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碎片测试和纳米孔隙力学颠覆了水泥水化收缩的传统范式。

The shard test and nanoporomechanics reverse classical paradigm of cement hydration being contractive.

作者信息

Rosa Raúl E Marrero, Bhibho Tapiwanashe, Dőnmez Ahmet A, Cusatis Gianluca, Bažant Zdeněk P

机构信息

Civil and Environmental Engineering Department, Northwestern University, Evanston, IL 60208.

United State Gypsum Co., Libertyville, IL 60048.

出版信息

Proc Natl Acad Sci U S A. 2024 Dec 17;121(51):e2418448121. doi: 10.1073/pnas.2418448121. Epub 2024 Dec 9.

Abstract

Le Chatelier in 1887 and Powers in 1947 demonstrated that the volume of nanoscale C-S-H (calcium silicate hydrate) particles formed during hydration is smaller than the combined volume of the reactants-the anhydrous Portland cement and water. Hydration has thus been considered as contractive. An experiment shows that the opposite is true above the nanoscale. The porous skeleton of cement paste expands as the growing C-S-H particles push each other apart, similar to crystal growth pressure. This is significant for high-performance concretes (HPC) with low water-cement ratios (w/c [Formula: see text] 0.4), where chemical self-desiccation lowers pore relative humidity by 40%, compared to just 1% in traditional concretes (w/c [Formula: see text] 0.5). Standard American Society for Testing and Materials (ASTM) C1608 tests, using 10 mm thick water-immersed specimens, show large shrinkage because the half-time of water ingress is many decades, unable to offset shrinkage-causing self-desiccation. The present experiment, using a laser microscopy-topography technique, proves the opposite-expansion, evidenced by measuring the length changes of water-immersed HPC shards 0.5 mm thick in which the diffusion halftime, only about one hour, allows continuous resaturation of pores, canceling self-desiccation. The faster diffusion (halftime of one hour) enables continuous pore resaturation, preventing shrinkage. When sealed with paraffin oil, the shards self-desiccate and shrink. These findings align with studies since 2015, showing that models excluding hydration expansion cannot fit test data across various specimen sizes and sealing conditions. The results suggest that standardized ASTM tests for the so-called chemical shrinkage in modern concretes with very low water-cement ratios are misleading and need revision.

摘要

1887年,勒夏特列以及1947年,鲍尔斯证明,水化过程中形成的纳米级C-S-H(硅酸钙水合物)颗粒的体积小于反应物(无水波特兰水泥和水)的总体积。因此,水化作用被认为是收缩性的。一项实验表明,在纳米尺度以上情况则相反。随着不断生长的C-S-H颗粒相互推开,水泥浆体的多孔骨架会膨胀,这类似于晶体生长压力。这对于水灰比低(w/c [公式:见原文] 0.4)的高性能混凝土(HPC)具有重要意义,与传统混凝土(w/c [公式:见原文] 0.5)中孔隙相对湿度仅降低1%相比,化学自干燥使高性能混凝土的孔隙相对湿度降低了40%。美国材料与试验协会(ASTM)标准C1608试验使用10毫米厚的水浸试件,结果显示出较大的收缩,因为水进入的半衰期长达数十年,无法抵消导致收缩的自干燥作用。本实验采用激光显微镜-形貌技术,证明了相反的情况——膨胀,这是通过测量0.5毫米厚的水浸高性能混凝土碎片的长度变化来证明的,其中扩散半衰期仅约一小时,能使孔隙持续再饱和,抵消自干燥作用。更快的扩散速度(半衰期为一小时)能使孔隙持续再饱和,防止收缩。当用石蜡油密封时,碎片会自干燥并收缩。这些发现与2015年以来的研究一致,表明排除水化膨胀的模型无法拟合各种试件尺寸和密封条件下的试验数据。结果表明,美国材料与试验协会对水灰比极低的现代混凝土中所谓化学收缩的标准化试验具有误导性,需要修订。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c39c/11665906/0f28302f9254/pnas.2418448121fig01.jpg

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