Edited by David J. Killick, University of Arizona, and accepted by the Editorial Board October 27, 2014 (received for review September 12, 2014)
A volcanic ash–lime mortar has been regarded for centuries as the principal material constituent that provides long-term durability to ancient Roman architectural concrete. A reproduction of Imperial-age mortar based on Trajan’s Markets (110 CE) wall concrete resists microcracking through cohesion of calcium–aluminum–silicate–hydrate cementing binder and in situ crystallization of platey strätlingite, a durable calcium-aluminosilicate mineral that reinforces interfacial zones and the cementitious matrix. In the 1,900-y-old mortar dense intergrowths of the platey crystals obstruct crack propagation and preserve cohesion at the micron scale. Trajanic concrete provides a proven prototype for environmentally friendly conglomeratic concretes that contain ∼88 vol % volcanic rock yet maintain their chemical resilience and structural integrity in seismically active environments at the millenial scale.
The pyroclastic aggregate concrete of Trajan’s Markets (110 CE), now Museo Fori Imperiali in Rome, has absorbed energy from seismic ground shaking and long-term foundation settlement for nearly two millenia while remaining largely intact at the structural scale. The scientific basis of this exceptional service record is explored through computed tomography of fracture surfaces and synchroton X-ray microdiffraction analyses of a reproduction of the standardized hydrated lime–volcanic ash mortar that binds decimeter-sized tuff and brick aggregate in the conglomeratic concrete. The mortar reproduction gains fracture toughness over 180 d through progressive coalescence of calcium–aluminum-silicate–hydrate (C-A-S-H) cementing binder with Ca/(Si+Al) ≈ 0.8–0.9 and crystallization of strätlingite and siliceous hydrogarnet (katoite) at ≥90 d, after pozzolanic consumption of hydrated lime was complete. Platey strätlingite crystals toughen interfacial zones along scoria perimeters and impede macroscale propagation of crack segments. In the 1,900-y-old mortar, C-A-S-H has low Ca/(Si+Al) ≈ 0.45–0.75. Dense clusters of 2- to 30-µm strätlingite plates further reinforce interfacial zones, the weakest link of modern cement-based concrete, and the cementitious matrix. These crystals formed during long-term autogeneous reaction of dissolved calcite from lime and the alkali-rich scoriae groundmass, clay mineral (halloysite), and zeolite (phillipsite and chabazite) surface textures from the Pozzolane Rosse pyroclastic flow, erupted from the nearby Alban Hills volcano. The clast-supported conglomeratic fabric of the concrete presents further resistance to fracture propagation at the structural scale.
Author contributions: M.D.J., E.N.L., P.F.B., M.V., H.-R.W., P.J.M.M., and A.R.I. designed research; M.D.J., E.N.L., P.F.B., M.V., M.K., H.-R.W., and A.R.I. performed research; M.D.J., E.N.L., P.F.B., H.C., Q.L., M.K., and A.R.I. analyzed data; and M.D.J., E.N.L., and P.F.B. wrote the paper.
The authors declare no conflict of interest.
This article is a PNAS Direct Submission. D.J.K. is a guest editor invited by the Editorial Board.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1417456111/-/DCSupplemental.
Freely available online through the PNAS open access option.
