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CN115716734A - Anti-cracking corrosion-resistant type ultrahigh-performance concrete with thixotropy and preparation method thereof - Google Patents

Anti-cracking corrosion-resistant type ultrahigh-performance concrete with thixotropy and preparation method thereof Download PDF

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CN115716734A
CN115716734A CN202211467366.0A CN202211467366A CN115716734A CN 115716734 A CN115716734 A CN 115716734A CN 202211467366 A CN202211467366 A CN 202211467366A CN 115716734 A CN115716734 A CN 115716734A
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composite
stirring
fiber
performance concrete
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CN115716734B (en
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李建永
李峰
李少力
许红彬
张帅
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Hebei Dingqiang New Material Technology Co ltd
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Shenzhen Haiwei Technology R&d Co ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention relates to the technical field of concrete, and discloses an anti-cracking corrosion-resistant type ultrahigh-performance concrete with thixotropy and a preparation method thereof. The paint comprises the following components in parts by weight: 600-700 parts of cement, 80-150 parts of silica fume powder, 700-800 parts of mineral powder admixture, 90-120 parts of quartz sand, 700-900 parts of slag making machine sand, 100-250 parts of modified composite fiber, 3-10 parts of composite thixotropic agent, 15-40 parts of water reducing agent composite slurry and 170-280 parts of water. By replacing part of cement with a large amount of mineral powder admixture, adding the composite thixotropic agent and the self-made anti-cracking and anti-corrosion type water reducing agent composite slurry, and replacing steel fibers with modified composite fibers, the synergistic effect among the components not only reduces the shrinkage stress and pumping resistance of the ultra-high performance concrete, reduces resilience and drying shrinkage, and reduces the risks of corrosion and cracking, but also enables the newly-mixed ultra-high performance concrete to have very high bending strength and compressive strength, and can well solve the problems of poor thixotropy, large resilience, easy cracking and poor durability of the ultra-high performance concrete in construction application.

Description

一种具有触变性的抗裂耐蚀型超高性能混凝土及其制备方法Thixotropic anti-crack and corrosion-resistant ultra-high performance concrete and preparation method thereof

技术领域technical field

本发明涉及混凝土技术领域,更具体地说,涉及一种具有触变性的抗裂耐蚀型超高性能混凝土及其制备方法。The invention relates to the technical field of concrete, in particular to a thixotropic anti-crack and anti-corrosion ultra-high performance concrete and a preparation method thereof.

背景技术Background technique

超高性能混凝土(Ultra-High Performance Concrete,UHPC)具有高抗压、抗折强度和优异的耐久性,满足了结构工程中高强度设施在严酷环境下使用的发展需求。广泛应用于桥梁、地下、军事等高科技工程领域中。Ultra-High Performance Concrete (UHPC) has high compressive strength, flexural strength and excellent durability, which meets the development needs of high-strength facilities used in severe environments in structural engineering. Widely used in bridges, underground, military and other high-tech engineering fields.

由于超高性能混凝土的水胶比极低,水泥和硅灰等活性矿物掺合料粒度细、掺量高,使其在硬化后伴随着较大的屈服应力,存在回弹和早期开裂的风险。同样的原因又使得新拌超高性能混凝土的粘度大,搅拌及泵送阻力大,难以进行规模化施工,并且在浇筑成型过程中超高性能混凝土易絮凝,严重损害了超高性能混凝土的力学性能,在一定程度上制约了超高性能混凝土的工程应用。Due to the extremely low water-to-binder ratio of ultra-high-performance concrete, the fine particle size and high content of active mineral admixtures such as cement and silica fume, it is accompanied by a large yield stress after hardening, and there is a risk of rebound and early cracking . For the same reason, the viscosity of freshly mixed ultra-high performance concrete is high, and the resistance of mixing and pumping is large, making it difficult to carry out large-scale construction. In addition, ultra-high performance concrete is easy to flocculate during the pouring process, which seriously damages the mechanical properties of ultra-high performance concrete. , to a certain extent restricts the engineering application of ultra-high performance concrete.

为了保证超高性能混凝土优异的力学性能,首先,要求新拌超高性能混凝土具有良好的体积稳定性、抗裂性能和适宜的触变性,也即降低搅拌及泵送阻力,在搅拌和泵送过程中容易呈现剪切变稀、降粘的特点;同时,在静置状态时包裹性提高,体积、粘度迅速恢复正常,具有低回弹性特点,纤维和骨料呈现均匀分布,防止超高性能混凝土回弹、流挂和开裂。其次,由于超高性能混凝土服役的环境大多是高温、低温、高盐、高湿、辐射、核电和应力疲劳等恶劣环境,对其耐腐蚀等耐久性能要求很高。因此,急需寻找一种超高性能混凝土,可以解决其在工程应用中,触变性差、回弹性高,易腐蚀、开裂和耐久性不良的问题。In order to ensure the excellent mechanical properties of ultra-high performance concrete, first of all, fresh ultra-high performance concrete is required to have good volume stability, crack resistance and suitable thixotropy, that is, to reduce the resistance of mixing and pumping. During the process, it is easy to show the characteristics of shear thinning and viscosity reduction; at the same time, when it is in a static state, the wrapping property is improved, the volume and viscosity quickly return to normal, and it has the characteristics of low resilience, and the fibers and aggregates are evenly distributed, preventing ultra-high performance. Concrete rebounds, sags and cracks. Secondly, because the environment in which ultra-high performance concrete is served is mostly harsh environments such as high temperature, low temperature, high salt, high humidity, radiation, nuclear power, and stress fatigue, the requirements for its durability such as corrosion resistance are very high. Therefore, there is an urgent need to find a kind of ultra-high performance concrete, which can solve the problems of poor thixotropy, high resilience, easy corrosion, cracking and poor durability in engineering applications.

发明内容Contents of the invention

针对现有超高性能混凝土存在的上述问题,本发明提供一种具有触变性的抗裂耐蚀型超高性能混凝土及其制备方法,该超高性能混凝土通过各组分之间的协同作用,不仅减小了超高性能混凝土的收缩应力和泵送阻力,降低开裂的风险,而且使新拌超高性能混凝土具有很高的抗折、抗压强度,可以很好地解决超高性能混凝土在施工应用中,触变性差、回弹性大,易开裂和耐久性不良的问题。Aiming at the above-mentioned problems existing in the existing ultra-high performance concrete, the present invention provides a thixotropic anti-crack and corrosion-resistant ultra-high performance concrete and a preparation method thereof. It not only reduces the shrinkage stress and pumping resistance of ultra-high performance concrete, reduces the risk of cracking, but also makes freshly mixed ultra-high performance concrete have high flexural and compressive strength, which can well solve the problem of ultra-high performance concrete in In construction and application, there are problems of poor thixotropy, large resilience, easy cracking and poor durability.

为达到上述发明目的,本发明采用了如下的技术方案:In order to achieve the above-mentioned purpose of the invention, the present invention has adopted following technical scheme:

第一方面,一种具有触变性的抗裂耐蚀型超高性能混凝土,包括以下重量份数的组分:水泥600~700份,硅灰粉80~150份,矿粉掺合料700~800份,石英砂90~120份,矿渣机制砂700~900份,改性复合纤维100~250份,复合触变剂3~10份,减水剂复合浆液15~40份,水170~280份;In the first aspect, a crack-resistant and corrosion-resistant ultra-high performance concrete with thixotropy, including the following components in parts by weight: 600-700 parts of cement, 80-150 parts of silica fume powder, and 700-700 parts of mineral powder admixture 800 parts, 90-120 parts of quartz sand, 700-900 parts of slag machine-made sand, 100-250 parts of modified composite fiber, 3-10 parts of composite thixotropic agent, 15-40 parts of composite slurry of water reducer, 170-280 parts of water share;

所述复合触变剂的制备方法包括:The preparation method of described composite thixotropic agent comprises:

将至少两种无机触变剂的混合物于105℃~115℃条件下搅拌、烘干,降温至25℃~35℃后,加入铝酸酯偶联剂,搅拌,再加入椰油酸二乙醇酰胺,继续搅拌,最后加入有机触变剂,搅拌均匀,即得所述复合触变剂;Stir and dry the mixture of at least two inorganic thixotropic agents at 105°C to 115°C. After cooling down to 25°C to 35°C, add aluminate coupling agent, stir, and then add coconut acid diethanolamide , continue to stir, finally add an organic thixotropic agent, stir evenly, and obtain the composite thixotropic agent;

所述减水剂复合浆液的制备方法包括:The preparation method of the composite slurry of the water reducing agent comprises:

步骤a:将4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体、甲基丁烯磺酸钠、2-羟基-2-甲基二丁烯酸、辛烯基琥珀酸单阿拉伯胶酯和3,4-二氨基苯甲酸甲酯,加入去离子水中,搅拌均匀,滴加引发剂,滴加时间为1h~1.5h,聚合反应,得聚羧酸减水剂;Step a: Add 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer, sodium methylbutenesulfonate, 2-hydroxy-2-methyldibutenoic acid, octenylsuccinate Acid monogum arabic ester and methyl 3,4-diaminobenzoate were added to deionized water, stirred evenly, and the initiator was added dropwise for 1h to 1.5h, and the polymerization reaction was carried out to obtain a polycarboxylate water reducer;

步骤b:向步骤a得到的所述聚羧酸减水剂中加入220℃高温氧化处理后的氮化硼纳米片和三羟丙基羟乙基乙二胺,于30℃~45℃继续搅拌,即得所述减水剂复合浆液。Step b: Add boron nitride nanosheets and trihydroxypropyl hydroxyethyl ethylenediamine after high temperature oxidation treatment at 220°C to the polycarboxylate water reducer obtained in step a, and continue stirring at 30°C to 45°C , to obtain the composite slurry of the water reducer.

与现有技术相比,本发明所述的具有触变性的抗裂耐蚀型超高性能混凝土至少具有如下有益效果:Compared with the prior art, the thixotropic anti-crack and anti-corrosion ultra-high performance concrete at least has the following beneficial effects:

(1)本申请中的减水剂复合浆液为抗裂耐蚀型减水复合浆液,可以增加超高性能混凝土各成分之间的相容性和稳定性;提高胶凝材料的分散性,降低水胶比;提高超高性能混凝土在固化和干燥过程中的刚性和韧性,克服了超高性能混凝土的开裂现象;同时阻止超高性能混凝土中腐蚀介质的转运和扩散,避免超高性能混凝土腐蚀失效,保证超高性能混凝土良好的力学性能和耐久性。(1) The water-reducing agent composite slurry in this application is a crack-resistant and corrosion-resistant water-reducing composite slurry, which can increase the compatibility and stability between the components of ultra-high performance concrete; improve the dispersion of cementitious materials, reduce Water-binder ratio; improve the rigidity and toughness of ultra-high-performance concrete during curing and drying, overcome the cracking phenomenon of ultra-high-performance concrete; prevent the transfer and diffusion of corrosive media in ultra-high-performance concrete, and avoid corrosion of ultra-high-performance concrete Failure to ensure good mechanical properties and durability of ultra-high performance concrete.

(2)复合触变剂中通过加入有机触变剂、无机触变剂,可以协同改善超高性能混凝土的剪切流动性和抗流挂性,在施工过程中使超高性能混凝土具有良好的体积稳定性,降低泵送阻力和施工难度。(2) By adding organic thixotropic agent and inorganic thixotropic agent to the compound thixotropic agent, it can synergistically improve the shear fluidity and sag resistance of ultra-high performance concrete, and make ultra-high performance concrete have good performance during construction. Volume stability, reducing pumping resistance and construction difficulty.

(3)改性复合纤维在抗裂耐蚀型减水复合浆液的作用下,能够在超高性能混凝土后期形成良好的握裹力,使超高性能混凝土的抗弯折性能和抗压强度显著提高。(3) Under the action of anti-crack and corrosion-resistant water-reducing composite grout, the modified composite fiber can form a good grip force in the later stage of ultra-high performance concrete, so that the bending resistance and compressive strength of ultra-high performance concrete are significantly improved improve.

(4)通过大量矿粉掺合料替代部分水泥、加入复合触变剂和自制抗裂耐蚀型减水剂复合浆液、用改性复合纤维替代钢纤维,各组分协同作用,不仅减小了超高性能混凝土的收缩应力和泵送阻力,降低开裂的风险,而且使新拌超高性能混凝土具有很高的抗折、抗压强度,可以很好地解决超高性能混凝土在施工应用中,触变性差、易开裂和耐久性不良的问题。(4) By replacing part of the cement with a large amount of mineral powder admixture, adding compound thixotropic agent and self-made anti-crack and anti-corrosion type superplasticizer compound slurry, and replacing steel fiber with modified composite fiber, the synergistic effect of each component not only reduces the It reduces the shrinkage stress and pumping resistance of ultra-high performance concrete, reduces the risk of cracking, and makes freshly mixed ultra-high performance concrete have high flexural and compressive strength, which can well solve the problem of ultra-high performance concrete in construction applications. , poor thixotropy, easy cracking and poor durability.

在其中一个实施例中,所述无机触变剂的混合物为菱镁矿微粉、硅镁土、层状蒙托土、坡缕缟石粉、伊利石粉和纳米勃姆石粉中的至少两种等质量混合。In one of the embodiments, the mixture of the inorganic thixotropic agent is equal to at least two of magnesite powder, attapulgite, layered montmorillonite, palygorskite powder, illite powder and nano boehmite powder mix.

在其中一个实施例中,所述有机触变剂为油酸酰胺、卡拉胶、褐藻胶、海藻酸乙二醇酯和微粉化聚酰胺蜡中的任一种。In one of the embodiments, the organic thixotropic agent is any one of oleic acid amide, carrageenan, alginate, ethylene glycol alginate and micronized polyamide wax.

在其中一个实施例中,所述复合触变剂的制备方法中,各原料的质量份数分别为:无机触变剂的混合物80~100份,铝酸酯偶联剂0.1~0.8份,椰油酸二乙醇酰胺0.1~0.5份,有机触变剂30~50份。In one of the embodiments, in the preparation method of the composite thixotropic agent, the parts by mass of each raw material are: 80-100 parts of a mixture of inorganic thixotropic agents, 0.1-0.8 parts of aluminate coupling agent, coconut 0.1-0.5 parts of oleic acid diethanolamide, 30-50 parts of organic thixotropic agent.

在其中一个实施例中,所述复合触变剂的制备方法中,所述铝酸酯偶联剂为铝酸三异丙酯。In one embodiment, in the preparation method of the composite thixotropic agent, the aluminate coupling agent is triisopropyl aluminate.

在复合触变剂的制备过程中,用铝酸酯偶联剂改性无机触变剂,不仅可以改善填充无机触变剂的机械性能,还可以改善其分散性,有利于改性无机触变剂与超高性能混凝土中其他组分进行充分混合,呈现良好的触变性和抗流挂性。In the preparation process of the composite thixotropic agent, modifying the inorganic thixotropic agent with an aluminate coupling agent can not only improve the mechanical properties of the filled inorganic thixotropic agent, but also improve its dispersibility, which is beneficial to modifying the inorganic thixotropic agent. The agent is fully mixed with other components in ultra-high performance concrete, showing good thixotropy and sag resistance.

在其中一个实施例中,所述复合触变剂的制备方法中,所述无机触变剂的混合物的搅拌时间为10min~20min,烘干后所述无机触变剂的混合物的含水量低于0.1%。In one of the embodiments, in the preparation method of the composite thixotropic agent, the stirring time of the mixture of the inorganic thixotropic agent is 10min to 20min, and the water content of the mixture of the inorganic thixotropic agent after drying is lower than 0.1%.

在其中一个实施例中,所述复合触变剂的制备方法中,加入所述铝酸酯偶联剂后搅拌时间为15min~20min,转速为180r/min~220r/min。In one embodiment, in the preparation method of the composite thixotropic agent, the stirring time after adding the aluminate coupling agent is 15 min to 20 min, and the rotation speed is 180 r/min to 220 r/min.

在其中一个实施例中,所述复合触变剂的制备方法中,加入所述椰油酸二乙醇酰胺后搅拌时间为5min~10min;加入所述有机触变剂后搅拌时间为3min~5min,转速为100r/min~200r/min。In one of the embodiments, in the preparation method of the composite thixotropic agent, the stirring time after adding the coconut acid diethanolamide is 5min~10min; the stirring time after adding the organic thixotropic agent is 3min~5min, The rotating speed is 100r/min~200r/min.

本发明实施例复合触变剂的制备工艺中,充分利用改性无机触变剂的触变特性和吸水结构,使制备的复合触变剂具有良好的抗裂、保水特点,在施工过程中使超高性能混凝土具有良好的泵送性能、剪切流动性和抗流挂性。In the preparation process of the composite thixotropic agent in the embodiment of the present invention, the thixotropic properties and water absorption structure of the modified inorganic thixotropic agent are fully utilized, so that the prepared composite thixotropic agent has good crack resistance and water retention characteristics. UHPC has good pumpability, shear flow and sag resistance.

在其中一个实施例中,所述减水剂复合浆液的制备方法中,各原料的质量份数分别为:4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体100~150份,甲基丁烯磺酸钠10~20份,2-羟基-2-甲基二丁烯酸20~40份,辛烯基琥珀酸单阿拉伯胶酯30~50份,3,4-二氨基苯甲酸甲酯20~40份,去离子水60~100份,引发剂5~15份,氮化硼纳米片1~5份,三羟丙基羟乙基乙二胺5~10份。In one of the examples, in the preparation method of the water reducer composite slurry, the parts by mass of each raw material are: 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer 100- 150 parts, 10-20 parts of sodium methylbutene sulfonate, 20-40 parts of 2-hydroxy-2-methylbutenoic acid, 30-50 parts of octenyl succinic acid mono-arabic ester, 3,4- 20-40 parts of methyl diaminobenzoate, 60-100 parts of deionized water, 5-15 parts of initiator, 1-5 parts of boron nitride nanosheets, 5-10 parts of trihydroxypropyl hydroxyethyl ethylenediamine .

其中,4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体的结构式为:Wherein, the structural formula of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer is:

Figure BDA0003956848930000041
其中,n表示聚合度。
Figure BDA0003956848930000041
Among them, n represents the degree of polymerization.

4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体的制备方法:对4,4-二甲基戊烯醇、环氧丙烷、环氧乙烷和NaOH溶液进行干燥预处理,然后将预处理后的4,4-二甲基戊烯醇和NaOH溶液混合,在N2保护下,加入预处理后的环氧丙烷和环氧乙烷混合物,用HCl溶液调节pH至5.0进行开环聚合反应,继续保温熟化一段时间,冷却至室温并真空脱气,即得4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体。The preparation method of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer: pre-drying 4,4-dimethylpentenol, propylene oxide, ethylene oxide and NaOH solution treatment, then mix the pretreated 4,4-dimethylpentenol and NaOH solution, add the pretreated propylene oxide and ethylene oxide mixture under the protection of N2 , and adjust the pH to 5.0 with HCl solution Carry out ring-opening polymerization reaction, continue heat preservation and aging for a period of time, cool to room temperature and vacuum degassing to obtain 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer.

具体过程如下:The specific process is as follows:

预处理:取如下原料:20份4,4-二甲基戊烯醇、300份环氧丙烷、300份环氧乙烷和1份1mol/L NaOH溶液,利用干燥N2对上述原料分别进行喷雾干燥处理,使上述原料含水率为0.01%;Pretreatment: Take the following raw materials: 20 parts of 4,4-dimethylpentenol, 300 parts of propylene oxide, 300 parts of ethylene oxide and 1 part of 1mol/L NaOH solution, and use dry N2 to treat the above raw materials respectively Spray drying treatment, so that the moisture content of the above raw materials is 0.01%;

开环聚合反应:将预处理后的4,4-二甲基戊烯醇和NaOH溶液混合,升温至60℃,在N2保护下,加入预处理后的环氧丙烷和环氧乙烷混合物,用1mol/L的HCl溶液调节pH至5.0进行开环聚合反应,反应2.0h,继续保温熟化2h,冷却至室温并真空脱气15min,即得4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体。Ring-opening polymerization reaction: Mix the pretreated 4,4-dimethylpentenol and NaOH solution, raise the temperature to 60°C, and add the pretreated propylene oxide and ethylene oxide mixture under the protection of N2 , Adjust the pH to 5.0 with 1mol/L HCl solution to carry out the ring-opening polymerization reaction, react for 2.0 hours, continue to heat and mature for 2 hours, cool to room temperature and vacuum degassing for 15 minutes to obtain 4,4-dimethylpentenol polyoxyethylene Polyoxypropylene ether macromonomer.

优选地,氮化硼纳米片是经过高温氧化处理后的,高温氧化处理的温度为220℃,时间为5h,具体地,可以直接用电磁炉将氮化硼纳米片加热到220℃保持5h后降温即可。Preferably, the boron nitride nanosheets are subjected to high-temperature oxidation treatment, the temperature of the high-temperature oxidation treatment is 220°C, and the time is 5h. Specifically, the boron nitride nanosheets can be directly heated to 220°C with an electromagnetic oven and kept for 5h before cooling down. That's it.

在其中一个实施例中,步骤a中,所述引发剂为质量分数为1.0%的过硫酸胺水溶液。In one embodiment, in step a, the initiator is an aqueous solution of ammonium persulfate with a mass fraction of 1.0%.

本发明实施例制备的减水剂复合浆液为抗裂耐蚀型减水剂复合浆液,具有乳化、分散无机粒子的作用,可以增加超高性能混凝土各成分之间的相容性和稳定性。其中的4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体为六碳大单体,能与防裂减水型功能单体辛烯基琥珀酸单阿拉伯胶酯、增韧缓蚀型功能单体3,4-二氨基苯甲酸甲酯聚合,形成具有高活性的侧链基团,侧链和主链中含有诸多带负电荷的羧基(-COO-)、磺酸基团(-RSO3 -)和氨基(-NH2 -)和酯基,在超高性能混凝土水化初期和后期释放颗粒间包裹的水分,减少胶凝材料的聚集,降低水胶比;酯基基团能够在水化反应后期通过水解反应进一步生成羧基(-COO-),缓慢释放颗粒间包裹的水分,使水分均匀分布,提高超高性能混凝土在固化和干燥过程中的刚性和韧性,进一步提升超高性能混凝土的力学性能。The superplasticizer composite slurry prepared in the embodiment of the present invention is a crack-resistant and corrosion-resistant superplasticizer composite slurry, which has the functions of emulsifying and dispersing inorganic particles, and can increase the compatibility and stability of the components of ultra-high performance concrete. Among them, the 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer is a six-carbon macromonomer, which can be combined with the anti-cracking and water-reducing functional monomer octenyl succinic acid mono-arabic ester, The tough corrosion-inhibiting functional monomer 3,4-diaminobenzoic acid methyl ester is polymerized to form a highly active side chain group. The side chain and the main chain contain many negatively charged carboxyl groups (-COO - ), sulfonic acid Group (-RSO 3 - ) and amino group (-NH 2 - ) and ester group, release the moisture wrapped between particles in the early and late stages of ultra-high performance concrete hydration, reduce the aggregation of cementitious materials, and reduce the water-binder ratio; ester The base group can further generate carboxyl group (-COO - ) through hydrolysis reaction in the later stage of hydration reaction, slowly release the water wrapped between particles, make the water evenly distributed, and improve the rigidity and toughness of ultra-high performance concrete during curing and drying. Further improve the mechanical properties of ultra-high performance concrete.

同时,减水剂复合浆液在超高性能混凝土内通过氢键、静电相互作用和酯化反应,形成三维空间网状结构,具有较高的锚固力和抗拉伸性能,可以降低超高性能混凝土硬化过程中的屈服应力,避免超高性能混凝土的回弹和收缩,有效阻止超高性能混凝土裂纹的产生。At the same time, the superplasticizer composite slurry forms a three-dimensional space network structure through hydrogen bonding, electrostatic interaction and esterification reaction in the ultra-high performance concrete, which has high anchoring force and tensile performance, and can reduce the ultra-high performance concrete. The yield stress in the hardening process avoids the rebound and shrinkage of ultra-high performance concrete, and effectively prevents the generation of cracks in ultra-high performance concrete.

此外,本发明实施例制备的减水剂复合浆液中,还加入了高温氧化处理后的氮化硼纳米片(市售产品),氮化硼纳米片是二维的纳米片状结构,具有分散性强、吸附性好的特点,可以均匀分散在超高性能混凝土中,降低超高性能混凝土毛细孔内液面干燥迁移时的负压拉应力,减少混凝土的收缩率。此外纳米层状复合材料具有阻隔环境中腐蚀介质Cl-和SO4 2-离子渗透的作用。而三羟丙基羟乙基乙二胺具有络合腐蚀产物的功能,起到固化Cl-和SO4 2-的作用,可以抑制混凝土内腐蚀离子的扩散,提高混凝土在高盐环境中的抗腐蚀能力。In addition, boron nitride nanosheets (commercially available products) after high-temperature oxidation treatment are also added to the water reducer composite slurry prepared in the embodiment of the present invention. Boron nitride nanosheets are two-dimensional nanosheet-like structures with dispersed It can be evenly dispersed in ultra-high performance concrete, reduce the negative pressure tensile stress when the liquid level in the pores of ultra-high performance concrete dries and migrates, and reduce the shrinkage of concrete. In addition, the nano-layered composite material has the function of blocking the penetration of corrosive medium Cl - and SO 4 2- ions in the environment. And trihydroxypropyl hydroxyethyl ethylenediamine has the function of complexing corrosion products, which can solidify Cl- and SO 4 2- , can inhibit the diffusion of corrosion ions in concrete, and improve the resistance of concrete in high-salt environments. Corrosion ability.

本发明实施例制备的减水剂复合浆液中各成分协同作用,达到使超高性能混凝土抗裂、增韧、耐腐蚀和力学性能提升的效果。The components in the water reducer composite slurry prepared in the embodiment of the present invention act synergistically to achieve the effects of crack resistance, toughening, corrosion resistance and mechanical performance improvement of ultra-high performance concrete.

在其中一个实施例中,步骤a中,搅拌时间为3min~5min,转速为90r/min~120r/min,聚合反应温度为30℃~45℃,聚合反应时间为2h~3h。In one embodiment, in step a, the stirring time is 3min-5min, the rotation speed is 90r/min-120r/min, the polymerization reaction temperature is 30°C-45°C, and the polymerization reaction time is 2h-3h.

在其中一个实施例中,步骤b中,搅拌时间为30min~50min,转速为90r/min~120r/min。In one embodiment, in step b, the stirring time is 30 min-50 min, and the rotation speed is 90 r/min-120 r/min.

在其中一个实施例中,所述改性复合纤维是由氮化硼纤维、聚对苯撑苯并双噁唑(PBO)纤维、芳纶纤维(芳香族聚酰胺纤维)和碳化硅纤维按体积比3~5.5:2~4.5:1~2.5:0.1~0.3共混后,经过环己胺基乙磺酸/乙醇溶液改性得到的。In one of the embodiments, the modified composite fiber is made of boron nitride fiber, poly-p-phenylene benzobisoxazole (PBO) fiber, aramid fiber (aromatic polyamide fiber) and silicon carbide fiber by volume Ratio 3~5.5:2~4.5:1~2.5:0.1~0.3 After blending, it is modified by cyclohexylaminoethanesulfonic acid/ethanol solution.

在其中一个实施例中,改性方法具体包括:将纤维混合物加入环己胺基乙磺酸/乙醇溶液中,所述纤维混合物中所述氮化硼纤维、所述聚对苯撑苯并双噁唑纤维、所述芳纶纤维和所述碳化硅纤维的体积比为3~5.5:2~4.5:1~2.5:0.1~0.3,然后向混合溶液加入乙醇胺,室温搅拌,反应完全后水洗、抽滤、干燥,向干燥后的滤饼中加入偶联剂、搅拌,得所述改性复合纤维。In one of the embodiments, the modification method specifically includes: adding a fiber mixture into a cyclohexylaminoethanesulfonic acid/ethanol solution, the boron nitride fiber, the polyparaphenylenebenzobis The volume ratio of the oxazole fiber, the aramid fiber and the silicon carbide fiber is 3-5.5:2-4.5:1-2.5:0.1-0.3, then add ethanolamine to the mixed solution, stir at room temperature, wash with water after the reaction is complete, Suction filtration, drying, adding a coupling agent to the dried filter cake and stirring to obtain the modified composite fiber.

在其中一个实施例中,所述氮化硼纤维、所述聚对苯撑苯并双噁唑纤维和所述芳纶纤维的长度为2mm~30mm,直径为0.05mm~0.5mm;所述碳化硅纤维的长度为50μm~150μm,直径为0.1μm~1μm。In one of the embodiments, the boron nitride fiber, the poly(p-phenylene benzobisoxazole fiber) and the aramid fiber have a length of 2 mm to 30 mm and a diameter of 0.05 mm to 0.5 mm; the carbonization The silicon fiber has a length of 50 μm to 150 μm and a diameter of 0.1 μm to 1 μm.

在其中一个实施例中,改性方法中各原料的质量份数分别为:所述纤维混合物20~30份,所述环己胺基乙磺酸/乙醇溶液20~30份,所述乙醇胺1~3份,所述偶联剂0.5~1.5份。In one of the embodiments, the parts by mass of each raw material in the modification method are: 20-30 parts of the fiber mixture, 20-30 parts of the cyclohexylaminoethanesulfonic acid/ethanol solution, and 10 parts of the ethanolamine ~3 parts, 0.5~1.5 parts of the coupling agent.

在其中一个实施例中,所述环己胺基乙磺酸/乙醇溶液中环己胺基乙磺酸与乙醇的体积比为5:1。In one embodiment, the volume ratio of cyclohexylaminoethanesulfonic acid to ethanol in the cyclohexylaminoethanesulfonic acid/ethanol solution is 5:1.

在其中一个实施例中,所述偶联剂为硅烷偶联剂、三硬脂酸钛酸异丙酯、二(乙酰丙酮基)钛酸二异丙酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯中的一种或两种按质量比1:1混合。In one of the embodiments, the coupling agent is a silane coupling agent, isopropyl titanate tristearate, diisopropyl di(acetylacetonate) titanate, tetraisopropyl bis(dioctyl Phosphite acyloxy) titanate, isopropyl tris (dioctyl phosphate acyl oxy) titanate, isopropyl tris (dioctyl pyrophosphate acyl oxy) titanate, isopropyl trioil One or two of acid acyloxy titanate and bis(dioctyloxypyrophosphate) ethylene titanate are mixed at a mass ratio of 1:1.

具体地,硅烷偶联剂可以为常规的硅烷偶联剂,如A-1100、KH550、KH560、KH570、KH590、YGO-1203,在此对硅烷偶联剂不做具体限定。Specifically, the silane coupling agent can be a conventional silane coupling agent, such as A-1100, KH550, KH560, KH570, KH590, YGO-1203, and the silane coupling agent is not specifically limited here.

在其中一个实施例中,改性方法中,所述室温搅拌的时间为1h~3h,所述抽滤为真空抽滤三次,所述干燥为在105℃~110℃条件下真空干燥10min~20min,加入所述偶联剂后搅拌时间为1h~3h。In one embodiment, in the modification method, the stirring time at room temperature is 1 h to 3 h, the suction filtration is vacuum filtration three times, and the drying is vacuum drying at 105°C to 110°C for 10min to 20min , the stirring time after adding the coupling agent is 1h-3h.

本发明实施例通过对纤维进行改性,环己胺基乙磺酸在乙醇的作用下成为强的质子供体,较容易的与纤维之间形成氢键,增加了纤维的韧性和强度,偶联剂与有机纤维(PBO、芳纶纤维)、无机纤维(氮化硼纤维、碳化硅纤维)之间产生羟基等大量活性基团,偶联剂改性后的纤维,表面能下降,提高了改性复合纤维在超高性能混凝土中的分散性,增加了改性复合纤维与减水剂复合浆液、胶凝材料和矿渣机制砂等混凝土其他组分的相容性。此外,改性复合纤维在超高性能混凝土内形成交错的三维网状,起到很好的加筋作用,对超高性能混凝土发生的形变具有很好的约束力,可以有效抑制裂隙的发展,使超高性能混凝土在没有钢纤维掺入的条件下,具备超高的抗压强度和抗折曲强度。In the embodiment of the present invention, by modifying the fiber, cyclohexylaminoethanesulfonic acid becomes a strong proton donor under the action of ethanol, and forms a hydrogen bond with the fiber more easily, increasing the toughness and strength of the fiber, even A large number of active groups such as hydroxyl groups are generated between the coupling agent and organic fibers (PBO, aramid fiber) and inorganic fibers (boron nitride fiber, silicon carbide fiber). The surface energy of the fiber modified by the coupling agent decreases, improving the The dispersibility of the modified composite fiber in ultra-high performance concrete increases the compatibility of the modified composite fiber with other concrete components such as superplasticizer composite slurry, cementitious material and slag machine-made sand. In addition, the modified composite fiber forms a staggered three-dimensional network in the ultra-high performance concrete, which plays a good role in reinforcement, has a good binding force on the deformation of the ultra-high performance concrete, and can effectively inhibit the development of cracks. The ultra-high-performance concrete has ultra-high compressive strength and flexural strength without the addition of steel fibers.

在其中一个实施例中,所述矿渣机制砂由钒钛转炉钢渣、铁尾矿渣、高铝矾土尾矿渣、水淬高炉矿渣和锰钢渣中的至少两种等质量混合、制砂而得,所述矿渣机制砂的平均粒径为0.070mm~4.3mm。In one embodiment, the slag machine-made sand is obtained by mixing equal masses of at least two of vanadium-titanium converter steel slag, iron tailings slag, high-alumina bauxite tailings slag, water-quenched blast furnace slag and manganese steel slag, and making sand, The average particle size of the slag machine-made sand is 0.070mm-4.3mm.

不同细度模数的矿渣机制砂合理级配,以提高骨料的支撑作用,通过优化矿粉掺合料和矿渣机制砂之间的配比,减少超高性能混凝土内微缺陷的产生,提高超高性能混凝土的力学性能。同时采用矿渣机制砂可以使固体废弃物再生和重新利用,有效节约资源,降低超高性能混凝土的成本。Reasonable grading of slag machine-made sand with different fineness modulus to improve the supporting effect of the aggregate, by optimizing the ratio between the slag admixture and slag machine-made sand, reducing the occurrence of micro-defects in ultra-high performance concrete and improving Mechanical properties of ultra-high performance concrete. At the same time, the use of slag machine-made sand can regenerate and reuse solid waste, effectively saving resources and reducing the cost of ultra-high performance concrete.

在其中一个实施例中,所述矿粉掺合料由锂辉石矿粉、高铝矾土、多孔钛磷灰石粉、莫来石粉和海浮石粉中的至少三种等质量复配而成,所述矿粉掺合料为S95级以上级别的料粉,所述矿粉掺合料的粒径为5μm~150μm。In one of the embodiments, the mineral powder admixture is composed of at least three equal masses of spodumene ore powder, high bauxite, porous titanium apatite powder, mullite powder and sea pumice powder. The mineral powder admixture is S95 or above material powder, and the particle size of the mineral powder admixture is 5 μm to 150 μm.

其中,多孔钛磷灰石粉(MP-TiHAP)可以按照常规方法合成或者购买市售产品。Among them, the porous titanium apatite powder (MP-TiHAP) can be synthesized according to a conventional method or purchased from a commercial product.

具体地,矿粉掺合料可以为S95级、S105级等级别的微粉。Specifically, the mineral powder admixture can be S95 grade, S105 grade and other grades of fine powder.

在其中一个实施例中,所述水泥为强度等级P.O 42.5以上的普通硅酸盐水泥或硅酸盐水泥,所述水泥的平均粒径为8μm~30μm。In one embodiment, the cement is ordinary Portland cement or Portland cement with a strength grade of P.O 42.5 or higher, and the average particle size of the cement is 8 μm to 30 μm.

在其中一个实施例中,所述硅灰粉的平均粒径为0.01μm~1μm,比表面积为12000m2/kg~30000m2/kg。In one embodiment, the silica fume powder has an average particle size of 0.01 μm-1 μm, and a specific surface area of 12000 m 2 /kg-30000 m 2 /kg.

在其中一个实施例中,所述石英砂的粒径为0.9mm~2.5mm。In one embodiment, the particle size of the quartz sand is 0.9mm-2.5mm.

本发明实施例超高性能混凝土中,用矿粉掺合料替代部分水泥,不同颗粒的硅灰粉、矿物掺合料颗粒互相填充支撑,形成堆积密实度较好的胶凝材料,有助于降低水化速率,更好地激发碱活性;并且小粒径的胶凝颗粒起到润滑降黏的作用,在超高性能混凝土固化干燥过程中不容易产生微隙,减少水泥水化反应的干缩现象,降低超高性能混凝土开裂的几率,提高超高性能混凝土的力学性能。In the ultra-high-performance concrete of the embodiment of the present invention, part of the cement is replaced by mineral powder admixture, and silica fume powder and mineral admixture particles of different particles are mutually filled and supported to form a cementitious material with better packing density, which helps Reduce the hydration rate and better stimulate the alkali activity; and the small-sized gel particles play the role of lubrication and viscosity reduction, and it is not easy to produce micro-voids during the curing and drying process of ultra-high performance concrete, reducing the dryness of cement hydration reaction. shrinkage phenomenon, reduce the cracking probability of ultra-high performance concrete, and improve the mechanical properties of ultra-high performance concrete.

第二方面,上述第一方面或任一实施例中具有触变性的抗裂耐蚀型超高性能混凝土的制备方法,包括以下步骤:In the second aspect, the preparation method of the anti-crack and corrosion-resistant ultra-high performance concrete with thixotropy in the above-mentioned first aspect or any one of the embodiments comprises the following steps:

S1:将600~700份水泥、80~150份硅灰粉和700~800份矿粉掺合料搅拌均匀,得到胶凝材料;S1: Stir 600-700 parts of cement, 80-150 parts of silica fume powder and 700-800 parts of mineral powder admixture evenly to obtain a cementitious material;

S2:将90~120份石英砂和700~900份矿渣机制砂加入所述胶凝材料中,搅拌均匀,得到第一混合料;S2: Add 90-120 parts of quartz sand and 700-900 parts of slag machine-made sand into the cementitious material, and stir evenly to obtain the first mixture;

S3:将15-40份减水剂复合浆液加入170~280份水中,搅拌均匀,得到混合浆液;先将所述混合浆液重量的二分之一加入所述第一混合料中,搅拌,得第二混合料,待所述第二混合料出现流动度后,再加入剩余二分之一的所述混合浆液,继续搅拌,得第三混合料;S3: Add 15-40 parts of superplasticizer composite slurry to 170-280 parts of water, stir evenly to obtain a mixed slurry; first add half of the weight of the mixed slurry to the first mixture, and stir to obtain For the second mixture, after the fluidity of the second mixture appears, add the remaining 1/2 of the mixed slurry and continue stirring to obtain the third mixture;

S4:向所述第三混合料中加入100-250份改性复合纤维,搅拌,然后加入3~10份复合触变剂,搅拌,即得到所述具有触变性的抗裂耐蚀型超高性能混凝土。S4: Add 100-250 parts of modified composite fiber to the third mixture, stir, then add 3-10 parts of composite thixotropic agent, and stir to obtain the thixotropic anti-crack and corrosion-resistant ultra-high performance concrete.

在其中一个实施例中,步骤S1和步骤S2中,搅拌时间均为3min~5min,搅拌速度均为30r/min~40r/min。In one embodiment, in both step S1 and step S2, the stirring time is 3 min-5 min, and the stirring speed is 30 r/min-40 r/min.

在其中一个实施例中,步骤S3具体过程为:将15-40份减水剂复合浆液加入170~280份水中,以100r/min~120r/min的搅拌速度快速搅拌1min~2.5min,搅拌均匀,得到混合浆液;先将所述混合浆液重量的二分之一以50r/min~60r/min的搅拌速度搅拌3min~5min,得第二混合料,待所述第二混合料出现流动度后,再加入剩余二分之一的所述混合浆液,以30r/min~40r/min的速度搅拌3min~5min,得第三混合料。In one of the embodiments, the specific process of step S3 is: add 15-40 parts of superplasticizer composite slurry to 170-280 parts of water, stir rapidly at a stirring speed of 100r/min-120r/min for 1min-2.5min, and stir evenly , to obtain a mixed slurry; first stir 1/2 of the weight of the mixed slurry at a stirring speed of 50r/min to 60r/min for 3min to 5min to obtain a second mixture, and after the fluidity of the second mixture appears , and then add the remaining 1/2 of the mixed slurry, and stir at a speed of 30r/min-40r/min for 3min-5min to obtain a third mixture.

在其中一个实施例中,步骤S4中,向所述第三混合料中加入所述改性复合纤维时,搅拌时间为3min~5min,搅拌速度为30r/min~40r/min;加入所述复合触变剂时,搅拌时间为3min~5min,搅拌速度为50r/min~60r/min。In one embodiment, in step S4, when adding the modified composite fiber to the third mixture, the stirring time is 3min-5min, and the stirring speed is 30r/min-40r/min; For thixotropic agent, the stirring time is 3min~5min, and the stirring speed is 50r/min~60r/min.

本发明提供的超高性能混凝土的制备方法,具有操作简单、设备要求低、施工性能好以及易大规模推广应用的优势。The preparation method of the ultra-high-performance concrete provided by the invention has the advantages of simple operation, low equipment requirements, good construction performance and easy large-scale popularization and application.

上述具有触变性的抗裂耐蚀型超高性能混凝土,可以制得不同流动性的混凝土砂浆;利用喷射法喷射混凝土砂浆进行施工;或者直接浇筑施工;或者以泵送方式浇筑施工;还包括以人工或机械方式进行抹压成型施工;或以震动加压的方式进行成型和施工。应用方式多样,实用性强。The above-mentioned thixotropic anti-crack and corrosion-resistant ultra-high performance concrete can be made into concrete mortars with different fluidities; the concrete mortar is sprayed by spraying method for construction; or direct pouring construction; or pouring construction by pumping; also includes Manually or mechanically carry out plastering and forming construction; or carry out forming and construction by means of vibration and pressure. Various application methods and strong practicability.

具体实施方式Detailed ways

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

此外,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在发明的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。在本发明的描述中,“若干”的含义是至少一个,例如一个,两个等,除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the invention, "plurality" means at least two, such as two, three, etc., unless specifically defined otherwise. In the description of the present invention, "several" means at least one, such as one, two, etc., unless otherwise specifically defined.

本发明中的词语“优选地”、“更优选地”等是指,在某些情况下可提供某些有益效果的本发明实施方案。然而,在相同的情况下或其他情况下,其他实施方案也可能是优选的。此外,对一个或多个优选实施方案的表述并不暗示其他实施方案不可用,也并非旨在将其他实施方案排除在本发明的范围之外。The words "preferably", "more preferably" etc. in the present invention refer to embodiments of the invention which may afford certain advantages, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

当本文中公开一个数值范围时,上述范围视为连续,且包括该范围的最小值及最大值,以及这种最小值与最大值之间的每一个值。进一步地,当范围是指整数时,包括该范围的最小值与最大值之间的每一个整数。此外,当提供多个范围描述特征或特性时,可以合并该范围。换言之,除非另有指明,否则本文中所公开之所有范围应理解为包括其中所归入的任何及所有的子范围。When a numerical range is disclosed herein, such range is considered continuous and includes the minimum and maximum values of that range and every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum of the range is included. Furthermore, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.

除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terminology used herein in the description of the present invention is only for the purpose of describing specific embodiments, and is not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

以下为具体的实施例,如无特别说明,实施例中采用的原料均为市售产品。The following are specific examples. Unless otherwise specified, the raw materials used in the examples are commercially available products.

实施例1Example 1

一种具有触变性的抗裂耐蚀型超高性能混凝土,包括以下重量份数的组分:水泥650份,硅灰粉110份,矿粉掺合料750份,石英砂110份,矿渣机制砂780份,改性复合纤维180份,复合触变剂6份,减水剂复合浆液25份,水240份。A thixotropic anti-crack and corrosion-resistant ultra-high performance concrete, including the following components in parts by weight: 650 parts of cement, 110 parts of silica fume powder, 750 parts of mineral powder admixture, 110 parts of quartz sand, and slag mechanism 780 parts of sand, 180 parts of modified composite fiber, 6 parts of composite thixotropic agent, 25 parts of composite slurry of water reducer, and 240 parts of water.

其中,水泥为强度等级为P.O 42.5普通硅酸盐水泥,平均粒径为30μm。Among them, the cement is ordinary Portland cement with a strength grade of P.O 42.5 and an average particle size of 30 μm.

其中,硅灰粉的平均粒径为0.3μm,比表面积为20000m2/kg。Among them, the average particle size of the silica fume powder is 0.3 μm, and the specific surface area is 20000 m 2 /kg.

矿粉掺合料为高铝矾土、多孔钛磷灰石粉、莫来石粉按质量比1:1:1复配而成,矿粉掺合料为S95级以上料粉,粒径为60μm左右。The mineral powder admixture is made of high bauxite, porous titanium apatite powder, and mullite powder in a mass ratio of 1:1:1. The mineral powder admixture is S95 grade or above, and the particle size is 60 μm about.

矿渣机制砂由钒钛转炉钢渣、铁尾矿渣和锰钢渣按照质量比1:1:1组成,平均粒径为1.2mm左右。The slag machine-made sand is composed of vanadium-titanium converter steel slag, iron tailings slag and manganese steel slag in a mass ratio of 1:1:1, with an average particle size of about 1.2mm.

复合触变剂的制备方法:The preparation method of compound thixotropic agent:

首先,取无机触变剂硅镁土、层状蒙托土和伊利石粉以质量比1:1:1混合,合计90份,在高速混合机中于110℃搅拌15min烘干,使其含水量低于0.1%,将温度降至30℃后,缓缓加入0.4份铝酸三异丙酯,然后以195r/min的转速,高速搅拌20min;再加入0.3份椰油二乙醇酰胺6501,继续搅拌10min,搅拌完成后将40份褐藻胶加入搅拌机中,以150r/min转速搅拌3min,即得到复合触变剂。First, take inorganic thixotropic attapulgite, layered montmorillonite and illite powder and mix them at a mass ratio of 1:1:1, totaling 90 parts, and stir and dry them in a high-speed mixer at 110°C for 15 minutes to make the water content Lower than 0.1%, after lowering the temperature to 30°C, slowly add 0.4 parts of triisopropyl aluminate, then stir at a high speed of 195r/min for 20 minutes; then add 0.3 parts of coconut oil diethanolamide 6501, and continue stirring After 10 minutes, after the stirring is completed, add 40 parts of alginate into the mixer, and stir for 3 minutes at a speed of 150 r/min to obtain a composite thixotropic agent.

减水剂复合浆液的制备方法:Preparation method of superplasticizer composite slurry:

步骤a:将130份4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体、15份甲基丁烯磺酸钠、35份2-羟基-2-甲基二丁烯酸、40份防裂减水型功能单体辛烯基琥珀酸单阿拉伯胶酯和30份增韧缓蚀型功能单体3,4-二氨基苯甲酸甲酯,加入90份去离子水中,以110r|/min的转速搅拌4min后,将13份质量分数为1.0%的过硫酸胺水溶液引发剂滴加到上述反应器中,控制引发剂的滴加时间为1.2h,于40℃聚合反应2.3h后,即得到聚羧酸减水剂。Step a: 130 parts of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer, 15 parts of sodium methylbutenesulfonate, 35 parts of 2-hydroxy-2-methyldibutene Acid, 40 parts of anti-cracking and water-reducing functional monomer octenyl succinic mono-arabic acid ester and 30 parts of toughening and corrosion-inhibiting functional monomer 3,4-diaminobenzoic acid methyl ester, add 90 parts of deionized water, After stirring at a speed of 110r|/min for 4min, add 13 parts of 1.0% ammonium persulfate aqueous solution initiator dropwise into the above reactor, control the dripping time of the initiator to 1.2h, and polymerize at 40°C After 2.3 hours, the polycarboxylate superplasticizer was obtained.

步骤b:向上述溶液中加入3.5份高温氧化处理后的氮化硼纳米片和6份三羟丙基羟乙基乙二胺,于35℃继续以100r|/min的转速搅拌45min,即得到减水剂复合浆液。Step b: Add 3.5 parts of boron nitride nanosheets after high temperature oxidation treatment and 6 parts of trihydroxypropyl hydroxyethyl ethylenediamine to the above solution, and continue to stir at 35°C at a speed of 100r|/min for 45min to obtain Water reducer composite slurry.

改性复合纤维由氮化硼纤维、聚对苯撑苯并双噁唑(PBO)纤维、芳纶纤维和碳化硅纤维按体积比4:3:2:0.2共混后,经过环己胺基乙磺酸/乙醇溶液改性得到的。The modified composite fiber is blended with boron nitride fiber, poly-p-phenylene benzobisoxazole (PBO) fiber, aramid fiber and silicon carbide fiber at a volume ratio of 4:3:2:0.2, and then passed through cyclohexylamine group Modified with ethanesulfonic acid/ethanol solution.

改性方法具体包括:Modification methods specifically include:

将氮化硼纤维、聚对苯撑苯并双噁唑纤维、芳纶纤维和碳化硅纤维按体积比为4:3:2:0.2的配比称量出共计26份,加入到26份环己胺基乙磺酸/乙醇溶液(环己胺基乙磺酸与乙醇的体积比为5:1)中,然后加入2份乙醇胺溶液,室温下搅拌2h,然后水洗,并用旋转真空过滤机抽滤三次,在108℃条件下真空干燥脱水15min后,加入1.2份双(二辛氧基焦磷酸酯基)乙撑钛酸酯偶联剂,搅拌2h后,得改性复合纤维。Weigh out a total of 26 parts of boron nitride fiber, poly-p-phenylene benzobisoxazole fiber, aramid fiber and silicon carbide fiber in a volume ratio of 4:3:2:0.2, and add them to 26 parts of ring Hexylaminoethanesulfonic acid/ethanol solution (the volume ratio of cyclohexylaminoethanesulfonic acid to ethanol is 5:1), then add 2 parts of ethanolamine solution, stir at room temperature for 2h, then wash with water, and use a rotary vacuum filter to pump Filter three times, vacuum dry and dehydrate at 108°C for 15 minutes, add 1.2 parts of bis(dioctyloxypyrophosphate)ethylene titanate coupling agent, and stir for 2 hours to obtain modified composite fibers.

其中氮化硼纤维、聚对苯撑苯并双噁唑纤维和芳纶纤维的长度为15mm,直径为0.25mm;碳化硅纤维的长度为75μm,直径为0.55μm。Among them, the length of boron nitride fiber, poly-p-phenylene benzobisoxazole fiber and aramid fiber is 15 mm, and the diameter is 0.25 mm; the length of silicon carbide fiber is 75 μm, and the diameter is 0.55 μm.

一种具有触变性抗裂耐蚀型超高性能混凝土的制备方法:A preparation method of thixotropic anti-crack and anti-corrosion ultra-high performance concrete:

S1:将650份水泥、110份硅灰粉放入混合机中,再加入750份上述矿粉掺合料,以38r/min的速度搅拌3min,混合均匀,得到胶凝材料;S1: Put 650 parts of cement and 110 parts of silica fume powder into the mixer, then add 750 parts of the above-mentioned mineral powder admixture, stir for 3 minutes at a speed of 38 r/min, and mix evenly to obtain a cementitious material;

S2:将110份石英砂、780份矿渣机制砂加入上述胶凝材料中,以38r/min的速度搅拌3.5min,混合均匀,得到第一混合料;S2: Add 110 parts of quartz sand and 780 parts of slag machine-made sand into the above-mentioned cementitious material, stir at a speed of 38 r/min for 3.5 minutes, and mix evenly to obtain the first mixture;

S3:将25份减水剂复合浆液加入240份水中,以110r/min的搅拌速度快速搅拌2.5min,搅拌均匀,得到混合浆液;先将其中的二分之一的混合浆液加入第一混合料中,以60r/min的搅拌速度搅拌3min,得第二混合料,再加入剩余二分之一的混合浆液,以30r/min的速度搅拌4min,得第三混合料;S3: Add 25 parts of superplasticizer composite slurry to 240 parts of water, stir rapidly at a stirring speed of 110r/min for 2.5min, and stir evenly to obtain a mixed slurry; first add half of the mixed slurry to the first mixture In, stir 3min with the stirring speed of 60r/min, obtain the second mixture, then add remaining 1/2 mixed slurry, stir 4min with the speed of 30r/min, obtain the 3rd mixture;

S4:在40r/min的转速搅拌的条件下,向第三混合料中加入180份改性复合纤维,搅拌3.5min,之后加入6份复合触变剂,再以50r/min的搅拌速度快速搅拌3min,即得到新拌具有触变性的抗裂耐蚀型超高性能混凝土。S4: Under the condition of stirring at a rotating speed of 40r/min, add 180 parts of modified composite fibers to the third mixture, stir for 3.5min, then add 6 parts of composite thixotropic agent, and then stir rapidly at a stirring speed of 50r/min In 3 minutes, freshly mixed anti-crack and corrosion-resistant ultra-high performance concrete with thixotropy is obtained.

实施例2Example 2

一种具有触变性的抗裂耐蚀型超高性能混凝土,包括以下重量份数的组分:水泥620份,硅灰粉100份,矿粉掺合料730份,石英砂90份,矿渣机制砂720份,改性复合纤维130份,复合触变剂5份,减水剂复合浆液20份,水200份。A thixotropic anti-crack and corrosion-resistant ultra-high performance concrete, including the following components in parts by weight: 620 parts of cement, 100 parts of silica fume powder, 730 parts of mineral powder admixture, 90 parts of quartz sand, and slag mechanism 720 parts of sand, 130 parts of modified composite fiber, 5 parts of composite thixotropic agent, 20 parts of composite slurry of water reducer, and 200 parts of water.

其中,水泥为普通硅酸盐水泥。Among them, the cement is ordinary Portland cement.

其中,硅灰粉的平均粒径为0.5μm,比表面积为25000m2/kg。Among them, the average particle size of the silica fume powder is 0.5 μm, and the specific surface area is 25000 m 2 /kg.

矿粉掺合料为锂辉石矿粉、多孔钛磷灰石粉、海浮石粉按质量比1:1:1复配而成,矿粉掺合料为S95级以上料粉,粒径为45μm。The mineral powder admixture is made of spodumene mineral powder, porous titanium apatite powder and sea pumice powder in a mass ratio of 1:1:1. The mineral powder admixture is S95 grade or above powder, and the particle size is 45 μm.

矿渣机制砂由铁尾矿渣、水淬高炉矿渣和高铝矾土尾矿渣按照质量比1:1:1组成,平均粒径为0.1mm。The slag machine-made sand is composed of iron tailings, water-quenched blast furnace slag and high-alumina bauxite tailings in a mass ratio of 1:1:1, with an average particle size of 0.1mm.

复合触变剂的制备方法:The preparation method of compound thixotropic agent:

首先,取无机触变剂坡缕缟石粉、伊利石粉和纳米勃姆石粉以质量比1:1:1混合,合计85份,在高速混合机中于108℃搅拌12min烘干,使其含水量低于0.1%,将温度降至28℃后,缓缓加入0.3份铝酸三异丙酯,然后以190r/min的转速,高速搅拌18min;再加入0.2份椰油二乙醇酰胺6501,继续搅拌8min,搅拌完成后将35份卡拉胶加入搅拌机中,以120r/min转速搅拌4min,即得到复合触变剂。First, take the inorganic thixotropic agent palygorskite powder, illite powder and nano-boehmite powder and mix them in a mass ratio of 1:1:1, totaling 85 parts, stir and dry at 108°C for 12 minutes in a high-speed mixer to make the water content Lower than 0.1%, after lowering the temperature to 28°C, slowly add 0.3 parts of triisopropyl aluminate, then stir at a high speed of 190r/min for 18 minutes; then add 0.2 parts of coconut oil diethanolamide 6501, and continue stirring 8 minutes, after the stirring is completed, add 35 parts of carrageenan into the mixer, and stir at a speed of 120r/min for 4 minutes to obtain a composite thixotropic agent.

减水剂复合浆液的制备方法:Preparation method of superplasticizer composite slurry:

步骤a:将120份4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体、13份甲基丁烯磺酸钠、25份2-羟基-2-甲基二丁烯酸、35份防裂减水型功能单体辛烯基琥珀酸单阿拉伯胶酯和25份增韧缓蚀型功能单体3,4-二氨基苯甲酸甲酯,加入70份去离子水中,以100r|/min的转速搅拌4min后,将8份质量分数为1.0%的过硫酸胺水溶液引发剂滴加到上述反应器中,控制引发剂的滴加时间为1.2h,于35℃聚合反应2.5h后,即得到聚羧酸减水剂。Step a: 120 parts of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer, 13 parts of sodium methylbutene sulfonate, 25 parts of 2-hydroxy-2-methyldibutene Acid, 35 parts of anti-cracking and water-reducing functional monomer octenyl succinic mono-arabic acid ester and 25 parts of toughening and corrosion-inhibiting functional monomer 3,4-diaminobenzoic acid methyl ester, add 70 parts of deionized water, After stirring at a speed of 100r|/min for 4min, add 8 parts of 1.0% ammonium persulfate aqueous solution initiator dropwise into the above reactor, control the dripping time of the initiator to 1.2h, and polymerize at 35°C After 2.5 hours, the polycarboxylate water reducer was obtained.

步骤b:向上述溶液中加入2份高温氧化处理后的氮化硼纳米片和7份三羟丙基羟乙基乙二胺,于35℃继续以100r|/min的转速搅拌40min,即得到减水剂复合浆液。Step b: Add 2 parts of boron nitride nanosheets after high temperature oxidation treatment and 7 parts of trihydroxypropyl hydroxyethyl ethylenediamine to the above solution, and continue to stir at 35 °C for 40 min at a speed of 100 r|/min to obtain Water reducer composite slurry.

改性复合纤维由氮化硼纤维、聚对苯撑苯并双噁唑(PBO)纤维、芳纶纤维和碳化硅纤维按体积比3.5:2.5:1.5:0.15共混后,经过环己胺基乙磺酸/乙醇溶液改性得到的。The modified composite fiber is blended with boron nitride fiber, poly-p-phenylene benzobisoxazole (PBO) fiber, aramid fiber and silicon carbide fiber at a volume ratio of 3.5:2.5:1.5:0.15, and then passed through cyclohexylamine group Modified with ethanesulfonic acid/ethanol solution.

改性方法具体包括:Modification methods specifically include:

将氮化硼纤维、聚对苯撑苯并双噁唑纤维、芳纶纤维和碳化硅纤维按体积比为3.5:2.5:1.5:0.15的配比称量出共计25份,加入到25份环己胺基乙磺酸/乙醇溶液(环己胺基乙磺酸与乙醇的体积比为5:1)中,然后加入1.5份乙醇胺溶液,室温下搅拌1.5h,然后水洗,并用旋转真空过滤机抽滤三次,在108℃条件下真空干燥脱水15min后,加入0.8份硅烷偶联剂A-1100,搅拌1.5h后,得改性复合纤维。Weigh boron nitride fiber, poly-p-phenylene benzobisoxazole fiber, aramid fiber and silicon carbide fiber according to the volume ratio of 3.5:2.5:1.5:0.15 and weigh out a total of 25 parts, and add them to 25 parts of ring Hexylaminoethanesulfonic acid/ethanol solution (the volume ratio of cyclohexylaminoethanesulfonic acid to ethanol is 5:1), then add 1.5 parts of ethanolamine solution, stir at room temperature for 1.5h, then wash with water, and use a rotary vacuum filter Suction filtration three times, after vacuum drying and dehydration at 108°C for 15 minutes, add 0.8 parts of silane coupling agent A-1100, and stir for 1.5 hours to obtain modified composite fibers.

其中氮化硼纤维、聚对苯撑苯并双噁唑纤维和芳纶纤维的长度为5mm,直径为0.1mm;碳化硅纤维的长度为75μm,直径为0.3μm。Among them, the length of boron nitride fiber, polyparaphenylene benzobisoxazole fiber and aramid fiber is 5 mm, and the diameter is 0.1 mm; the length of silicon carbide fiber is 75 μm, and the diameter is 0.3 μm.

一种具有触变性抗裂耐蚀型超高性能混凝土的制备方法:A preparation method of thixotropic anti-crack and anti-corrosion ultra-high performance concrete:

S1:将620份水泥、100份硅灰粉放入混合机中,再加入730份上述矿粉掺合料,以35r/min的速度搅拌4min,混合均匀,得到胶凝材料;S1: Put 620 parts of cement and 100 parts of silica fume powder into the mixer, then add 730 parts of the above-mentioned mineral powder admixture, stir for 4 minutes at a speed of 35 r/min, and mix evenly to obtain a cementitious material;

S2:将90份石英砂、720份矿渣机制砂加入上述胶凝材料中,以35r/min的速度搅拌4min,混合均匀,得到第一混合料;S2: Add 90 parts of quartz sand and 720 parts of slag machine-made sand into the above cementitious material, stir at a speed of 35 r/min for 4 minutes, and mix evenly to obtain the first mixture;

S3:将20份减水剂复合浆液加入200份水中,以105r/min的搅拌速度快速搅拌2min,搅拌均匀,得到混合浆液;先将其中的二分之一的混合浆液加入第一混合料中,以55r/min的搅拌速度搅拌4min,得第二混合料,再加入剩余二分之一的混合浆液,以35r/min的速度搅拌4min,得第三混合料;S3: Add 20 parts of superplasticizer composite slurry to 200 parts of water, stir rapidly at a stirring speed of 105r/min for 2 minutes, and stir evenly to obtain a mixed slurry; first add half of the mixed slurry to the first mixture , stirred at a stirring speed of 55r/min for 4min to obtain the second mixture, then added remaining 1/2 of the mixed slurry, stirred at a speed of 35r/min for 4min to obtain the third mixture;

S4:在35r/min的转速搅拌的条件下,向第三混合料中加入130份改性复合纤维,搅拌3min,之后加入5份复合触变剂,再以55r/min的搅拌速度快速搅拌3.5min,即得到新拌具有触变性的抗裂耐蚀型超高性能混凝土。S4: Under the condition of stirring at a rotating speed of 35r/min, add 130 parts of modified composite fibers to the third mixture, stir for 3 minutes, then add 5 parts of composite thixotropic agent, and then stir rapidly at a stirring speed of 55r/min for 3.5 min, that is, the newly mixed anti-crack and corrosion-resistant ultra-high performance concrete with thixotropy.

实施例3Example 3

一种具有触变性的抗裂耐蚀型超高性能混凝土,包括以下重量份数的组分:水泥600份,硅灰粉80份,矿粉掺合料700份,石英砂100份,矿渣机制砂700份,改性复合纤维100份,复合触变剂3份,减水剂复合浆液15份,水170份。A thixotropic anti-crack and corrosion-resistant ultra-high performance concrete, including the following components in parts by weight: 600 parts of cement, 80 parts of silica fume powder, 700 parts of mineral powder admixture, 100 parts of quartz sand, and slag mechanism 700 parts of sand, 100 parts of modified composite fiber, 3 parts of composite thixotropic agent, 15 parts of composite slurry of water reducer, and 170 parts of water.

其中,水泥为强度等级为P.O 42.5普通硅酸盐水泥。Among them, the cement is ordinary Portland cement with a strength grade of P.O 42.5.

其中,硅灰粉的平均粒径为0.01μm,比表面积为30000m2/kg。Among them, the average particle size of the silica fume powder is 0.01 μm, and the specific surface area is 30000 m 2 /kg.

矿粉掺合料为锂辉石矿粉、多孔钛磷灰石粉、莫来石粉按质量比1:1:1复配而成,矿粉掺合料为S95级以上料粉,粒径为5μm。The mineral powder admixture is made of spodumene mineral powder, porous titanium apatite powder, and mullite powder in a mass ratio of 1:1:1. The mineral powder admixture is S95 grade or above, and the particle size is 5 μm.

矿渣机制砂由钒钛转炉钢渣、铁尾矿渣和高铝矾土尾矿渣按照质量比1:1:1组成,平均粒径为0.07mm。The slag machine-made sand is composed of vanadium-titanium converter steel slag, iron tailings slag and high-alumina bauxite tailings slag in a mass ratio of 1:1:1, with an average particle size of 0.07mm.

复合触变剂的制备方法:The preparation method of compound thixotropic agent:

首先,取无机触变剂菱镁矿微粉、层状蒙托土和坡缕缟石粉以质量比1:1:1混合,合计80份,在高速混合机中于105℃搅拌10min烘干,使其含水量低于0.1%,将温度降至25℃后,缓缓加入0.1份铝酸三异丙酯,然后以180r/min的转速,高速搅拌15min;再加入0.1份椰油二乙醇酰胺6501,继续搅拌5min,搅拌完成后将30份油酸酰胺加入搅拌机中,以100r/min转速搅拌3min,即得到复合触变剂。First, take inorganic thixotropic agent magnesite micropowder, layered montmorillonite and palygorskite powder and mix them in a mass ratio of 1:1:1, totaling 80 parts, and stir and dry them at 105°C for 10 minutes in a high-speed mixer to make Its water content is lower than 0.1%. After lowering the temperature to 25°C, slowly add 0.1 part of triisopropyl aluminate, then stir at a high speed of 180r/min for 15 minutes; then add 0.1 part of coconut oil diethanolamide 6501 , continue to stir for 5 minutes, after the stirring is completed, add 30 parts of oleic acid amide into the mixer, and stir at a speed of 100 r/min for 3 minutes to obtain a composite thixotropic agent.

减水剂复合浆液的制备方法:Preparation method of superplasticizer composite slurry:

步骤a:将100份4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体、10份甲基丁烯磺酸钠、20份2-羟基-2-甲基二丁烯酸、30份防裂减水型功能单体辛烯基琥珀酸单阿拉伯胶酯和20份增韧缓蚀型功能单体3,4-二氨基苯甲酸甲酯,加入60份去离子水中,以90r|/min的转速搅拌3min后,将5份质量分数为1.0%的过硫酸胺水溶液引发剂滴加到上述反应器中,控制引发剂的滴加时间为1h,于30℃聚合反应2h后,即得到聚羧酸减水剂。Step a: 100 parts of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer, 10 parts of sodium methylbutene sulfonate, 20 parts of 2-hydroxy-2-methyldibutene Acid, 30 parts of anti-cracking and water-reducing functional monomer octenyl succinic acid monogum arabic ester and 20 parts of toughening and corrosion-inhibiting functional monomer 3,4-diaminobenzoic acid methyl ester, add 60 parts of deionized water, After stirring at a speed of 90r|/min for 3min, add 5 parts of 1.0% ammonium persulfate aqueous solution initiator dropwise into the above reactor, control the dripping time of the initiator to 1h, and polymerize at 30°C for 2h After that, the polycarboxylate water reducer is obtained.

步骤b:向上述溶液中加入1份高温氧化处理后的氮化硼纳米片和5份三羟丙基羟乙基乙二胺,于30℃继续以90r|/min的转速搅拌30min,即得到减水剂复合浆液。Step b: Add 1 part of boron nitride nanosheets after high temperature oxidation treatment and 5 parts of trihydroxypropyl hydroxyethyl ethylenediamine to the above solution, and continue to stir at 30°C at a speed of 90r|/min for 30min to obtain Water reducer composite slurry.

改性复合纤维由氮化硼纤维、聚对苯撑苯并双噁唑(PBO)纤维、芳纶纤维和碳化硅纤维按体积比3:2:1:0.1共混后,经过环己胺基乙磺酸/乙醇溶液改性得到的。The modified composite fiber is blended by boron nitride fiber, poly-p-phenylene benzobisoxazole (PBO) fiber, aramid fiber and silicon carbide fiber at a volume ratio of 3:2:1:0.1, and then passed through cyclohexylamine group Modified with ethanesulfonic acid/ethanol solution.

改性方法具体包括:Modification methods specifically include:

将氮化硼纤维、聚对苯撑苯并双噁唑纤维、芳纶纤维和碳化硅纤维按体积比为3:2:1:0.1的配比称量出共计20份,加入到20份环己胺基乙磺酸/乙醇溶液(环己胺基乙磺酸与乙醇的体积比为5:1)中,然后加入1份乙醇胺溶液,室温下搅拌1h,然后水洗,并用旋转真空过滤机抽滤三次,在105℃条件下真空干燥脱水10min后,加入0.5份二(乙酰丙酮基)钛酸二异丙酯偶联剂,搅拌1h后,得改性复合纤维。Weigh out 20 parts of boron nitride fiber, poly-p-phenylene benzobisoxazole fiber, aramid fiber and silicon carbide fiber according to volume ratio of 3:2:1:0.1, add to 20 parts ring Add hexylaminoethanesulfonic acid/ethanol solution (the volume ratio of cyclohexylaminoethanesulfonic acid to ethanol is 5:1), then add 1 part of ethanolamine solution, stir at room temperature for 1h, then wash with water, and use a rotary vacuum filter to pump Filter three times, vacuum dry and dehydrate at 105°C for 10 minutes, add 0.5 parts of diisopropyl bis(acetylacetonate) titanate coupling agent, and stir for 1 hour to obtain modified composite fibers.

其中氮化硼纤维、聚对苯撑苯并双噁唑纤维和芳纶纤维的长度为5mm,直径为0.05mm;碳化硅纤维的长度为50μm,直径为0.1μm。The boron nitride fiber, poly-p-phenylene benzobisoxazole fiber and aramid fiber have a length of 5 mm and a diameter of 0.05 mm; the silicon carbide fiber has a length of 50 μm and a diameter of 0.1 μm.

一种具有触变性抗裂耐蚀型超高性能混凝土的制备方法:A preparation method of thixotropic anti-crack and anti-corrosion ultra-high performance concrete:

S1:将600份水泥、80份硅灰粉放入混合机中,再加入700份上述矿粉掺合料,以30r/min的速度搅拌3min,混合均匀,得到胶凝材料;S1: Put 600 parts of cement and 80 parts of silica fume powder into the mixer, then add 700 parts of the above-mentioned mineral powder admixture, stir for 3 minutes at a speed of 30 r/min, and mix evenly to obtain a cementitious material;

S2:将100份石英砂、700份矿渣机制砂加入上述胶凝材料中,以30r/min的速度搅拌3min,混合均匀,得到第一混合料;S2: Add 100 parts of quartz sand and 700 parts of slag machine-made sand into the above cementitious material, stir at a speed of 30 r/min for 3 minutes, and mix evenly to obtain the first mixture;

S3:将15份减水剂复合浆液加入170份水中,以100r/min的搅拌速度快速搅拌1min,搅拌均匀,得到混合浆液;先将其中的二分之一的混合浆液加入第一混合料中,以50r/min的搅拌速度搅拌3min,得第二混合料,再加入剩余二分之一的混合浆液,以30r/min的速度搅拌3min,得第三混合料;S3: Add 15 parts of superplasticizer composite slurry to 170 parts of water, stir rapidly at a stirring speed of 100r/min for 1min, and stir evenly to obtain a mixed slurry; first add half of the mixed slurry to the first mixture , stirred at a stirring speed of 50r/min for 3min to obtain the second mixture, then added remaining 1/2 of the mixed slurry, and stirred for 3min at a speed of 30r/min to obtain the third mixture;

S4:在30r/min的转速搅拌的条件下,向第三混合料中加入100份改性复合纤维,搅拌3min分钟,之后加入3份复合触变剂,再以50r/min的搅拌速度快速搅拌3min,即得到新拌具有触变性的抗裂耐蚀型超高性能混凝土。S4: Under the condition of stirring at a rotating speed of 30r/min, add 100 parts of modified composite fibers to the third mixture, stir for 3 minutes, then add 3 parts of composite thixotropic agent, and then stir rapidly at a stirring speed of 50r/min In 3 minutes, freshly mixed anti-crack and corrosion-resistant ultra-high performance concrete with thixotropy is obtained.

实施例4Example 4

一种具有触变性的抗裂耐蚀型超高性能混凝土,包括以下重量份数的组分:水泥700份,硅灰粉150份,矿粉掺合料800份,石英砂120份,矿渣机制砂900份,改性复合纤维250份,复合触变剂10份,减水剂复合浆液40份,水280份。A thixotropic anti-crack and corrosion-resistant ultra-high performance concrete, including the following components in parts by weight: 700 parts of cement, 150 parts of silica fume powder, 800 parts of mineral powder admixture, 120 parts of quartz sand, and slag mechanism 900 parts of sand, 250 parts of modified composite fiber, 10 parts of composite thixotropic agent, 40 parts of composite slurry of water reducer, and 280 parts of water.

其中,水泥为强度等级为P.I 42.5R的硅酸盐水泥,平均粒径为30μm。Among them, the cement is Portland cement with a strength grade of P.I 42.5R and an average particle size of 30 μm.

其中,硅灰粉的平均粒径为1μm,比表面积为12000m2/kg。Among them, the silica fume powder has an average particle diameter of 1 μm and a specific surface area of 12000 m 2 /kg.

矿粉掺合料为锂辉石矿粉、高铝矾土、莫来石粉按质量比1:1:1复配而成,矿粉掺合料为S95级以上料粉,粒径为150μm。The mineral powder admixture is made of spodumene mineral powder, high bauxite, and mullite powder in a mass ratio of 1:1:1. The mineral powder admixture is S95 grade or above, with a particle size of 150 μm.

矿渣机制砂由铁尾矿渣、高铝矾土尾矿渣和锰钢渣按照质量比1:1:1组成,平均粒径为4.3mm。The slag machine-made sand is composed of iron tailings, high alumina bauxite tailings and manganese steel slag in a mass ratio of 1:1:1, with an average particle size of 4.3mm.

复合触变剂的制备方法:The preparation method of compound thixotropic agent:

首先,取无机触变剂菱镁矿微粉、层状蒙托土和坡缕缟石粉以质量比1:1:1混合,合计100份,在高速混合机中于115℃搅拌20min烘干,使其含水量低于0.1%,将温度降至35℃后,缓缓加入0.8份铝酸三异丙酯,然后以220r/min的转速,高速搅拌18min;再加入0.5份椰油二乙醇酰胺6501,继续搅拌8min,搅拌完成后将50份微粉化聚酰胺蜡加入搅拌机中,以200r/min转速搅拌5min,即得到复合触变剂。First, take the inorganic thixotropic agent magnesite micropowder, layered montmorillonite and palygorskite powder and mix them in a mass ratio of 1:1:1, totaling 100 parts, and stir and dry them at 115°C for 20 minutes in a high-speed mixer to make Its water content is lower than 0.1%. After lowering the temperature to 35°C, slowly add 0.8 parts of triisopropyl aluminate, then stir at a high speed of 220r/min for 18 minutes; then add 0.5 parts of coconut oil diethanolamide 6501 , and continue to stir for 8 minutes. After the stirring is completed, add 50 parts of micronized polyamide wax into the mixer, and stir for 5 minutes at a speed of 200 r/min to obtain a composite thixotropic agent.

减水剂复合浆液的制备方法:Preparation method of superplasticizer composite slurry:

步骤a:将150份4,4-二甲基戊烯醇聚氧乙烯聚氧丙烯醚大单体、20份甲基丁烯磺酸钠、40份2-羟基-2-甲基二丁烯酸、50份防裂减水型功能单体辛烯基琥珀酸单阿拉伯胶酯和40份增韧缓蚀型功能单体3,4-二氨基苯甲酸甲酯,加入100份去离子水中,以120r|/min的转速搅拌5min后,将15份质量分数为1.0%的过硫酸胺水溶液引发剂滴加到上述反应器中,控制引发剂的滴加时间为1.5h,于45℃聚合反应3h后,即得到聚羧酸减水剂。Step a: 150 parts of 4,4-dimethylpentenol polyoxyethylene polyoxypropylene ether macromonomer, 20 parts of sodium methylbutene sulfonate, 40 parts of 2-hydroxy-2-methyldibutene Acid, 50 parts of anti-cracking and water-reducing functional monomer octenyl succinic mono-arabic acid ester and 40 parts of toughening and corrosion-inhibiting functional monomer 3,4-diaminobenzoic acid methyl ester, add 100 parts of deionized water, After stirring at a speed of 120r|/min for 5min, add 15 parts of ammonium persulfate aqueous solution initiator with a mass fraction of 1.0% dropwise into the above reactor, control the dripping time of the initiator to 1.5h, and polymerize at 45°C After 3 hours, the polycarboxylate water reducer was obtained.

步骤b:向上述溶液中加入5份高温氧化处理后的氮化硼纳米片和10份三羟丙基羟乙基乙二胺,于45℃继续以120r|/min的转速搅拌50min,即得到减水剂复合浆液。Step b: Add 5 parts of boron nitride nanosheets after high-temperature oxidation treatment and 10 parts of trihydroxypropyl hydroxyethyl ethylenediamine to the above solution, and continue to stir at 45°C at a speed of 120r/min for 50min to obtain Water reducer composite slurry.

改性复合纤维由氮化硼纤维、聚对苯撑苯并双噁唑(PBO)纤维、芳纶纤维和碳化硅纤维按体积比5.5:4.5:2.5:0.3共混后,经过环己胺基乙磺酸/乙醇溶液改性得到的。The modified composite fiber is blended with boron nitride fiber, poly-p-phenylene benzobisoxazole (PBO) fiber, aramid fiber and silicon carbide fiber at a volume ratio of 5.5:4.5:2.5:0.3, and then passed through cyclohexylamine group Modified with ethanesulfonic acid/ethanol solution.

改性方法具体包括:Modification methods specifically include:

将氮化硼纤维、聚对苯撑苯并双噁唑纤维、芳纶纤维和碳化硅纤维按体积比为5.5:4.5:2.5:0.3的配比称量出共计30份,加入到30份环己胺基乙磺酸/乙醇溶液(环己胺基乙磺酸与乙醇的体积比为5:1)中,然后加入3份乙醇胺溶液,室温下搅拌3h,然后水洗,并用旋转真空过滤机抽滤三次,在110℃条件下真空干燥脱水20min后,加入1.5份质量比1:1的KH570和三硬脂酸钛酸异丙酯混合偶联剂,搅拌3h后,得改性复合纤维。Weigh boron nitride fiber, poly-p-phenylene benzobisoxazole fiber, aramid fiber and silicon carbide fiber in a volume ratio of 5.5:4.5:2.5:0.3, and add a total of 30 parts to 30 parts of ring Hexylaminoethanesulfonic acid/ethanol solution (the volume ratio of cyclohexylaminoethanesulfonic acid to ethanol is 5:1), then add 3 parts of ethanolamine solution, stir at room temperature for 3h, then wash with water, and use a rotary vacuum filter to pump Filter three times, vacuum dry and dehydrate at 110°C for 20 minutes, add 1.5 parts of KH570 and isopropyl tristearate titanate mixed coupling agent with a mass ratio of 1:1, and stir for 3 hours to obtain modified composite fibers.

其中氮化硼纤维、聚对苯撑苯并双噁唑纤维和芳纶纤维的长度为30mm,直径为0.5mm;碳化硅纤维的长度为150μm,直径为1μm。The length of the boron nitride fiber, the poly-p-phenylene benzobisoxazole fiber and the aramid fiber is 30 mm, and the diameter is 0.5 mm; the length of the silicon carbide fiber is 150 μm, and the diameter is 1 μm.

一种具有触变性抗裂耐蚀型超高性能混凝土的制备方法:A preparation method of thixotropic anti-crack and anti-corrosion ultra-high performance concrete:

S1:将700份水泥、150份硅灰粉放入混合机中,再加入800份上述矿粉掺合料,以40r/min的速度搅拌5min,混合均匀,得到胶凝材料;S1: Put 700 parts of cement and 150 parts of silica fume powder into the mixer, then add 800 parts of the above-mentioned mineral powder admixture, stir at a speed of 40r/min for 5min, mix evenly, and obtain a cementitious material;

S2:将120份石英砂、900份矿渣机制砂加入上述胶凝材料中,以40r/min的速度搅拌5min,混合均匀,得到第一混合料;S2: Add 120 parts of quartz sand and 900 parts of slag machine-made sand into the above-mentioned cementitious material, stir at a speed of 40 r/min for 5 minutes, and mix evenly to obtain the first mixture;

S3:将40份减水剂复合浆液加入280份水中,以120r/min的搅拌速度快速搅拌1min,搅拌均匀,得到混合浆液;先将其中的二分之一的混合浆液加入第一混合料中,以60r/min的搅拌速度搅拌5min,得第二混合料,再加入剩余二分之一的混合浆液,以40r/min的速度搅拌5min,得第三混合料;S3: Add 40 parts of superplasticizer composite slurry to 280 parts of water, stir rapidly at a stirring speed of 120r/min for 1min, and stir evenly to obtain a mixed slurry; first add half of the mixed slurry to the first mixture , stirred at a stirring speed of 60r/min for 5min to obtain the second mixture, then added remaining 1/2 of the mixed slurry, and stirred at a speed of 40r/min for 5min to obtain the third mixture;

S4:在40r/min的转速搅拌的条件下,向第三混合料中加入250份改性复合纤维,搅拌5min分钟,之后加入10份复合触变剂,再以60r/min的搅拌速度快速搅拌5min,即得到新拌具有触变性的抗裂耐蚀型超高性能混凝土。S4: Under the condition of stirring at a rotating speed of 40r/min, add 250 parts of modified composite fibers to the third mixture, stir for 5 minutes, then add 10 parts of composite thixotropic agent, and then stir rapidly at a stirring speed of 60r/min After 5 minutes, freshly mixed anti-crack and corrosion-resistant ultra-high performance concrete with thixotropy is obtained.

对比例1Comparative example 1

用等量磨细石英粉替代实施例1中的矿粉掺合料,用等量普通高性能减水剂(常规减水剂)替代实施例1中的减水剂复合浆液,其他组分和制备条件均与实施例1相同。Replace the mineral powder admixture in Example 1 with an equal amount of finely ground quartz powder, replace the composite slurry of the water reducer in Example 1 with an equal amount of common high-performance water reducer (conventional water reducer), other components and The preparation conditions were all the same as in Example 1.

对比例2Comparative example 2

用等量普通天然河沙替代实施例1中的矿渣机制砂,其他组分和制备条件均与实施例1相同。The same amount of ordinary natural river sand was used to replace the slag machine-made sand in Example 1, and the other components and preparation conditions were the same as in Example 1.

对比例3Comparative example 3

用等量等长度和直径的普通钢纤维替代实施例1中的改性复合纤维,其他组分和制备条件均与实施例1相同。The modified composite fibers in Example 1 were replaced with ordinary steel fibers of equal length and diameter, and the other components and preparation conditions were the same as in Example 1.

对比例4Comparative example 4

用等量商用CAS71205-22型工业级硅酸镁铝触变剂(山东国华化工新材料有限公司)替代实施例1中的复合触变剂,其他组分和制备条件均与实施例1相同。Replace the composite thixotropic agent in Example 1 with an equivalent commercial CAS71205-22 type industrial grade magnesium aluminum silicate thixotropic agent (Shandong Guohua Chemical New Material Co., Ltd.), and other components and preparation conditions are all the same as in Example 1 .

对比例5Comparative example 5

用等量商用CP701X型高性能聚羧酸减水剂(南京新义合成科技有限公司)替代实施例1中的减水剂复合浆液,其他组分和制备条件均与实施例1相同。The same amount of commercial CP701X high-performance polycarboxylate water reducer (Nanjing Xinyi Synthetic Technology Co., Ltd.) was used to replace the water reducer composite slurry in Example 1, and other components and preparation conditions were the same as in Example 1.

试验例Test case

将实施例1~4和对比例1~5所得的新拌超高性能混凝土装料并浇筑成型,浇筑过程中让超高性能混凝土自动填充模具;将所得超高性能混凝土连同模具一起置于养护室中,养护28小时后拆模,置于常温水中标准养护28天,即得超高性能混凝土试件。养护室的湿度为90%以上,温度为16℃~25℃;然后参照《混凝土物理力学性能试验方法标准》(GB/T50081-2019),测量超高性能混凝土的抗压强度、抗折强度。泵送阻力通过摩擦计测试结果获得,以单位距离泵送压力损失表征;耐硫酸盐、耐酸腐蚀性能按GB/T749-2008规定的方法,测定其28d和180d耐硫酸盐侵蚀系数;28d干缩率按JC/T 2381-2016中规定的试验方法测定;28d自由膨胀率按JC/T 313-2009中规定的试验方法测定,并记录混凝土试件是否有裂缝。具体结果如下表1所示。The freshly mixed ultra-high-performance concrete obtained in Examples 1-4 and Comparative Examples 1-5 is charged and poured into shape, and the ultra-high-performance concrete is automatically filled in the mold during the pouring process; the obtained ultra-high-performance concrete is placed together with the mold for curing After 28 hours of curing in the chamber, the formwork was removed and placed in normal temperature water for 28 days of standard curing to obtain ultra-high performance concrete specimens. The humidity in the curing room is above 90%, and the temperature is 16°C to 25°C; then, the compressive strength and flexural strength of ultra-high performance concrete are measured by referring to the "Standards for Test Methods of Physical and Mechanical Properties of Concrete" (GB/T50081-2019). The pumping resistance is obtained through the test results of the tribometer, and is characterized by the pumping pressure loss per unit distance; the sulfate resistance and acid corrosion resistance are determined according to the method specified in GB/T749-2008, and the 28d and 180d sulfate corrosion resistance coefficients are measured; 28d drying shrinkage The rate is measured according to the test method specified in JC/T 2381-2016; the 28d free expansion rate is measured according to the test method specified in JC/T 313-2009, and records whether there are cracks in the concrete specimen. The specific results are shown in Table 1 below.

表1实施例和对比例超高性能混凝土的性能指标The performance index of table 1 embodiment and comparative example ultra-high performance concrete

Figure BDA0003956848930000201
Figure BDA0003956848930000201

由实施例1-4和对比例1的性能指标数据可以看出,通过硅灰粉和矿粉掺合料尺寸和颗粒的优选,有助于降低颗粒的团聚,增大颗粒表面的水膜层厚度,提升矿物掺合料的碱激发活性,有效替代水泥作为胶凝材料,降低水胶比,提高混凝土后期强度,并提高对外加剂的吸附效率,降低开裂现象和泵送阻力。From the performance index data of Examples 1-4 and Comparative Example 1, it can be seen that through the optimization of silica fume powder and mineral powder admixture size and particles, it helps to reduce the agglomeration of particles and increase the water film layer on the particle surface Thickness, improve the alkali-excited activity of mineral admixtures, effectively replace cement as a cementitious material, reduce the water-binder ratio, improve the strength of concrete in the later stage, improve the adsorption efficiency of admixtures, and reduce cracking and pumping resistance.

由实施例1-4和对比例2的性能指标数据可以看出,矿渣机制砂的选用和复配对混凝土的强度、骨架支撑和应力传导起到积极作用,提升了混凝土力学性能,并能降低混凝土成本。From the performance index data of Examples 1-4 and Comparative Example 2, it can be seen that the selection and compounding of slag machine-made sand play a positive role in the strength, skeleton support and stress conduction of concrete, improve the mechanical properties of concrete, and reduce the cost.

从实施例1-4以及对比例3的性能指标数据可以看出,改性高复合纤维在混凝土中起到复配协同作用,形成纵横相互搭接的三维网状结构,起到很好的抗冲击和抗弯曲性能,能大大提高混凝土的抗折强度和抗裂性能。From the performance index data of Examples 1-4 and Comparative Example 3, it can be seen that the modified high-composite fiber plays a compound and synergistic role in concrete, forming a three-dimensional network structure overlapping vertically and horizontally, and playing a good role in anti-corrosion. Impact and bending resistance can greatly improve the flexural strength and crack resistance of concrete.

由实施例1-4和对比例4的性能指标数据可以看出,复合触变剂的加入显著降低了泵送阻力,降低了混凝土的干燥收缩率和粘度,提升了水中自由膨胀率,有助于降低施工难度,减少后期干缩开裂的风险。From the performance index data of Examples 1-4 and Comparative Example 4, it can be seen that the addition of the composite thixotropic agent significantly reduces the pumping resistance, reduces the drying shrinkage and viscosity of concrete, improves the free expansion rate in water, and helps To reduce the difficulty of construction and reduce the risk of shrinkage and cracking in the later stage.

由实施例1-4和对比例5的性能指标数据可见,抗裂耐蚀型减水剂复合浆液加入后,提升了无机粉体的分散度和流动性,释放颗粒包裹的水分,显著降低了水胶比,提升了混凝土的力学强度、抗裂性能和耐腐蚀性能。没有添加抗裂耐蚀型减水剂复合浆液的对比样本出现了开裂现象,抗折强度大大降低。From the performance index data of Examples 1-4 and Comparative Example 5, it can be seen that after adding the anti-cracking and anti-corrosion water reducer composite slurry, the dispersion and fluidity of the inorganic powder are improved, and the moisture wrapped in the particles is released, which significantly reduces the The water-binder ratio improves the mechanical strength, crack resistance and corrosion resistance of concrete. The comparative sample without adding the anti-cracking and anti-corrosion superplasticizer composite slurry cracked and the flexural strength was greatly reduced.

由表1可见,本发明实施例的具有触变性的抗裂耐蚀型超高性能混凝土,具有较高的抗折和抗压强度,混凝土28d抗折强度可达44.5MPa、抗压强度可达199.5MPa;制成的超高性能混凝土28d水中自由膨胀率可达0.16%,干燥收缩率只有-0.020%左右;其28d和180d耐硫酸盐侵蚀系数分别高达1.18和1.12,说明本发明的一种具有触变性的抗裂耐蚀型超高性能混凝土具有良好的耐硫酸盐、耐酸腐蚀性能。As can be seen from Table 1, the thixotropic anti-crack and corrosion-resistant ultra-high performance concrete of the embodiment of the present invention has higher flexural and compressive strengths, and the concrete 28d flexural strength can reach 44.5MPa, and the compressive strength can reach 199.5MPa; the free expansion rate of the made ultra-high performance concrete in 28d water can reach 0.16%, and the drying shrinkage rate is only about -0.020%; its 28d and 180d sulfate erosion resistance coefficients are respectively as high as 1.18 and 1.12, illustrating a kind of method of the present invention Thixotropic anti-crack and anti-corrosion ultra-high performance concrete has good resistance to sulfate and acid corrosion.

综上所述,本发明实施例的超高性能混凝土通过矿粉掺合料、矿渣机制砂、改性复合纤维、复合触变剂和自制的抗裂耐蚀型减水剂复合浆液协同作用,调整各组分比例,使制备的超高性能混凝土不仅具有较高的力学强度、良好的触变性、减缩性、同时具有优异的抗裂性能和耐蚀性,以及较低的泵送阻力和良好的工作性能。此外,本发明中采用矿粉掺合料替代部分水泥,采用矿渣机制砂替代石英砂、河沙,具有典型的低水泥含量特点,显著减少了资源消耗,实现了固废资源的再利用,节约了成本,具有良好的经济效益和社会效益。In summary, the ultra-high-performance concrete of the embodiment of the present invention is synergistically effected by mineral powder admixture, slag machine-made sand, modified composite fiber, composite thixotropic agent and self-made anti-crack and corrosion-resistant water reducer composite slurry, Adjust the proportion of each component so that the prepared ultra-high performance concrete not only has high mechanical strength, good thixotropy, shrinkage reduction, but also has excellent crack resistance and corrosion resistance, as well as low pumping resistance and good work performance. In addition, in the present invention, mineral powder admixture is used to replace part of cement, and slag machine-made sand is used to replace quartz sand and river sand, which has typical characteristics of low cement content, significantly reduces resource consumption, realizes the reuse of solid waste resources, saves It reduces the cost and has good economic and social benefits.

以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement or improvement made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1. The crack-resistant corrosion-resistant ultrahigh-performance concrete with thixotropy is characterized in that: the paint comprises the following components in parts by weight: 600-700 parts of cement, 80-150 parts of silica fume powder, 700-800 parts of mineral powder admixture, 90-120 parts of quartz sand, 700-900 parts of slag making machine sand, 100-250 parts of modified composite fiber, 3-10 parts of composite thixotropic agent, 15-40 parts of water reducing agent composite slurry and 170-280 parts of water;
the preparation method of the composite thixotropic agent comprises the following steps:
stirring and drying a mixture of at least two inorganic thixotropic agents at 105-115 ℃, cooling to 25-35 ℃, adding an aluminate coupling agent, stirring, adding coconut diethanolamide, continuing stirring, finally adding an organic thixotropic agent, and uniformly stirring to obtain the composite thixotropic agent;
the preparation method of the water reducing agent composite slurry comprises the following steps:
step a: adding 4, 4-dimethyl pentenol polyoxyethylene polyoxypropylene ether macromonomer, methyl butylene sodium sulfonate, 2-hydroxy-2-methyl dibutenoic acid, octenyl succinic acid mono-Arabic ester and 3, 4-diaminobenzoic acid methyl ester into deionized water, stirring uniformly, dripping an initiator for 1-1.5 h, and carrying out polymerization reaction to obtain a polycarboxylic acid water reducing agent;
step b: b, adding the boron nitride nanosheet and the trihydroxypropyl hydroxyethyl ethylenediamine which are subjected to high-temperature oxidation treatment at 220 ℃ into the polycarboxylic acid water reducer obtained in the step a, and continuously stirring at 30-45 ℃ to obtain the water reducer composite slurry.
2. The anti-cracking and corrosion-resistant type ultrahigh-performance concrete with thixotropy according to claim 1, characterized in that: the mixture of the inorganic thixotropic agent is a mixture of at least two of magnesite micropowder, attapulgite, layered montmorillonite, palygorskite powder, illite powder and nano boehmite powder in equal mass; and/or
The organic thixotropic agent is any one of oleamide, carrageenan, algin, glycol alginate and micronized polyamide wax; and/or
In the preparation method of the composite thixotropic agent, the mass parts of the raw materials are respectively as follows: 80 to 100 parts of mixture of inorganic thixotropic agent, 0.1 to 0.8 part of aluminate coupling agent, 0.1 to 0.5 part of coconut diethanolamide and 30 to 50 parts of organic thixotropic agent;
in the preparation method of the composite thixotropic agent, the aluminate coupling agent is triisopropyl aluminate; and/or
In the preparation method of the composite thixotropic agent, the stirring time of the mixture of the inorganic thixotropic agent is 10-20 min, and the water content of the dried mixture of the inorganic thixotropic agent is lower than 0.1%; and/or
In the preparation method of the composite thixotropic agent, the aluminate coupling agent is added and then stirred for 15min to 20min at the rotating speed of 180r/min to 220r/min;
in the preparation method of the composite thixotropic agent, the coconut diethanolamide is added and then stirred for 5-10 min; the stirring time is 3min to 5min after the organic thixotropic agent is added, and the rotating speed is 100r/min to 200r/min.
3. The anti-cracking and corrosion-resistant type ultrahigh-performance concrete with thixotropy according to claim 1, characterized in that: in the preparation method of the water reducer composite slurry, the raw materials in parts by weight are as follows: 100-150 parts of 4, 4-dimethyl pentenol polyoxyethylene polyoxypropylene ether macromonomer, 10-20 parts of methyl butene sodium sulfonate, 20-40 parts of 2-hydroxy-2-methyl dibutenoic acid, 30-50 parts of octenyl succinic acid mono-acacia, 20-40 parts of methyl 3, 4-diaminobenzoate, 60-100 parts of deionized water, 5-15 parts of initiator, 1-5 parts of boron nitride nanosheet and 5-10 parts of trihydroxypropyl hydroxyethyl ethylenediamine; and/or
In the step a, the initiator is 1.0 mass percent of aqueous solution of ammonium persulfate; and/or
In the step a, the stirring time is 3 min-5 min, the rotating speed is 90 r/min-120 r/min, the polymerization reaction temperature is 30 ℃ to 45 ℃, and the polymerization reaction time is 2 h-3 h; and/or
In the step b, the stirring time is 30min to 50min, and the rotating speed is 90r/min to 120r/min.
4. The thixotropic crack-resistant and corrosion-resistant ultra-high performance concrete according to claim 1, wherein: the modified composite fiber is obtained by blending boron nitride fiber, poly (p-phenylene-benzobisoxazole) fiber, aramid fiber and silicon carbide fiber according to the volume ratio of 3-5.5; and/or
The modification method specifically comprises the following steps: adding a fiber mixture into a cyclohexylamine ethanesulfonic acid/ethanol solution, wherein the volume ratio of the boron nitride fiber to the poly (p-phenylene benzobisoxazole) fiber to the aramid fiber to the silicon carbide fiber in the fiber mixture is 3-5.5; and/or
The boron nitride fiber, the poly-p-phenylene benzobisoxazole fiber and the aramid fiber have the length of 2-30 mm and the diameter of 0.05-0.5 mm; the length of the silicon carbide fiber is 50-150 mu m, and the diameter of the silicon carbide fiber is 0.1-1 mu m; and/or
The modification method comprises the following raw materials in parts by weight: 20-30 parts of the fiber mixture, 20-30 parts of the cyclohexylaminoethanesulfonic acid/ethanol solution, 1-3 parts of ethanolamine and 0.5-1.5 parts of a coupling agent; and/or
The volume ratio of the cyclohexylaminoethanesulfonic acid to the ethanol in the cyclohexylaminoethanesulfonic acid/ethanol solution is 5; and/or
The coupling agent is one or two of silane coupling agent, isopropyl tristearate, diisopropyl di (acetylacetonate) titanate, tetraisopropyl di (dioctyl phosphite acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, isopropyl trioleate acyloxy titanate and bis (dioctyl pyrophosphate) ethylene titanate which are mixed according to the mass ratio of 1; and/or
The stirring time at room temperature is 1-3 h, the vacuum filtration is three times, the drying is vacuum drying at 105-110 ℃ for 10-20 min, and the stirring time is 1-3 h after the coupling agent is added.
5. The thixotropic crack-resistant and corrosion-resistant ultra-high performance concrete according to claim 1, wherein: the mineral powder admixture is formed by compounding at least three of spodumene mineral powder, high-alumina, porous titanium apatite powder, mullite powder and pumice powder in equal mass, is powder with the grade of S95, and has the particle size of 5-150 microns.
6. The thixotropic crack-resistant and corrosion-resistant ultra-high performance concrete according to claim 1, wherein: the sand manufactured by the slag-making machine is obtained by mixing and sand-manufacturing at least two of vanadium-titanium converter steel slag, iron tailing slag, high-alumina bauxite tailing slag, water-quenched blast furnace slag and manganese steel slag in equal mass, and the average grain diameter of the sand manufactured by the slag-making machine is 0.070 mm-4.3 mm.
7. The thixotropic crack-resistant and corrosion-resistant ultra-high performance concrete according to claim 1, wherein: the cement is ordinary portland cement or portland cement with strength grade of more than P.O 42.5, and the average grain diameter of the cement is 8-30 μm.
8. The thixotropic crack-resistant and corrosion-resistant ultra-high performance concrete according to claim 1, wherein: the average grain diameter of the silica fume powder is 0.01-1 mu m, and the specific surface area is 12000m 2 /kg~30000m 2 Per kg; and/or
The particle size of the quartz sand is 0.9 mm-2.5 mm.
9. The method for preparing the crack-resistant and corrosion-resistant ultra-high performance concrete with thixotropy according to any one of claims 1 to 8, wherein: the method comprises the following steps:
s1: uniformly stirring 600-700 parts of cement, 80-150 parts of silica fume and 700-800 parts of mineral powder admixture to obtain a cementing material;
s2: adding 90-120 parts of quartz sand and 700-900 parts of slag machine-made sand into the cementing material, and uniformly stirring to obtain a first mixture;
s3: adding 15-40 parts of water reducer composite slurry into 170-280 parts of water, and uniformly stirring to obtain mixed slurry; adding one half of the mixed slurry into the first mixture, stirring to obtain a second mixture, adding the remaining one half of the mixed slurry after the second mixture has fluidity, and continuously stirring to obtain a third mixture;
s4: and adding 100-250 parts of modified composite fibers into the third mixture, stirring, then adding 3-10 parts of composite thixotropic agent, and stirring to obtain the thixotropic anti-cracking corrosion-resistant ultra-high performance concrete.
10. The method for producing according to claim 9, characterized in that: in the step S1 and the step S2, the stirring time is 3min to 5min, and the stirring speed is 30r/min to 40r/min; and/or
The specific process of the step S3 is as follows: adding 15-40 parts of water reducer composite slurry into 170-280 parts of water, quickly stirring at a stirring speed of 100-120 r/min for 1-2.5 min, and uniformly stirring to obtain mixed slurry; firstly, stirring one half of the mixed slurry by weight at a stirring speed of 50 r/min-60 r/min for 3 min-5 min to obtain a second mixed material, adding the remaining one half of the mixed slurry after the second mixed material has fluidity, and stirring at a speed of 30 r/min-40 r/min for 3 min-5 min to obtain a third mixed material; and/or
In the step S4, when the modified composite fiber is added into the third mixture, the stirring time is 3-5 min, and the stirring speed is 30-40 r/min; when the composite thixotropic agent is added, the stirring time is 3min to 5min, and the stirring speed is 50r/min to 60r/min.
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