固废协同与低碳再造:地聚物再生混凝土研究与展望

石宵爽 ,  王清远

工程科学与技术 ›› 2026, Vol. 58 ›› Issue (5) : 230 -251.

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工程科学与技术 ›› 2026, Vol. 58 ›› Issue (5) : 230 -251. DOI: 10.12454/j.jsuese.202600465
四川大学建校130周年特刊约稿

固废协同与低碳再造:地聚物再生混凝土研究与展望

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Solid Waste Synergistic and Low-carbon Recycling: Research Progress and Outlook of Geopolymer Recycled Aggregate Concrete

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摘要

面向中国“双碳”目标和“无废城市建设”的双重战略需求,建筑垃圾与工业固废的大规模堆存已成为制约城镇化绿色转型的核心问题。地聚物再生混凝土(geopolymer recycled aggregate concrete,GRAC)以固废基胶凝材料替代硅酸盐水泥、以再生骨料替代天然骨料,实现了“固废处置‒建材制备‒碳减排”三重协同,是当前低碳建筑材料研究的前沿热点。本文系统梳理了近年来GRAC研究的核心进展,涵盖三大主线:1)固废协同胶凝理论与多维界面科学,包括Si/Al比调控机理及三重界面过渡区的识别与强化策略;2)性能调控体系,涵盖响应面法和机器学习驱动的配合比智能设计、单一与混杂纤维增韧机制;3)低碳先进技术,包括地聚物基体碳化行为的差异化规律、再生骨料加速碳化改性技术以及基于生命周期评价(LCA)的多目标评价体系量化研究。综述发现,GRAC相较传统再生混凝土(recycled aggregate concrete,RAC)具有更优的界面致密性和更低的全球变暖潜势(GWP)(可降低50%~63%),但再生骨料引入的多尺度孔隙缺陷、碱激发体系对CO2的高敏感性,以及机器学习数据库偏小等问题是制约其工程应用的技术瓶颈。最后,本文提出了未来亟须突破的六大研究方向,以推动GRAC向规模化工程化迈进。

Abstract

Objective The rapid urbanization of China generates more than 3.5 billion tons of construction waste annually, along with enormous quantities of industrial solid waste, including fly ash, slag, and red mud, with cumulative stockpiles exceeding 20 billion tons, severely constraining green development. Simultaneously, the cement industry contributes approximately 8% of global anthropogenic CO2 emissions. Geopolymer recycled aggregate concrete (GRAC), which replaces ordinary Portland cement (OPC) with alkali‑activated solid‑waste precursors and natural aggregates with recycled concrete aggregates (RCA), provides a threefold solution involving waste disposal, low‑carbon building material production, and CO2 mitigation. This review systematically synthesizes recent advances in GRAC, focusing on three interconnected themes: cementitious chemistry and interfacial science, performance optimization, and low‑carbon technologies, to identify scientific bottlenecks and guide future engineering implementation. Progress 1) Si/Al regulation and gel chemistry. The Si/Al molar ratio was established as the most critical parameter governing geopolymerization kinetics, gel nanostructure, and mechanical strength. Optimal Si/Al ratios generally ranged from 1.5 to 2.5, although the exact value varied with precursor reactivity, activator type, and admixtures. Low‑calcium systems produced N‒A‒S‒H gels, whereas high‑calcium slag‑based systems formed C‒(A)‒S‒H gels. The interactions among the Si/Al ratio, Ca content, and precursor activity determined the dominant gel type and final performance. 2) Triple interfacial transition zones (ITZs). GRAC exhibited a unique three‑phase ITZ structure (old aggregate‒old mortar, old aggregate‒new geopolymer mortar, old mortar‒new geopolymer mortar), which was more complex than the single ITZ in conventional RCA concrete. Unlike OPC systems with wide, porous ITZs, the geopolymer binder provided pronounced pore filling and densification at the interfaces because of alkaline pore‑solution migration into the porous old mortar and in‑situ formation of supplementary gels. Advanced characterization techniques (BSE‑EDS, CLAHE‑based segmentation, X‑ray CT, SEM‑DIC) enabled quantitative identification of ITZs. Among the strengthening strategies, surface coating with slag or silica fume combined with alkali activation improved compressive strength by more than 60%, whereas carbonation pretreatment of RCA, which was effective for conventional RAC, showed limited or negative effects on GRAC because carbonate ions induced efflorescence and disrupted the aluminosilicate network. 3) Fiber reinforcement. Single fibers, particularly steel fibers (SF) at 1.0%‒1.5% (volume fraction), significantly enhanced toughness, ductility, crack resistance, and post‑peak residual strength, compensating for RCA defects, including high porosity, microcracks, and weak bonding. Other fibers (basalt, PVA, PE, and carbon nanotubes) provided specific benefits, such as thermal stability or sulfate resistance. Hybrid fiber systems (steel-PVA, basalt-CNT) produced synergistic multiscale bridging and outperformed single‑fiber systems in terms of energy absorption and durability, although compatibility between hydrophobic and hydrophilic fibers required careful control. 4) Machine learning (ML) for mix design. Ensemble boosting algorithms, particularly XGBoost, consistently outperformed other models (BPNN, SVR, random forest) in compressive strength prediction because of their robustness in handling high‑dimensional nonlinear interactions. SHAP (SHapley Additive exPlanations) analysis revealed that, unlike conventional geopolymer concrete, in which curing temperature dominated, the most influential features for GRAC were testing age, natural fine aggregate content, RCA replacement ratio, and slag content, which highlighted the distinctive role of RCA. However, ML studies were constrained by small, heterogeneous databases; CTGAN (Conditional Tabular Generative Adversarial Networks) was explored as a data‑augmentation approach. An open, standardized, multiscale GRAC database was urgently needed to facilitate the transition from strength prediction to performance‑directed design. 5) Carbonation behavior and CO2 mineralization. The carbonation response of GRAC differed fundamentally from that of OPC. In low‑calcium systems, carbonation consumed alkaline cations (Na+, K+) to form soluble carbonates (Na2CO3), while the N‒A‒S‒H skeleton remained relatively stable, although Na⁺ leaching eventually caused pore coarsening and strength loss. In high‑calcium slag systems, carbonation induced the decalcification of C‒(A)‒S‒H with simultaneous CaCO3 precipitation, which produced short‑term pore refinement and temporary strength gain, followed by long‑term degradation. The presence of RCA, with its attached old mortar, pre‑existing cracks, and higher porosity, accelerated CO2 diffusion and resulted in carbonation depths approximately 2.2 times those of OPC concrete of a comparable grade. Accelerated carbonation of RCA effectively densified the pore structure, reduced water absorption, and improved crushing resistance through CaCO3 deposition but required strict control of humidity (50%‒70%), CO2 concentration (20%‒50%), temperature (20‒30 °C), and duration to prevent efflorescence. Various carbonation routes (high‑purity CO2, flue gas, gas‑solid, wet, semi‑wet, pressurized) exhibited distinct trade‑offs among reaction rate, carbonation degree, and engineering feasibility. 6) Life cycle assessment (LCA). GRAC reduced global warming potential (GWP) by 50%‒63% compared to OPC, primarily because of avoided clinker calcination and reduced virgin aggregate extraction. However, the production of alkaline activators (NaOH, Na2SiO3) introduced higher burdens in marine ecotoxicity, human toxicity, and freshwater ecotoxicity, which represented a "carbon‑toxicity" trade‑off that required activator reduction or the development of lower‑impact alternatives. Transport distance, regional energy mixes, and allocation methods (cut‑off, economic, mass) substantially influenced LCA outcomes, which emphasized the need for standardized methodological frameworks. Multi‑criteria decision‑making (MCDM) approaches that integrated strength, durability, and environmental metrics emerged as promising tools for holistic GRAC optimization. Conclusions and Prospects This review confirmed that GRAC possesses superior interfacial density and a significantly lower GWP than conventional RAC; however, several bottlenecks hinder its large‑scale application: 1) multi‑solid‑waste interaction requires precise regulation and standardization through rapid characterization‒reactivity prediction‒mix adjustment closed-loop systems; 2) long‑term durability prediction under coupled environmental actions (freeze‒thaw, wet‒dry, chloride, and carbonation) requires in‑situ X‑CT and nanoindentation to model ITZ evolution; 3) the integration of ML with materials genomics requires open, multiscale, standardized databases that bridge macrostructural and microstructural features; 4) hybrid fiber systems beyond binary blends, including natural plant fibers (jute and sisal) and basalt fibers, warrant systematic investigation of interfacial compatibility and long‑term performance; 5) accelerated carbonation technology requires industrial-scale development to address batch uniformity and flue gas adaptability, along with unified carbon accounting for carbon trading; and 6) structural‑component‑level studies (beams, columns, slabs, and joints) are essential for establishing design codes and standards. GRAC represents a paradigm‑shifting material that integrates waste recycling, low‑carbon manufacturing, and intelligent design, providing a viable pathway toward sustainable infrastructure. This review provides a critical and forward‑looking synthesis that can facilitate fundamental research and engineering adoption in the global pursuit of carbon neutrality.

Graphical abstract

关键词

地聚物再生混凝土 / 界面过渡区 / 碱激发 / 纤维增强 / 机器学习 / 生命周期评价 / CO2矿化

Key words

geopolymer recycled aggregate concrete / interface transition zone / alkali activation / fiber reinforcement / machine learning / life cycle assessment / CO2 mineralization

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石宵爽,王清远. 固废协同与低碳再造:地聚物再生混凝土研究与展望[J]. 工程科学与技术, 2026, 58(5): 230-251 DOI:10.12454/j.jsuese.202600465

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全球气候变暖已成为人类发展面临的最大非传统安全挑战。中国作为世界最大的碳排放国家之一,已向世界郑重宣示“2030年前碳达峰、2060年前碳中和”的“双碳”目标,各行各业面临巨大挑战的同时也迎来了实现绿色发展的最大机遇。党的二十大报告提出深入推进“无废城市”建设、践行新发展理念。新《固废法》(2020年修订的《中华人民共和国固体废弃物污染防治法》)着重强调了工业固废资源化利用;《建材行业碳达峰实施方案》指出需加快提升固废利用水平,减量使用高碳建材产品,加快发展新型低碳胶凝材料。水泥的“两高(高能耗、高排放)”属性已经迫使传统水泥基胶凝材料领域掀起了技术创新与改革的高潮,并成为当今学术研究的热点。
混凝土作为世界上用量最大的工程材料,全球每年消耗量约40亿t,其生产过程产生的CO2排放占全球人为碳排放总量的约8%[1]。与此同时,中国每年产生的建筑垃圾超过35亿t,累计堆存量已突破200亿t,占用大量土地并引发严重环境污染[2]。粉煤灰、矿渣等工业固废年排放量同样超过10亿t量级,综合利用率虽逐步提升,但仍有相当比例未能实现高值化利用[3]。
地聚物(geopolymer)是一类以硅铝质固废为前驱体、以碱性激发剂促进聚合反应所形成的无机聚合物胶凝材料,其合成过程中CO2排放仅为普通硅酸盐水泥的20%~40%[4],且具有高早强、耐高温、抗腐蚀等突出优点,被认为是最具工程应用前景的新型低碳胶凝材料之一。将再生骨料(recycled concrete aggregate,RCA)引入地聚物混凝土体系构建地聚物再生混凝土(geopolymer recycled aggregate concrete,GRAC),可实现建筑固废的闭环利用,进一步降低材料全生命周期碳足迹,是当前绿色建材研究最具代表性的前沿方向之一。
然而,GRAC并非简单的材料组合,其内部蕴含的科学问题具有高度复杂性。再生骨料本身的多孔性和残余旧砂浆的存在,使GRAC形成了旧骨料‒旧砂浆界面(ITZ1)、旧骨料‒新砂浆界面(ITZ2)和旧砂浆‒新砂浆界面(ITZ3)的三重界面体系。界面结构对材料整体性能具有决定性作用。地聚物基体独特的碱性反应环境与碳化机制,既可对界面区形成凝胶填充强化,也可能在外界CO2侵入时引发泛碱劣化,使其呈现出与普通水泥混凝土截然不同的耐久性演变规律。此外,GRAC体系中多元固废、再生骨料比例、碱激发剂类型等变量的耦合效应,大幅增加了配合比设计与性能预测的难度。
近十年来,国内外学者在GRAC研究领域取得了大量系统性成果,但相关研究呈现较强的分散性,对界面科学、性能调控与低碳技术的跨体系整合研究较为欠缺,亟须从宏观战略视角加以系统梳理。本文以“固废协同胶凝理论与界面科学—多尺度性能调控体系—低碳先进技术应用”为三大主线,系统评述GRAC领域的最新研究进展,深入剖析已有研究的共识与争议,明确当前科学研究瓶颈,并提出未来需要重点突破的研究方向,为GRAC的基础研究深化和工程应用推广提供全面的参考依据。

1 固废协同胶凝理论与再生体系界面科学

1.1 Si/Al比对地聚物胶凝反应调控机理

地聚物混凝土的性能高度依赖其网络结构中硅氧四面体与铝氧四面体,原材料中的Si与Al物质的量之比(Si/Al比)是影响地聚物性能的重要因素。Si/Al比通过调控凝胶形成、微孔结构、网络连续性和基体致密度,直接影响地聚物的力学强度[5‒7]。研究普遍显示,随着Si/Al比的升高,地聚物抗压强度先升高后降低,因此为了保证地聚物的性能,必须严格将Si/Al比控制在一定区间。

已有研究解释了产生这种现象的原因[6,8‒10]:低Si/Al比限制了地聚物的缩聚反应,具体表现为Al(OH)4‒直接与硅酸盐缩聚产生聚硅铝结构,这种结构强度低。而高Si/Al比会抑制凝胶生成,并且使得N‒A‒S‒H凝胶中Si—O和Al—O的键长变长,分子间距变大,结构不稳定,加剧了结构的无序,使得凝胶模量降低。只有Si/Al比在合适的区间内,才能实现动力学的平衡并且增加反应过程中的放热量,从而使聚合反应更完全,此时硅酸盐会先自缩聚为低聚体再和Al(OH)4‒反应生成聚硅铝‒硅氧结构,这类结构强度较高。

不同体系的最佳Si/Al比相关研究见表1。大量研究表明,最佳Si/Al比范围为1.5~2.5[11‒22],但部分研究最佳Si/Al比超过2.5,这是因为其他因素同样起到调控Si/Al比的作用,例如碱激发剂类型、外加剂、前驱体活性等。其中,前驱体与碱激发剂的质量之比(B/S)越高,最佳Si/Al比越小[23],这是因为碱激发剂可以促进前驱体中的Al的溶出,从而影响最佳Si/Al比。外加剂的填入同样影响最佳Si/Al比,在地聚物混凝土(GPC)中加入含Si或Al的外加剂也会改变原本体系的最佳Si/Al比[24]。传统碱激发剂由Na2SiO3和NaOH组成,若添加含Al的材料作为碱激发剂,由于Al的添入需要更多的Si元素进行反应生成C(N)‒A‒S‒H凝胶,因此体系中最佳Si/Al比升高[25]。若前驱体体系中含有活性较低的以Si为主的原材料,则需要增加Si含量来弥补低活性的缺点,这会导致最佳Si/Al比偏高[26]。当体系中不含外加剂且前驱体、碱激发剂为常规材料时,通常Si/Al比范围为1.5~2.5。当地聚物体系中引入特殊材料时,在设计地聚物混凝土的过程中需要考虑最佳Si/Al比是否发生变化。目前,关于外加剂对于Si/Al比的调控作用的研究较少,需要后续学者的补充。

综合来看,Si/Al比作为地聚物混凝土性能调控的核心参数,其影响机理主要有3种:一是调控凝胶网络的交联程度和结构致密性;二是调控化学产物、化学键合作用;三是与激发剂类型、前驱体反应特性和外加剂协同作用,共同决定地聚物在强度上的表现。合理优化Si/Al比,使其与其他体系参数匹配,可在保证强度的同时实现耐久性和力学性能的最优平衡,为工业固废利用及高性能地聚物混凝土设计提供理论依据。

1.2 再生骨料‒地聚物基体的多维界面问题

1.2.1 三重界面体系的精确识别与表征

在地聚物再生混凝土中,界面过渡区是材料性能的关键控制区域。GRAC的ITZ总共分为3种,分别是旧骨料和旧砂浆ITZ1、旧骨料和新砂浆ITZ2、旧砂浆和新砂浆ITZ3。其中,由于再生骨料被大量的旧砂浆包裹,但是依旧有部分骨料裸露在表面,其与新砂浆可以形成ITZ2,目前ITZ2已被证实存在[27]。与普通混凝土类似,GRAC的ITZ呈现出孔隙率高、微裂纹集中的特征,但是由于基体反应机理不同,GRAC的ITZ与普通再生混凝土依然存在差异。

与传统硅酸盐水泥体系相比,地聚物基体对界面具有更强的凝胶填充作用[27]。普通再生混凝土的新砂浆与再生骨料的旧砂浆黏合性较差,导致ITZ宽度较大且存在大量孔隙[28],同时,旧砂浆与新砂浆之间的ITZ厚度和弹性模量均小于其余两种界面,因此,旧砂浆与新砂浆之间的界面薄弱是普通再生混凝土强度降低的主要原因[29]。对于GRAC来说,再生骨料的多孔性可以使得部分碱性溶液留存在旧砂浆中,与旧砂浆中的Na、Si、Al、Ca等元素发生聚合反应,形成一层凝胶层,增强了GRAC的新砂浆与旧砂浆的黏结能力[29]。地聚物再生混凝土与普通混凝土的ITZ结构如图1所示。Shi等[30]对地聚物净浆与再生骨料界面进行了能量色散谱仪(EDS)测试,研究发现,在旧砂浆界面过渡区附近存在Na、Si、Al,其认为在界面过渡区形成了一层N‒A‒S‒H凝胶,侧面反映了GRAC界面的黏结性较好。普通再生混凝土的ITZ较为明显,而GRAC的ITZ较为模糊,无法通过肉眼精准定位。因此出现了较多ITZ识别方法,例如巴西圆盘取样[31]、BSE‒EDS识别[32]、CLAHE算法[33]、CT重构[34]、SEM‒DIC定位[35]。

由于凝胶优异的黏结性能以及碱溶液与旧砂浆的反应作用,GRAC的ITZ更为密实、高强。这些微观机制共同作用,使GRAC在力学性能上优于普通再生混凝土,也为后续通过配比优化进一步改善界面性能提供了理论依据。

1.2.2 再生骨料‒地聚物基体界面强化策略

通过对再生骨料‒基体界面的强化处理,可在微观尺度显著改善ITZ结构,从而提升混凝土整体力学性能与耐久性。目前,界面强化的处理方法有物理改性、化学改性和复合改性,3种界面改性方式机理如图2所示。GRAC的界面强化方式大部分来源于对普通再生混凝土的研究,大部分界面强化方式在GRAC和普通再生混凝土中的效果相似,少量方式效果不一致。

物理改性方式对于GRAC和普通再生混凝土的性能提升均有限。物理改性方式有机械研磨、热处理、预湿。Kumar[36]、Zhang[37]等采用物理改性的方式对再生骨料进行预处理,研究表明,物理改性对GRAC的力学性能提升相比于未处理组提升不到10%。Yoon[38]、Ogawa[39]和Kou[40]等将物理改性应用于普通再生混凝土,提升效果同样不到10%。这是因为物理改性只能将部分附着砂浆去除,无法深入改善再生骨料‒新砂浆界面。

化学改性通过改变再生骨料的化学成分实现改性效果,通常包括化学浸泡、碳化、微生物矿化[41]等方法。碳化改性对GRAC和普通再生混凝土的提升效果存在差异,其对普通再生混凝土力学性能提升较为显著[42‒43],碳化将旧砂浆中的C‒S‒H凝胶转化为CaCO3,改善了旧骨料和新砂浆的界面。而碳化改性对GRAC提升效果较差甚至出现力学性能下降的情况[31,37],这是因为碳化过程向再生骨料中引入大量CO32‒,引发GRAC内部泛碱现象,进而破坏了地聚物的三维网格结构。目前,将化学改性的方式应用在GRAC的研究较少,例如微生物矿化、化学浸泡等方式仍需探索,同时,其在GRAC与普通再生混凝土界面改性提升机理上的差异也有待研究。

复合改性通过改变化学成分和物理填充效应协同调控界面性能。表面涂层是一种主要的复合改性方式,通过将粉末材料涂在再生骨料上实现界面改性,该方法可以在再生骨料表面生成新的化学物质并依赖粉末的物理填充作用强化界面。Zhao[44]和Zhang[45]等均采用表面涂层的方法对再生骨料进行改性,抗压强度均比未处理再生骨料组提升30%以上。Qin[46]和Singh[47]等发现,表面涂层可使GRAC的抗压强度提升60%以上。

GRAC界面强化方法总结如表2所示。虽然复合改性在普通再生混凝土和GRAC中的效果均为3种方式中的最佳方式,但是复合改性在GRAC中的提升效果更显著。复合改性在普通再生混凝土和GRAC中的性能提升机理还需要更多学者研究。

1.3 纤维增强与混杂增韧机制

纤维的掺入能够有效提升地聚物混凝土体系的韧性与强度,单一纤维的增强机理与效果因纤维类型和基体条件而异;不同复合混杂纤维的掺入则更为混乱,在静态力学和动态力学上的行为展现出复杂的协同效果。对GRAC体系而言,纤维的掺入往往能弥补其因为再生骨料造成的材料缺陷,起到互补作用,其原理与效应见图3。

1.3.1 地聚物再生混凝土单一纤维增强体系的机理与效应

单一纤维掺入地聚物再生混凝土体系的效应已得到广泛研究,其增强效果主要通过裂纹桥接、改善纤维‒基体界面结合,以及抑制裂纹扩展、避免脆性集中破坏等来实现,从而提升GRAC的韧性和残余强度。钢纤维(SF)是地聚物再生混凝土中被研究最多的单一纤维,Zhu等[49]研究了SF掺量在塑造再生地聚物砂浆性能和微观结构机制中的作用,发现SF的添加对干燥收缩有显著抑制作用,且有助于抑制砂浆内部裂纹的产生,使基质变得更加均匀和致密。同时,SF表面呈现出密集的水合凝胶产物层,显著改善了与砂浆的界面结合,提升了界面摩擦力,增强了基体的承载能力和延性。Zhao等[50]发现含有100%再生骨料和1.5%钢纤维的GRAC比天然骨料的普通水泥混凝土的抗压强度高38%,抗拉强度高83%,抗弯强度高41%,而压缩和抗弯韧性指标分别提高了160%以上和170%以上,并提出预测SF‒GRAC力学强度的经验公式。Li等[51]研究了不同SF和再生骨料含量对GRAC的力学性能和可持续性影响,综合考虑力学强度、碳排放和单位成本后发现再生骨料占比应小于50%,SF占比应小于0.5%。Li等[52]进一步研究钢纤维下Ca/Si比和再生骨料含量对地聚物再生混凝土孔隙结构、力学强度和干燥收缩行为的影响,发现钢纤维增强地聚物再生混凝土表现出显著的早期强度,3 d强度达到28 d强度的61%~84%,且高Ca/Si比能增强强度但会降低延性,而纤维的存在刚好弥补了这一缺陷。Jiang等[53]在Gao等[54]的基础上研究了带有箍筋约束的SFGRC的单轴压缩应力‒应变行为,分析了箍筋的配置方式、钢纤维体积分数及再生骨料替代率对混凝土性能的影响,发现SF的掺入显著影响了试件的破坏形式,其裂缝桥接效应导致延性破坏,并且随着SF体积分数的增加,主裂缝与加载轴之间的夹角增大,试件表现出更显著的塑性变形特征和更高的耗能能力。Jiang等[53]建立了一个应力‒应变模型,该模型准确描述了约束‒SFRGRAC的单轴压缩行为,改善了由再生骨料带来的试件破坏后完整性差的问题。在碳化的情况下,钢纤维的掺入还能与碳化修饰协同提升试件强度[53,55]。

除钢纤维外,Rezzoug等[56]系统结合了碳纳米管(CNTs)、玄武岩纤维(BF)和经过硅酸钙处理的再生骨料开发超高性能纤维增强地聚物再生混凝土,发现BF可进一步提高早期抗压强度、抗弯能力和裂缝抵抗性,同时改善耐高温和耐硫酸盐性能。Guo等[57]关注GRAC掺入聚乙烯(PE)纤维后的工作性、力学性能和碳减排性能研究,发现添加PE纤维会降低GRAC的抗压强度和工作性,但显著提高了拉伸试样的延展性,在纤维含量为1.5%时观察到试样峰值延展性,比无纤维试样高47倍。

总体而言,对地聚物混凝土体系的纤维掺入研究在增强机理上存在共性:通过桥接裂纹和改善纤维‒基体界面结合,提高开裂后的韧性;同时,纤维掺量对性能具有明显调控作用,存在最佳掺量范围,过量的纤维可能导致工作性下降或孔隙增加[49‒50,56,58‒59]。不同纤维增强地聚物基混凝土最佳纤维掺量情况见表3。对地聚物再生混凝土而言,单一纤维的掺入往往能改善再生骨料或者地聚物基体带来的诸多缺陷,如再生骨料与基体界面结合不良、再生骨料受外力破坏后完整性差、再生骨料与地聚物基体延性差、结构构件呈现脆性破坏等,有效提升地聚物再生混凝土的综合性能[49,51,53,55]。

1.3.2 地聚物再生混凝土混杂纤维体系的性能与行为

混杂纤维体系相较于单一纤维体系的优势在于可以通过不同纤维的协同作用显著增强地聚物混凝土的耐久性能、静态和动态力学性能。不同的混杂方案可以展现出互补的混合效果,其协同效应可以解决不同发展阶段和规模的各种性能需求。

在地聚物体系中,复合纤维的协同作用至关重要。Zhang等[58]研究主轴状碳酸钙(SCC)‒PVA混杂体系,PVA纤维提供宏观下高刚度桥接,SCC纤维则起到了抑制微裂纹萌生的作用,作为成核位点促进水化反应,通过微填充优化孔结构与干燥收缩率。Li等[68]提出玻璃纤维(GF)‒PVA纤维的复合体系,利用玻璃纤维的热稳定性,即在高温条件下能维持更有效的裂纹桥接,弥补PVA纤维在高温下性能会急剧劣化的不足,两者结合的体系保证了常温‒高温多环境下的长期性能。而在高应变率条件下(如SHPB动态分裂试验),混杂纤维体系表现出明显的动态增强效应。研究表明,掺杂玄武岩纤维或钢纤维后,材料裂纹萌生延迟,裂缝呈分布式扩展,能量吸收能力显著提升。数字图像相关(DIC)技术揭示,在动态荷载下,裂纹首先从接触区域萌生并沿加载方向迅速扩展,而静态荷载下裂纹沿中心对称扩展[69]。混杂纤维通过多尺度桥接作用显著改善了抗冲击性能和残余强度,体现了纤维‒基体界面在高应变率下的能量耗散机制[58]。此外,微观分析显示,混杂纤维体系能够优化孔隙结构、降低总孔隙率并增强界面密实性,进一步提升韧性和耐久性[49,58]。

对比地聚物再生混凝土体系,纯粹的复合纤维研究基本呈现空白,仅有Ma等[61]探索钢纤维(SF)的体积分数和长径比与聚丙烯纤维(PF)体积分数,以及再生骨料替代率对GRAC的影响,结果显示,SF和PF对GRAC机械性能具有显著的协同效应,然而,SF的亲水性与PF的疏水性相悖,削弱了纤维‒基体界面的结合,这在一定程度上降低了混凝土的机械性能,说明在复合纤维增强的地聚物再生混凝土体系中需要考虑纤维之间的互补性。于是Sun等[60]关注了纳米SiO2和钢纤维等复合体系,分析再生骨料和复合纤维掺量对GRAC力学性能和轴向压缩应力‒应变特性的影响,得到最佳掺量为1.5%SiO2、1.5%SF,其轴向抗压强度、抗折强度和抗拉强度相较于对照组分别提高了31.5%、80.49%和51.84%;在微观层面,纳米SiO2通过填充孔隙和促进C‒S‒H凝胶的形成来细化孔结构,而钢纤维则通过机械阻塞效应抑制裂纹扩展。Rezzoug等[56]则提出了玄武岩纤维(BF)‒碳纳米管(CNT)复合体系来提升地聚物再生混凝土的耐久性,在超高性能GRAC中,BF与碳纳米管协同作用,碳纳米管用于优化孔隙结构、增强界面密实性,BF则桥接微小裂缝,同时改善耐高温和耐硫酸盐性能,提高早期抗压和抗弯强度。

综合来看,相较于GPC,混杂纤维体系对于GRAC的补强更为关键。针对再生骨料天然的结构性劣势,合理的复合纤维协同作用能在微观上弥补再生骨料自身缺陷和再生骨料与基体结合缺陷,优化孔隙结构,同时在宏观上桥接裂缝,延缓裂缝发展,抑制干缩,提升能量吸收能力[56,58,60‒61],是地聚物再生混凝土提升耐久性、力学性能的绝佳方案。目前,对于复合纤维增强地聚物再生骨料体系还需要参考地聚物体系研究内容,在高温环境、动态力学环境、长期耐久性环境下探索互相协同的混杂纤维方案,推动地聚物再生混凝土力学性能和耐久性能的提升,也需要进一步研究不同复合纤维与再生骨料的耦合后对GRAC性能的影响和对应机理。

2 低碳先进技术在GRAC中的应用

2.1 CO2 矿化技术与碳化调控策略

2.1.1 地聚物基体的碳化行为

地聚物体系中通常缺乏大量Ca(OH)2,因此其碳化过程主要表现为碱性离子消耗、凝胶脱钙及硅铝骨架重组等过程[75‒77]。并且地聚物碳化不仅会改变孔结构与离子平衡,还会进一步影响材料的力学性能与长期耐久性[76,78]。Bernal等[76]的研究指出,碱激发材料的耐久性高度依赖其凝胶结构稳定性与孔隙传输特征,因此不能简单套用OPC体系的碳化规律。现有研究[77‒78]表明,不同地聚物体系之间的碳化行为也存在显著差异,其根本原因在于前驱体类型及Ca含量不同所形成的凝胶结构存在差异。低钙和高钙地聚物碳化反应机理如图4所示。

低钙粉煤灰或偏高岭土基地聚物体系主要形成N‒A‒S‒H凝胶,CO2进入孔隙后主要与孔溶液中的Na+、K+等碱性离子反应,并生成Na2CO3等碳化产物[77]。低钙体系地聚物在长期碳化过程中表现出较大的碳化深度,主要与体系中Ca含量较低、碱储备不足有关[79]。Luan等[80]进一步研究发现,低钙粉煤灰基地聚物混凝土28 d碳化深度超过25 mm,而普通水泥混凝土仅约11 mm,前者碳化速率约为后者的2.2倍。作者认为,该现象主要与地聚物体系中可用于中和CO2的碱性物质较少有关,其初始pH值仅约10.9,明显低于普通水泥体系的12.5。

此外,对于低钙体系中N‒A‒S‒H凝胶在碳化过程中的稳定性目前仍存在一定争议。Bernal等[77]通过XRD和FTIR分析发现,低钙地聚物碳化后虽然孔溶液碱度明显下降,但N‒A‒S‒H凝胶主骨架并未发生明显破坏,因此认为CO2主要消耗孔隙中的碱性离子,而非直接破坏凝胶结构。相反,Puertas等[75]则观察到长期碳化后体系中Na+持续流失,并伴随孔径增大及凝胶结构重组等现象,认为碳化可能导致凝胶稳定性下降。Luan等[80]进一步指出,低钙地聚物碳化初期由于Na2CO3填充孔隙会出现短期致密化,但后期随着Na2CO3溶解迁移,孔结构重新粗化,材料强度又会下降。因此N‒A‒S‒H凝胶在长期碳化环境中的真实稳定性仍需进一步研究。

相比之下,高钙矿渣基地聚物体系由于含有较多C‒(A)‒S‒H凝胶,其碳化过程主要表现为脱钙反应。CO2进入体系后会促使C‒(A)‒S‒H凝胶中的Ca2+析出,并进一步形成CaCO3沉积[75]。因此,高钙体系碳化过程中通常同时存在“凝胶脱钙导致结构劣化”与“CaCO3填充孔隙导致局部致密化”两种竞争机制。Li等[78]也指出,矿渣基地聚物由于Ca含量较高,在碳化初期可能因CaCO3填孔作用而出现强度短暂提升,但随着脱钙持续进行,后期仍会出现强度衰减。

除凝胶结构外,孔隙结构演化也是决定地聚物碳化行为的重要因素。Li等[78]研究表明,CO2在地聚物中的扩散能力与孔隙率、孔径分布及孔连通性密切相关,较高的连通孔比例会加速CO2向内部扩散。Huang等[81]进一步指出,碳化过程中凝胶结构变化会使得部分微孔向中大孔转化,从而提高CO2扩散效率。

近年来,关于再生骨料对地聚物体系碳化行为影响的研究逐渐增多。Xiao等[82]研究发现,与普通地聚物混凝土相比,地聚物再生骨料混凝土因再生骨料表面附着旧砂浆,内部存在大量原生裂缝与孔隙,其CO2传输路径更加复杂。再生骨料的引入会提高材料整体孔隙率和界面过渡区缺陷水平,从而加速CO2扩散并增加碳化深度。

此外,为提高地聚物体系的抗碳化性能,近年来研究主要集中于纳米SiO2、矿渣协同激发和纤维增强等改性方法。Huang等[83]发现,适量引入矿渣或熟石灰能够提高体系Ca含量,从而增强对CO2的缓冲能力并降低碳化深度,进而提高地聚物材料的抗碳化性能。Li等[84]研究表明,纤维增强能够通过抑制微裂缝扩展减少CO2传输通道。Yang等[85]则指出,纳米SiO2能够促进硅铝凝胶聚合并降低大孔比例,从而优化孔结构并提高地聚物再生混凝土的抗碳化性能。

综上所述,地聚物体系碳化行为并不存在统一规律,而是受到多因素的共同影响。因此,在分析地聚物材料碳化行为时,应结合具体体系特征进行针对性研究。

2.1.2 再生骨料的加速碳化处理

近年来,CO2加速碳化技术被认为是提升再生骨料(RCA)性能并实现碳封存的有效途径,其本质在于通过调控碳化工艺和环境参数,促进骨料孔隙结构致密化和界面特性优化。再生混凝土骨料在碳化过程中表现为典型的气‒液‒固三相反应体系,CO2与骨料中氢氧化钙及部分C‒S‒H凝胶反应生成CaCO3,从而导致孔隙填充及结构致密化,并伴随一定程度的C‒S‒H脱钙作用[86‒87]。该微观结构演化过程被认为是吸水率降低以及界面过渡区性能提升的主要原因[87‒88]。微观结构的优化最终表现为宏观性能的改善。碳化处理后再生骨料吸水率显著降低,表观密度提高,压碎指标减小,采用碳化再生骨料制备的再生混凝土通常表现出更高的抗压强度和更好的耐久性能[89‒90]。因此,碳化改性的强化机制本质上来源于CaCO3沉积引起的孔隙填充效应和界面致密化效应,如图5所示。

在工艺参数方面,相对湿度、CO2浓度、温度及碳化时间被普遍认为是影响再生混凝土骨料碳化效率和性能提升的关键因素,表4总结了不同工艺参数对RCA碳化效果的影响。其中,相对湿度被认为是控制碳化反应的核心参数之一。Ali等[89]的综述研究指出,50%~70%的湿度范围通常可获得较优的碳化速率且使力学性能明显提升。这一现象主要源于中等湿度条件下孔隙表面形成的薄水膜既能促进CO2溶解和Ca2+迁移,又不会显著阻碍CO2在孔隙中的扩散。当含水量过高时,孔隙被水填充会抑制CO2扩散,而水分过少时,碳化反应和胶结能力会变弱从而降低碳化效率。在CO2浓度方面,适当提高CO2浓度可有效加快碳化反应动力学并促进CaCO3生成。20%~50%的CO2浓度通常可实现较高的碳化效率,但过高的CO2浓度可能导致CaCO3在骨料表面快速沉积,形成致密层,从而阻碍CO2向内部扩散[91]。因此,在保证碳化效率的前提下,采用中等浓度CO2具有良好的工程应用可行性。在温度方面,其主要通过影响反应动力学及CO2在水中的溶解行为对碳化过程产生重要作用。碳化反应的适宜温度通常位于20~30 ℃范围内[89],在该区间内能够兼顾CO2扩散、溶解以及反应速率,从而获得较优的碳化效果。在碳化时间方面,碳化反应通常呈现先快后慢的特征。Gao等[88]发现,在半湿法碳化条件下,30 min内即可实现约10.6%的碳化程度;而Kaddah等[87]指出,碳化初期以氢氧化钙反应为主,后期逐渐转向水化硅酸钙的碳化,同时伴随孔隙结构演化及可能的微裂纹产生。此外,延长碳化时间虽有助于提高碳化程度,但其增长效果会随反应进行逐渐减弱[89]。

不同碳化方式在反应速率、碳化程度及工程适应性方面表现出明显差异[89,93],因此需根据具体应用场景进行合理选择与优化,如表5所示。

Leemann等[91]研究表明,在高浓度CO2条件下,CO2能够快速与再生骨料表面的氢氧化钙反应生成CaCO3,并在短时间内形成致密碳化层,从而显著降低吸水率并提高再生混凝土的抗压强度。相比之下,Pu等[90]指出,虽然烟气碳化CO2浓度较低,但仍可实现有效碳化,并具有更高的工程应用可行性与经济性。气固碳化主要依赖CO2在孔隙中的扩散及其与残余水化产物的反应,整体反应速率较慢,碳化过程受扩散控制,易在骨料表层形成碳化产物,从而限制进一步反应,导致碳化程度有限,但该方法工艺简单、设备要求较低,适用于工程推广。相比之下,湿法碳化通过引入液相环境显著提高CO2溶解度并促进Ca2+迁移,使碳化反应更加充分,碳化程度较高,但其反应过程受CO2在液相中的扩散速率限制,能耗和工艺复杂性相对较大[94]。半湿法碳化作为一种介于气固与湿法之间的改进方式,通过在骨料表面形成薄水膜,在保证CO2扩散能力的同时促进其溶解与反应,从而显著提高碳化效率,并在较短时间内实现较高碳化程度,表现出较好的综合性能[88]。另一方面,虽然提高CO2分压(如加压碳化)能够增强CO2向材料内部扩散的能力,从而加快碳化速率并提高碳封存能力,但同时对设备密封性及运行成本提出更高要求,工程应用受到一定限制[89]。

综合来看,现有研究已从机理、参数调控和工艺路径等方面较为系统地阐明了再生骨料加速碳化的作用机制以及性能演化规律,不同研究之间在碳化方式选择与性能评价指标上虽存在差异,但均表明CO2矿化过程能够在一定程度上实现骨料性能改善与碳封存的协同效果。但是对碳化再生骨料(CRA)在地聚物基体中的影响与在普通水泥基混凝土中的影响具有明显的差异。Shi等[31]的研究发现,CRA虽然能改善骨料物理性能(如降低吸水率),但其引入的大量CO32‒会与地聚物体系中的Na⁺结合,生成碳酸钠晶体,从而影响地聚物胶凝体系中N‒A‒S‒H凝胶的形成,削弱了ITZ的黏结性能。同时研究结果指出,要达到可接受的强度,用CRA制备GRAC的碳化时间需要96 h。然而,碳化再生骨料在地聚物再生混凝土中的长期性能表现仍有待进一步研究。

2.2 生命周期环境影响评价与碳减排量化

2.2.1 生命周期评价方法

基于生命周期评价(LCA)方法,现有研究从原材料获取—生产—运输—使用全过程系统分析了地聚物混凝土和再生骨料体系的环境影响特征。整体而言,LCA作为“从摇篮到大门”或“从摇篮到坟墓”的评价工具,能够有效量化不同混凝土体系在全球变暖潜势(GWP)、酸化潜势(AP)和生态毒性(ET)等多维指标下的环境表现,为低碳材料设计提供重要依据[95]。其系统边界通常涵盖原材料获取、再生处理、运输、混凝土制备、使用与拆除回收等过程,如图6所示。

近年来,不同研究之间的LCA结果存在差异,主要因为方法学参数对碳排放计算路径的改变。改变系统边界会直接改变碳排放被计入的阶段,当采用“从摇篮到大门”时,仅统计原材料获取与生产阶段排放;当扩展至“从摇篮到坟墓”时,还需叠加使用、拆除和再利用阶段排放,从而得到更高的总碳排放值[95‒96]。在分配方法方面,不同研究对工业固废的处理方式存在较大差异,会直接改变地聚物混凝土体系的碳排放水平。Zhang等[96]指出,不同分配方法会显著改变地聚物体系的LCA结果。采用cut-off模型时,仅考虑工业固废的收集、运输和再加工过程,因此GWP结果通常较低;而采用economic allocation或mass allocation方法时,则需将上游工业生产过程中的部分环境负荷分摊至粉煤灰或矿渣,因此提高了其生命周期碳排放计算值。

此外,运输距离通过改变燃油消耗量影响碳排放构成。Estanqueiro等[97]研究表明,再生骨料在短距离运输条件下可通过减少天然骨料开采排放实现净减排;当运输距离增加时,运输阶段产生的CO2逐步累积并抵消前述减排收益,当超过临界运输距离后,再生骨料体系的总碳排放可能高于天然骨料体系。区域能源结构同样会影响计算结果,当电力以煤电为主时,NaOH、Na2SiO3制备以及再生骨料加工过程的单位排放增加,使GPC体系碳减排幅度下降;当可再生能源占比较高时,上述高耗电环节排放降低,GPC相对优势进一步扩大。

因此,开展地聚物及再生混凝土碳减排量化研究时,需要在统一系统边界、功能单位和分配方法的前提下进行对比分析,以保证不同研究结果的可比性。

2.2.2 环境影响与碳减排研究

现有研究普遍认为,地聚物混凝土相比普通硅酸盐水泥混凝土具有碳减排优势,但不同文献报道的减排幅度差异较大,从9%到70%以上不等。Turner等[98]研究发现,地聚物混凝土相较OPC混凝土的CO2排放仅降低约9%,主要因为其计入了碱激发剂生产、高温养护以及运输过程的能耗。Meshram等[99]发现粉煤灰基地聚物混凝土的碳排放降低幅度约为26%,说明在部分配合比和评价边界下,地聚物的减碳优势并不一定十分突出。Luan等[100]则基于粉煤灰基地聚物混凝土的CO2避免成本分析指出,其相较普通水泥混凝土至少可降低43.15%的CO2排放,中位减排率约为50.06%。与此相比,Shi等[101]得到的粉煤灰基地聚物混凝土CO2减排率为62.73%,Luo等[102]报道建筑垃圾复合粉和粉煤灰基地聚物材料可实现62%~73%的CO2减排。在此基础上,引入再生骨料(RCA),通过减少天然骨料开采、爆破及破碎过程的能源消耗,实现额外减排[97],并且可将整体碳排放降低至传统OPC体系的约50%~80%[102‒103]。由此可见,不同研究结果之间的差异主要来自LCA系统边界、功能单位、碱激发剂用量、原材料来源、运输距离以及养护制度等因素,而不能简单归因于地聚物材料本身的减碳能力差异。图7展示了GRAC体系与OPC体系在生命周期各阶段CO2排放对比。

从多环境指标对比来看,GRAC体系在全球变暖潜势、酸化潜势和光化学氧化物(POF)上低于OPC,但海洋生态毒性、人类毒性及富营养化指标更高,这源于碱激发剂生产中的化学品排放,形成了减碳与增毒性的权衡。但在GRAC体系中,再生骨料替代进一步降低碳排放,但碱激发剂环境负荷占比提高,使该权衡更加显著[95],因此降低激发剂用量或开发低碳激发体系成为优化核心。为进一步明确GRAC体系与OPC体系在不同生命周期阶段及环境指标上的差异,本文对其进行系统对比,如表6所示。

GRAC体系的生命周期评价研究逐渐由单一碳排放评价转向环境‒力学‒经济‒耐久多目标协同优化。GRAC体系在降低全球变暖潜势的同时,可能导致生态毒性和人类毒性(HT)指标增加[95],因此仅采用单一减碳指标难以全面反映材料综合性能。近年来,针对地聚物再生混凝土环境效益与工程性能之间的权衡问题,研究者开始采用多目标评价方法(MCDM)开展综合可持续性分析。与传统研究仅关注抗压强度或碳排放等单一指标不同,多目标评价强调在满足结构性能要求的前提下,同时兼顾耐久性、环境影响及资源消耗等多个目标,实现材料综合性能最优。

例如,Turner等[98]以粉煤灰基地聚物混凝土为研究对象,构建了基于生命周期评价与多准则决策分析相结合的综合评价模型。该模型将28 d抗压强度、抗硫酸盐侵蚀性能以及环境影响指标(全球变暖潜势GWP、酸化潜势AP和一次能源消耗PED)共同纳入评价体系,从力学性能、耐久性能和环境性能3个维度对不同配合比方案进行综合评估。该研究中首先利用LCA量化各配合比的环境负荷,然后采用层次分析法(AHP)和熵权法(EWM)确定主客观组合权重,再通过灰色聚类分析(GCA)、优劣解距离法(TOPSIS)和多准则妥协优化法(VIKOR)等多准则决策方法对各方案进行排序和优选。结果表明,虽然不同评价方法的排序过程存在差异,但均确认同一配合比在强度、耐久性和环境性能上达到最佳平衡,说明该方法能够有效协调各性能指标之间的矛盾关系,实现多目标协同优化。

综上所述,地聚物和地聚物再生混凝土在全球变暖潜势方面具有明确减排优势,但在生态毒性等指标上存在增加趋势,且不同研究结果受方法学参数和材料组成影响较大。未来研究应在统一LCA方法框架的基础上,结合微观结构演化与力学性能,构建环境效益‒力学性能‒耐久性多维耦合评价体系,以推动地聚物再生混凝土的工程应用。

3 数据驱动的配合比设计方法:机器学习在地聚物再生混凝土中的发展应用

由于地聚物配合比设计中各组分之间存在复杂的非线性耦合作用,传统的试验试错方法难以高效挖掘材料性能潜力。近年来,机器学习在地聚物材料领域的应用研究快速兴起,形成了以强度预测为主干、逐步向多目标优化和智能设计拓展的发展格局,机器学习的预测流程如图8所示。针对地聚物这种多影响因素的体系,多数研究通过多源文献数据整合和清洗构建综合数据库、对比不同模型性能、进行可解释性分析和特征工程等手段来解读地聚物混凝土体系下的“黑盒子”。XGBoost模型在诸多研究方法中成为了最佳选择,就是因为其在多维非线性背景下具有优越性能。不同计算模型在不同地聚物体系中的研究对比如表7所示。在特征工程方面,针对地聚物配比的非线性与异质性,采用SHAP(shapley additive explanations)方法量化各输入特征对输出的贡献,可帮助寻找各体系中的关键影响因素,进而反馈到模型的优化修正中,提升模型的泛化性。

机器学习在地聚物再生混凝土方面的应用整体呈现出前期研究数据库总量小、模型选择多样、研究材料环境多变和泛化性存疑的问题。针对数据库小的问题,有研究采用表格式生成对抗网络(CTGAN)来合成数据库,增大数据总量,进而提升模型性能[104]。在模型选择方面,Maganti等[105]对比了6种机器学习模型(BPNN、SVR、RF、GDBT、XGB和LGB)预测ARC抗压强度(CS)的表现,发现XGB精度最高。Golafshani等[104]对8种集成模型进行比较,同样发现Boosting模型,尤其是极端梯度提升回归器(XGBR),在GRAC抗压强度预测中表现最佳。这些针对模型选择的研究中,XGBoost模型都展现了更好的结果[104‒108],可见,针对大部分预测强度的研究场景下,XGBoost模型目前是最适配的模型选择。在研究材料环境多变问题上,地聚物混凝土对养护温度、时间和Ca/Si比等因素极为敏感,而GRAC由于采用了再生骨料,引入了额外的影响因素。Golafshani[104]、Maganti[105]等采用SHAP分析发现:常规的地聚物混凝土中养护环境是敏感性因素;GRAC的敏感性因素是养护龄期、天然细骨料含量(NFA)、再生骨料比例和矿渣水泥含量,即地聚物再生混凝土龄期和再生骨料比率对其的强度预测影响十分显著。对于采用再生粉煤灰而非再生骨料的情况,Shen等[108]发现液固比与其抗压强度呈负相关,而预处理温度、热处理时间和养护龄期与CDWG抗压强度呈正相关,说明GRAC体系对再生骨料的利用极大地影响了其抗压强度的预测规律,需要进一步探索再生骨料对机器学习敏感性分析的影响。关于模型泛化性的问题,Rathnayaka等[109]在粉煤灰基地聚物混凝土机器学习方法泛化性的研究中指出,泛化性的核心关键是模型的训练数据库是否全面以及数据是否经过了标准化处理,全面的数据库可以避免因实际使用时加入了全新材料而带来的不可预测性,而标准化的处理有助于对相同数据库背景下不同模型的效果进行对比。

总体而言,人工智能与机器学习的方法在地聚物再生混凝土强度预测领域仍旧需要更多的应用探索和深度拓展,目前虽然能基于数据驱动进行合理配合比设计和优化,但再生骨料对模型的影响情况还不明确,需要更深度理解其对地聚物再生混凝土性能的作用机制,且数据标准化方案还需统一,模型的泛化性还需要探索。

4 结 论

本文从固废协同胶凝理论、性能调控体系与低碳先进技术三大维度,系统综述了地聚物再生混凝土GRAC的研究现状与进展,主要结论如下:

1)Si/Al比是地聚物性能调控的核心参数,最佳范围通常为2.0~2.5,但其受碱激发剂类型、前驱体特性和外加剂的影响显著,需要在具体体系中进行针对性优化。多元固废协同使用时,Si/Al比与Ca含量、前驱体活性的耦合效应是决定胶凝产物类型(N‒A‒S‒H或C‒A‒S‒H)和材料最终性能的关键。

2)GRAC具有独特的三重界面体系,地聚物基体的凝胶填充作用使GRAC的ITZ整体优于普通再生混凝土,其中旧砂浆与新砂浆之间是最薄弱界面。表面涂层类化学强化方式(矿渣/硅灰包覆)可显著提升界面强度(抗压强度最高提升62.8%以上),而碳化处理对GRAC的强化效果不如普通再生混凝土,主要是因为引入过量CO32‒会导致GRAC泛碱劣化。

3)响应面法RSM作为GRAC传统配合比优化工具,适合初步筛选关键因素,但对高度非线性体系存在局限。机器学习方法(尤其是XGBoost及集成模型)在GRAC抗压强度预测中表现优异,但受限于GRAC数据库规模,CTGAN数据增强是有效的应对策略。SHAP分析表明,GRAC的强度预测中再生骨料比例和养护龄期的重要性显著高于常规GPC,提示建立专用GRAC数据库的迫切性。

4)单一纤维(尤其是钢纤维)可显著改善GRAC的韧性、延性和裂缝控制能力,弥补再生骨料引入的结构缺陷,但最优掺量通常不超过2%,过量会导致工作性下降。混杂纤维体系通过多尺度协同桥接作用,在微观孔隙优化与宏观裂缝控制上的表现均优于单一纤维,但纤维之间的物化相容性需要作为设计约束条件。

5)地聚物基体的碳化行为高度依赖凝胶类型:低钙N‒A‒S‒H体系碳化后产生可溶性Na2CO3,碳化深度远大于OPC(约为其2.2倍);高钙C‒(A)‒S‒H体系碳化初期因CaCO3填孔而强度短暂提升,后期则因脱钙而劣化。GRAC中再生骨料的原生孔隙加速了CO2扩散,碳化深度进一步增大,抗碳化设计须特别关注。

6)LCA研究表明,GRAC体系的全球变暖潜势相比OPC可降低50%~63%,但碱激发剂(NaOH、Na2SiO3)的制备会带来较高的生态毒性排放,需寻求“减碳‒增毒”的平衡。再生骨料加速碳化技术在改性骨料性能的同时实现额外碳封存,是GRAC实现协同减排的重要技术路径。

5 展 望

基于以上综合评述,未来地聚物再生混凝土领域亟须在以下6个方向实现突破:

1)多元固废协同机理的精准调控与标准化。当前多元固废体系(粉煤灰、矿渣、赤泥、建筑垃圾等)中,各固废种类来源波动性大、活性差异显著,导致GRAC性能批次稳定性差,是制约工程规模化应用的核心障碍之一。未来应建立基于固废组分快速表征‒反应活性预测‒配合比实时调整的闭环智能设计系统,并逐步推动行业相关固废表征标准的建立。

2)三重界面体系的动态演化机制与长期耐久性预测。目前大量研究集中于GRAC界面的静态表征,对界面在干湿循环、冻融、氯盐侵蚀、碳化等复合环境下的动态演化规律认识不足。建议采用原位X‒CT成像、原位纳米压痕等先进表征技术,建立多时间尺度下的界面损伤演化模型,进而构建GRAC的可靠寿命预测框架。

3)机器学习与材料基因组学的深度融合。现有GRAC机器学习研究受限于数据库规模,且特征工程多停留在宏观配合比参数层面,缺乏微观结构特征的融合。未来需构建跨研究机构的开放GRAC数据库,集成微观‒宏观多尺度特征,借助材料基因组学思路实现从“预测强度”到“设计性能”的跨越。

4)复合纤维优化设计与绿色纤维体系探索。目前GRAC复合纤维研究多停留于双组分体系,对三元以上混杂纤维、纳米纤维与宏观纤维结合等新型体系研究不足。与此同时,天然植物纤维(黄麻、剑麻、玄武岩天然纤维等)因来源广泛、可再生的特点,有望成为GRAC绿色纤维体系的重要组成部分,其与地聚物基体的界面相容性和长期性能演变值得系统探索。

5)加速碳化技术的规模化工程应用与碳核算方法统一。再生骨料加速碳化技术已在实验室层面证明了有效性,但其工业化放大(批量处理效率、碳化均匀性、烟气适配性)和全流程碳核算方法仍不统一,制约了该技术的推广。未来需建立针对不同固废来源再生骨料的标准化碳化工艺参数数据库,并与LCA方法结合,建立GRAC碳封存量的可信核算体系,服务于碳市场交易需求。

6)GRAC结构构件的工程应用与设计规范研究。现有研究绝大多数停留于材料层面,对GRAC在实际结构构件(梁、柱、板、节点)中的力学行为、耐久性表现以及设计方法研究极为匮乏。未来应加快推动GRAC构件级试验研究,基于系统的试验数据提出适用于GRAC的结构设计方法,并推动其纳入相关行业规范和地方标准,为GRAC的工程化应用奠定制度基础。

总体而言,地聚物再生混凝土作为融合固废资源化、低碳建材制备与智能设计技术的新型绿色建筑材料,发展前景广阔。面对未来“双碳”目标的约束与城市建设的巨大固废压力,GRAC有望成为新型建筑工业化进程中的核心低碳材料之一,值得学界和工程界持续投入力量、协同推进。

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【校友简介】

[117]

王清远,博士(法国,四川大学教授,博士生导师,部省重点实验室主任,原成都大学校长,欧洲科学院院士、欧洲科学与艺术院院士、中国工程院有效院士候选人、国家杰青、国务院学位委员会第七届力学学科评议组成员,国际期刊Green Buildings and Materials主编。主要从事新型材料与结构力学问题、低碳与长寿命建筑材料、固废资源化再生利用及低碳可持续发展等方面的研究,在Constr . Build Mater.、J. Cleaner Prod.、Cem. Concr. Compos.、J. Hazard Mater.、Adv. Mater.、Prog. Mater. Sci.、Nat. Commun.、Nature等中科院1区Top刊物发表论文100余篇,连续十余年入选Elsevier中国高被引学者,入选全球2%顶尖科学家年度和生涯榜单。授权发明专利50余项,出版学术专著5部。以第一完成人获国家自然科学奖二等奖、教育部自然科学奖一等奖、四川省科技进步奖一等奖2项、中国力学学会科技进步一等奖等。

基金资助

国家自然科学基金面上项目(52578313)

四川省国际科技创新合作(重点项目)(25GJHZ0191)

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