phosphate The purpose of selecting this type of calcium source is to be able to provide calcium ions required for microbial mineralization reactions, and at the same time have little impact on the performance of the concrete matrix;
  • the cement includes sulphoaluminate cement or Portland cement. The purpose of cement is to act as the shell part of the remedial agent particles to prevent the premature activation of the microbial self-healing agent, resulting in a decrease in the activity of the remediation process.
  • the process of microbial powder-induced mineralization is: when the concrete cracks, the outside air and water enter the crack area, and the spores are activated to produce ammonia and carbon dioxide in the concrete through metabolism. With the hydrolysis of ammonia and carbon dioxide, the system It is alkaline, the calcium source releases free Ca 2+ and mineralizes under alkaline conditions to form calcium carbonate so that the fracture area can be repaired.
  • the added dopamine can further react with the mineralized product.
  • the main reaction process is as follows:
  • the present invention also protects a method for preparing a color-adjustable restoration agent, which includes the following steps:
  • step (1) Take an appropriate amount of adhering substance, spray distilled water on the surface and pour it into the sugar coating machine; spray the mixed powder and water mist prepared in step (1) into the sugar coating machine in batches for powder coating and granulation. particle sieving;
  • the mass ratio of microbial powder, dopamine and calcium source is 10-45:10-45:1.
  • the adhesive substance is sucrose particles.
  • Adhesive substances are adhesive particles that can act as an inner core to attach powder and are harmless to bacteria.
  • the particle size after sieving is 1.75-2.36 mm; in the step (3), the particle size after sieving is 3.5-4.0 mm.
  • the reason for controlling the particle size is that repairing agent particles are used instead of some aggregates to add to concrete components. If the particle size is too large, the mechanical properties of the concrete component will be reduced. If the particle size is too small, the content of self-repairing agent will be low and the repairing effect will be reduced. .
  • step (3) it also includes maintenance of the repairing agent granules
  • the maintenance process is: placing the repairing agent granules in a constant temperature and ventilated environment at 20-30°C for 45-50 hours, and every 6-8 hours to the Spray water mist on the surface of the repair agent to keep the surface moist.
  • the purpose of curing is to increase the hardness of the cement shell and reduce the premature cracking of repair agent particles during the concrete mixing process.
  • the invention also protects a kind of concrete, the composition of which includes the above-mentioned repairing agent whose color can be adjusted, and the repairing agent is added instead of the fine aggregate, and the dosage of the repairing agent is 0.5-4%.
  • the formula of the concrete is: the raw materials in the concrete include P ⁇ O42.5 ordinary Portland cement, basalt stone, river sand, and repair agent particles, and the ratio of the concrete is calculated according to the performance requirements in the actual project.
  • the principle of preparation is to adhere the cement powder to the surface of the restoration agent, and carry out immobilization protection for the restoration agent, so as to prevent the self-repair effect from being degraded due to the premature activation of microorganisms.
  • the cement shell is compatible with the concrete matrix. The performance of concrete members has less influence.
  • the present invention has the following significant advantages: (1) The present invention uses a method of combining organic matter and inorganic matter to regulate the color of microbial mineralization products and reduce the distance between the mineralization products and the concrete matrix. (2) The dopamine used in the present invention reacts with microbial mineralization products to produce an organic-inorganic composite structure with certain adhesion, which is beneficial to the mineralization products in the concrete crack area (3) The mineralizing microorganism adopted in the present invention can produce spores, is suitable for the field of engineering materials, is harmless to the human body and has good ecology.
  • Fig. 1 is the schematic diagram of the repairing part of the sample crack that is mixed with dopamine-containing repairing agent particles in embodiment 1;
  • Fig. 2 is the schematic diagram of the repairing part of the sample crack in Example 1 which does not contain dopamine repairing agent particles;
  • Fig. 3 is the schematic diagram of the crack repair part of the sample mixed with dopamine-containing repair agent particles in Example 2;
  • Fig. 4 is the variation situation of the supersonic velocity of the concrete sample in embodiment 3 along with repair time;
  • Fig. 5 is the change situation of the recovery rate of water penetration resistance of concrete sample with repair time in embodiment 3;
  • Fig. 6 is the synthetic product powder that mixes dopamine among the embodiment 4;
  • Fig. 7 is not mixed with the synthetic product powder of dopamine in embodiment 4;
  • FIG. 8 is an infrared analysis spectrum of the mineralization product of Example 1.
  • the filling condition of repair products in concrete cracks was analyzed by water resistance penetration recovery test, as shown in Figure 5, compared with samples mixed with dopamine repair agent particles and samples without repair agent particles ;
  • the water penetration recovery rate of the concrete sample mixed with dopamine is slightly lower than the water penetration recovery rate of the sample without dopamine, and is much higher than the boiling water penetration recovery rate of the sample without repair agent particles, indicating that the dopamine content
  • the filling has little effect on the filling of repair products in concrete cracks.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)

Abstract

一种可调控颜色的修复剂及制法和含有该修复剂的混凝土，修复剂为水泥固载微生物菌粉、多巴胺和钙源的混合物，其中，按混合物总质量计，微生物菌粉的质量百分比为44～54％，多巴胺的质量百分比为1～5％，钙源的质量百分比为44～54％。将多巴胺掺入微生物自修复剂中，使用水泥固载微生物自修复剂制备修复剂颗粒，对微生物自修复混凝土的裂缝区域进行修复，检验混凝土的修复性能以及裂缝区域修复产物的颜色。使用有机物与无机物结合的方法，对微生物矿化产物的颜色进行调控，降低矿化产物与混凝土基体之间的色差，满足自修复混凝土表面外观美学需求。

Description

一种可调控颜色的修复剂及制法和含有该修复剂的混凝土 技术领域
本发明属于一种水泥基材料及制备方法，具体涉及一种用于微生物自修复混凝土裂缝区的修复剂及其制备方法以及采用该修复剂的微生物自修复混凝土。
背景技术
自修复混凝土是指采用修复胶粘剂和混凝土材料相复合的方法，对材料损伤破坏具有自修复和再生的功能，恢复甚至提高材料性能的混凝土材料。自修复混凝土可以解决传统的被动修复方法中修复不及时，施工困难等难以解决的问题，在重大土木基础设施的及时修复以及减轻台风、地震的冲击等诸多方面有很大的潜力，对确保建筑物的安全和耐久性都极具重要性。
微生物自修复混凝土属于自修复混凝土中的一类，该类混凝土基于微生物诱导碳酸钙沉淀技术，通过微生物诱导矿化沉积碳酸钙填充裂缝的方式修复混凝土在使用过程中产生的裂缝。相较于基于化学原理或物理原理的自修复方法，微生物自修复过程更加绿色温和，在如今绿色发展的方向的指引下，微生物诱导碳酸钙沉淀技术被广泛关注，在诸多工程中得到应用。
然而，这项技术在混凝土自修复的领域仍存在诸多问题急需解决，如微生物矿化产物的颜色调控问题，通过微生物诱导矿化沉积的碳酸钙呈现为白色，与混凝土基体颜色不协调，使得修复后的混凝土表面存在颜色差异，对混凝土外观的整体性产生影响。目前对于微生物自修复混凝土的研究均体现在提高修复性能的方面，但对矿化产物颜色进行调控的研究鲜有报道。
发明内容
发明目的：本发明的目的在于提供一种可以对微生物矿化产物进行颜色调控，降低修复产物与混凝土基体之间色差的修复剂；本发明的第二目的在于提供上述修复剂的制备方法；本发明的第三目的在于提供一种含有上述修复剂的微生物自修复混凝土。
技术方案：本发明的一种可调控颜色的修复剂，所述修复剂为水泥固载微生物菌粉、多巴胺和钙源的混合物，其中，按混合物总质量计，微生物菌粉的质量百分比为44～54％，多巴胺的质量百分比为1～5％，钙源的质量百分比为44～54％
上述的方案中，使用水泥固载多巴胺、微生物菌粉和钙源的混合物粉末，得到可调控颜色的修复剂，所述的微生物菌粉选用胶质芽孢杆菌、嗜碱芽孢杆菌等，该菌粉购自中国工业微生物菌种保藏管理中心，可产芽孢，能诱导矿化产物生成，对人体无害且生态性良好；所述钙源包括甲酸钙、磷酸钙中的一种或多种固体粉 末，选用此类钙源的目的是能够提供微生物矿化反应所需的钙离子，同时对混凝土基体造成的性能影响较小；所述水泥包括硫铝酸盐水泥或硅酸盐水泥，采用此类水泥的目的是作为修复剂颗粒的外壳部分，防止微生物自修复剂提前激活导致修复过程活性下降。
微生物菌粉诱导矿化的过程为：当混凝土产生裂缝后，外界的空气和水进入裂缝区，芽孢被激活通过代谢作用使混凝土中产生氨气和二氧化碳，随着氨气和二氧化碳的水解使得体系呈碱性，钙源释放出游离的Ca 2+在碱性条件下矿化形成碳酸钙从而可以对裂缝区域进行修补。
同时，加入的多巴胺可以进一步与矿化的产物反生反应，主要反应过程参见如下：
Figure PCTCN2021113384-appb-000001
首先，多巴胺中-NH 2与碳酸钙之间通过反应连接生成具有-N···H-O-氢键结构的有机-无机复合结构，然后，多巴胺结构中的羟基在空气中会发生氧化形成醌，生成黑色聚合物，对有机-无机复合产物进行颜色调控。
本发明还保护一种可调控颜色的修复剂的制备方法，包括以下步骤：
(1)将微生物菌粉、多巴胺、钙源混合，搅拌均匀成混合粉末备用；
(2)取适量黏附物质，在表面喷洒蒸馏水后将其倒入糖衣机；分批次向糖衣机中喷洒步骤(1)制备的混合粉末和水雾进行裹粉造粒，造粒完成后将颗粒过筛；
(3)将过筛后的颗粒再次倒入糖衣机，分批次向糖衣机中喷洒水泥粉末和水雾进行裹粉造粒，造粒完成后过筛得到修复剂颗粒。
进一步的，所述步骤(1)中，微生物菌粉、多巴胺和钙源的质量比为10～45：10～45：1。
进一步的，所述步骤(2)中，黏附物质为蔗糖颗粒。黏附物质为具有黏附性， 能够作为内核附着粉末且对细菌无害的颗粒。
进一步的，所述步骤(2)中，过筛后的粒径为1.75～2.36mm；所述步骤(3)中，过筛后的粒径为3.5～4.0mm。控制粒径的原因在于后续使用修复剂颗粒代替部分骨料加入到混凝土构件中，若粒径过大会降低混凝土构件的力学性能，若粒径过小会导致自修复剂含量较低，修复效果下降。
进一步的，在步骤(3)之后还包括对修复剂颗粒的养护，所述养护过程为：将修复剂颗粒置于20～30℃恒温通气环境下静置45～50h，每隔6～8h向修复剂表面喷洒水雾使表面保持湿润。进行养护的目的在于提高水泥外壳的硬度，减少混凝土搅拌的过程中修复剂颗粒提前开裂的现象。
本发明还保护一种混凝土，其组分中包括上述的可调控颜色的修复剂，修复剂代替细骨料掺入，所述修复剂的掺量为0.5～4％。混凝土的配方为：混凝土中的原料包括P·O42.5普通硅酸盐水泥，玄武岩石子，河砂，修复剂颗粒，根据实际工程中的性能要求对混凝土的配比进行计算。
上述的制备方法中，制备的原理是将水泥粉末黏附在修复剂表面，对修复剂进行固载保护，防止微生物被提前激活导致自修复效果下降，同时水泥外壳与混凝土基体具有相容性，对混凝土构件的性能造成的影响较小。
有益效果：与现有技术相比，本发明的具有如下显著优点：(1)本发明使用有机物与无机物结合的方法，对微生物矿化产物的颜色进行调控，降低矿化产物与混凝土基体之间的色差，满足自修复混凝土表面外观美学需求；(2)本发明使用的多巴胺与微生物矿化产物发生反应产生有机-无机复合结构具有一定的粘附性，有利于矿化产物在混凝土裂缝区的填充修复；(3)本发明采用的矿化微生物可产芽孢，适用于工程材料领域，对人体无害且生态性良好。
附图说明
图1为实施例1掺入含多巴胺修复剂颗粒的试样裂缝修复部位示意图；
图2为实施例1掺入不含多巴胺修复剂颗粒的试样裂缝修复部位示意图；
图3为实施例2掺入含多巴胺修复剂颗粒的试样裂缝修复部位示意图；
图4为实施例3中混凝土试样的超声波速随修复时间的变化情况；
图5为实施例3中混凝土试样的抗水渗透回收率随修复时间的变化情况；
图6为实施例4中掺入多巴胺的合成产物粉末；
图7为实施例4中不掺多巴胺的合成产物粉末；
图8为实施例1的矿化产物的红外分析图谱。
具体实施方式
下面结合附图和实施例对本发明的技术方案做进一步详细说明。
实施例1
(1)将胶质芽孢杆菌菌粉：甲酸钙：多巴胺以30：30：1的质量比例混合制成混合粉末，以蔗糖为内核，将蔗糖颗粒平铺，在颗粒表面喷洒水雾后将其倒入糖衣机，分批次向糖衣机中喷洒混合粉末与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为1.75mm～2.36mm的颗粒；
(2)再次使用糖衣机在颗粒外部包裹硫铝酸盐水泥，将过筛后的颗粒再次倒入糖衣机，分批次向糖衣机中喷洒硫铝酸盐水泥与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为3.5mm～4.0mm的颗粒即为修复剂；
(3)将修复剂颗粒置于20℃恒温通气环境下养护48h，每隔6h向载体表面喷洒水雾使载体表面保持湿润；
(4)称取P·O42.5普通硅酸盐水泥1037g/L，修复剂47g/L，水546g/L，拌和净浆试样，将净浆试样置于标准条件下养护3d后制造裂缝；
(5)将开裂后的净浆试样在20℃的环境下置于水中养护，养护7d后使用体式显微镜观察裂缝区域(如图1所示)，裂缝被微生物矿化产物填充，可见多巴胺的掺入对裂缝表面修复效果的影响较小，同时相比于未掺入多巴胺的试样裂缝修复区域(如图2所示)，掺加多巴胺的试样在裂缝区域的修复产物的颜色呈灰白色，修复产物与混凝土基体之间的色差减小，可见多巴胺的掺入可以使调控修复产物的颜色。
提取调控颜色后得到的修复产物，将产物进行烘干研磨处理使用傅立叶变换红外吸收光谱仪进行检测，分析多巴胺对矿化产物进行颜色调控的可行性。得到矿化产物的红外图谱如图8所示，其中波数3405.47cm -1处存在N···H-O氢键振荡峰，表明多巴胺与碳酸钙之间通过氢键连接生成有机-无机复合结构。
实施例2
(1)将嗜碱芽孢杆菌菌粉：氯化钙：多巴胺以10：10：1的质量比例混合制成混合粉末，以蔗糖为内核，将蔗糖颗粒平铺，在颗粒表面喷洒水雾后将其倒入糖衣机，分批次向糖衣机中喷洒混合粉末与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为1.75mm～2.36mm的颗粒；
(2)再次使用糖衣机在颗粒外部包裹硅酸盐水泥，将过筛后的颗粒再次倒入糖衣机，分批次向糖衣机中喷洒硅酸盐水泥与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为3.5mm～4.0mm的颗粒即为修复剂；
(3)将修复剂颗粒置于30℃恒温通气环境下养护50h，每隔8h向载体表面喷洒水雾使载体表面保持湿润；
(4)称取P·O42.5普通硅酸盐水泥347g/L，修复剂40g/L，河砂746g/L， 玄武岩石子1187g/L，水170g/L，拌和混凝土试样，将混凝土试样置于标准条件下养护3d后制造裂缝；
(5)将开裂后的净浆试样在20℃的环境下置于水中养护，养护7d后使用体式显微镜观察修复情况，裂缝修复区域如图3所示。
实施例3
(1)将胶质芽孢杆菌菌粉：磷酸钙：多巴胺以45：45：1的质量比例混合制成混合粉末，以蔗糖为内核，将蔗糖颗粒平铺，在颗粒表面喷洒水雾后将其倒入糖衣机，分批次向糖衣机中喷洒混合粉末与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为1.75mm～2.36mm的颗粒；
(2)再次使用糖衣机在颗粒外部包裹硫铝酸盐水泥，将过筛后的颗粒再次倒入糖衣机，分批次向糖衣机中喷洒硫铝酸盐水泥与水雾进行裹粉造粒，造粒完成后将修复剂颗粒过筛取粒径为3.5mm～4.0mm的颗粒即为修复剂；
(3)将修复剂颗粒置于25℃恒温通气环境下养护45h，每隔7h向载体表面喷洒水雾使载体表面保持湿润；
(4)称取P·O42.5普通硅酸盐水泥347g/L，修复剂23g/L，河砂764g/L，玄武岩石子1187g/L，水170g/L，拌和混凝土试样，将混凝土试样置于标准条件下养护3d后制造裂缝；
(5)将开裂后的净浆试样在20℃的环境下置于水中养护，当养护时间为7d，14d，28d时，通过超声波速检测对修复产物在混凝土裂缝中的粘结情况进行分析，如图4所示，与掺入不含多巴胺修复剂颗粒的试样和不掺修复剂颗粒的试样进行对比分析；掺入多巴胺的混凝土试样的超声波速与未掺入多巴胺的试样超声波速相近，说明多巴胺的掺入几乎不影响修复产物在混凝土裂缝中的粘结情况。通过抗水渗透回收率检测对修复产物在混凝土裂缝中的填充情况进行分析，如图5所示，与掺入不含多巴胺修复剂颗粒的试样和不掺修复剂颗粒的试样进行对比分析；掺入多巴胺的混凝土试样的抗水渗透回收率略低于未掺入多巴胺的试样抗水渗透回收率，远高于不掺修复剂颗粒的试样开水渗透回收率，说明多巴胺的掺入对修复产物在混凝土裂缝中的填充情况影响较小。
实施例4
为了验证多巴胺与微生物矿化产物发生反应，进行如下实验：
(1)将菌液，钙源与多巴胺粉末加水溶解混合，制备成反应液体；
(2)将液体置于遮光常温的环境下静置反应7d，待矿化反应结束后得到含矿化产物的悬浊液；
(3)对悬浊液进行过滤，使用去离子水与无水乙醇洗涤沉淀物；
(4)对沉淀物进行烘干处理，得到合成产物粉末。
(5)将掺有多巴胺(PDA)的合成产物粉末(如图5所示)与未掺多巴胺的合成产物粉末(如图6所示)进行对比分析，含多巴胺的合成产物的呈现为棕灰色，未掺多巴胺的合成产物呈现为白色。使用ImageJ软件对合成产物的灰度值进行检测(黑色的灰度值为0，白色的灰度值为255)，两种合成产物的灰度值分别为110.136与177.489，多巴胺的掺入能够降低合成产物的灰度值，使产物颜色变深。

Claims (10)

  1. 一种可调控颜色的修复剂，其特征在于：所述修复剂为水泥固载微生物菌粉、多巴胺和钙源的混合物，其中，按修复剂总质量计，微生物菌粉的质量百分比为44～54％，多巴胺的质量百分比为1～5％，钙源的质量百分比为44～54％。
  2. 根据权利要1所述的可调控颜色的修复剂，其特征在于：所述微生物菌粉选自胶质芽孢杆菌或嗜碱芽孢杆菌。
  3. 根据权利要1所述的可调控颜色的修复剂，其特征在于：所述钙源包括甲酸钙、氯化钙、磷酸钙中的一种或多种固体粉末。
  4. 根据权利要1所述的可调控颜色的修复剂，其特征在于：所述水泥包括硫铝酸盐水泥或硅酸盐水泥。
  5. 一种权利要求1-4任一项所述的可调控颜色的修复剂的制备方法，其特征在于，包括以下步骤：
    (1)将微生物菌粉、多巴胺、钙源混合，搅拌均匀成混合粉末备用；
    (2)取适量黏附物质，在表面喷洒蒸馏水后将其倒入糖衣机；分批次向糖衣机中喷洒步骤(1)制备的混合粉末和水雾进行裹粉造粒，造粒完成后将颗粒过筛；
    (3)将过筛后的颗粒再次倒入糖衣机，分批次向糖衣机中喷洒水泥粉末和水雾进行裹粉造粒，造粒完成后过筛得到修复剂颗粒。
  6. 根据权利要求5所述的可调控颜色的修复剂的制备方法，其特征在于；所述步骤(1)中，微生物菌粉、多巴胺和钙源的质量比为10～45：10～45：1。
  7. 根据权利要求5所述的可调控颜色的修复剂的制备方法，其特征在于；所述步骤(2)中，黏附物质为蔗糖颗粒。
  8. 根据权利要求5所述的可调控颜色的修复剂的制备方法，其特征在于；所述步骤(2)中，过筛后的粒径为1.75～2.36mm；所述步骤(3)中，过筛后的粒径为3.5～4.0mm。
  9. 根据权利要求5所述的可调控颜色的修复剂的制备方法，其特征在于；在步骤(3)之后还包括对修复剂颗粒的养护，所述养护过程为：将修复剂颗粒置于20～30℃恒温通气环境下静置45～50h，每隔6～8h向修复剂表面喷洒水雾使表面保持湿润。
  10. 一种混凝土，其特征在于：以权利要求1-4任一项所述的修复剂代替细骨料掺入得到，所述修复剂的掺量为0.5～4％。
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