Richard A. Livingston

Cements in the 21st Century: Challenges, Perspectives, and Opportunities

In a book published in 1906, Richard Meade outlined the history of portland cement up to that point1. Since then there has been great progress in portland cement-based construction materials technologies brought about by advances in the materials science of composites and the development of chemical additives (admixtures) for applications. The resulting functionalities, together with its economy and the sheer abundance of its raw materials, have elevated ordinary portland cement (OPC) concrete to the status of most used synthetic material on Earth. While the 20th century was characterized by the emergence of computer technology, computational science and engineering, and instrumental analysis, the fundamental composition of portland cement has remained surprisingly constant. And, although our understanding of ordinary portland cement (OPC) chemistry has grown tremendously, the intermediate steps in hydration and the nature of calcium silicate hydrate (C-S-H), the major product of OPC hydration, remain clouded in uncertainty. Nonetheless, the century also witnessed great advances in the materials technology of cement despite the uncertain understanding of its most fundamental components. Unfortunately, OPC also has a tremendous consumption-based environmental impact, and concrete made from OPC has a poor strength-to-weight ratio. If these challenges are not addressed, the dominance of OPC could wane over the next 100 years. With this in mind, this paper envisions what the 21st century holds in store for OPC in terms of the driving forces that will shape our continued use of this material. Will a new material replace OPC, and concrete as we know it today, as the preeminent infrastructure construction material?

Use of tombstones in investigation of deterioration of stone monuments

A number of researchers have used tombstones to study the deterioration of stone. The tombstones can provide a large number of samples for statistical analyses. Measurements have included index of legibility, microrelief of resistant inclusions, and loss of thickness. Lack of information about past exposure conditions makes it difficult to derive quantitative relationships. The most useful results involve ranking of stone durability, and identification of time periods or geographic regions with high rates of stone deterioration.

Numerical simulation of the PGNA signal from chlorine diffusion gradients in concrete.

A nondestructive test method for detecting chlorides in concrete has been developed based on prompt gamma neutron activation (PGNA). Its performance has been modeled using a hybrid MCNP/optical ray tracing approach. Since the chlorides often come from de-icing salts applied to the concrete surface, the Cl concentration has a non-linear depth profile which is typically modeled by the erfc function. The signals from this distribution have been simulated for several significant Cl capture peaks to estimate the erfc function parameters.

Rock varnish on architectural stone: microscopy and analysis of nanoscale manganese oxide deposits on the Smithsonian Castle, Washington, DC

The Smithsonian Institution Building, commonly referred to as the Castle, is located on the National Mall in Washington, DC, and was constructed in the mid-nineteenth century for the purpose of housing all museum and scientific functions for the newly formed institution. Matching gateposts designed by the Castle’s architect were erected more than a century later in the Enid A. Haupt Garden opposite the Castle. Black patches were recently noted on both structures, which are clad with locally quarried Seneca red sandstone. Portable x-ray fluorescence (XRF) spectrometry links the discoloration with elevated Mn concentrations. The discolored patches resemble rock varnish, a Mn-rich coating observed on rock surfaces formed in a variety of environments. Bulk rock and varnish chemistry, in addition to microscopy and microanalysis of the varnish, are presented here. On a bulk chemical basis, the Seneca sandstone is relatively poor in Mn, containing ~500xa0ppmw. In contrast, the rock varnish is greatly enriched in Mn relative to the stone and to a lesser degree in Pb, Ca, Zn, Cu and Ni. Cross sections of the black encrusted regions show that the stone’s red coloration has been modified by black pigmentation from the surface down to ~250xa0μm. X-ray diffraction of blackened particles produced no discernable pattern, indicating concentrations below the detection limit, poor crystallinity, or both. Scanning electron microscopy and EDS-based x-ray microanalysis of the uppermost portion of the cross section reveal nanometer scale (<20–200xa0nm) Mn-rich and clay particles concentrated in a thin film (≪1xa0μm) at the surface. Additionally, Mn oxide particles decorate the surfaces of fine-grained minerals in sandstone pores within the discolored zone. Imaging and microanalysis of the rock surface reveal that the Mn-rich varnish is a discontinuous film ≪1xa0μm in thickness with an estimated composition of Na0.2Ca0.1Mg0.1Al0.1Si0.5Mn1.9Fe0.5O6.7. This composition most likely represents a nanoscale mixture of a Mn oxide (e.g., birnessite or todorokite) and an Al-rich silicate mineral. Seneca sandstone on the Smithsonian Castle and gateposts is discolored in patches owing to the Mn-rich phase being deposited into two zones: (1) a vanishingly thin patina, and (2) nanoparticles coating grain boundaries and pores in the uppermost ~200–250xa0μm of the stone. While the mineralogy is similar to well-studied varnish formed in arid settings, rock varnish on the Smithsonian structures is significantly thinner. Because this architectural rock varnish is young, it may represent the earliest stages of formation of the more commonly described varnishes reported in the literature.Graphical abstractRock varnish on the red sandstone of the Smithsonian’s Castle is associated with elevated Mn concentrations. Fragments of the garden gateposts have been sampled for detailed analysis, including portable x-ray fluorescence spectrometry, light microscopy, and scanning electron microscopy/x-ray microanalysis. The varnish discolors the red stone down to ~0.25 mm, and forms a discontinuous surface coating enriched in Mn relative to Fe

Neutron/gamma-ray techniques for investigating the deterioration of historic buildings

Abstract The degradation of building materials is a major problem for the preservation of historic structures. The presence of contaminants in the constituent materials is often a cause of the deterioration. Neutron-induced, prompt gamma-ray techniques for nondestructive elemental analysis are used to determine the distribution of contaminants in building walls. The application of these methods for the diagnosis of an 18th century historic building indicates that the distributions within the building walls of moisture, salt and bulk density can be obtained. The results of an analysis of the gamma-ray spectra are confirmed by independent measurements on two sample cores taken through one wall.

Heavy ion beam measurement of the hydration of cementitious materials.

The setting and development of strength of Portland cement concrete depends upon the reaction of water with various phases in the Portland cement. Nuclear resonance reaction analysis (NRRA) involving the (1)H((15)N,alpha,gamma)(12)C reaction has been applied to measure the hydrogen depth profile in the few 100 nm thick surface layer that controls the early stage of the reaction. Specific topics that have been investigated include the reactivity of individual cementitious phases and the effects of accelerators and retarders.

Manganese in Black Crusts on Seneca Sandstone

Introduction: Scattered black deposits are found on surfaces of the Smithsonian Castle (1849-1855) and Enid Haupt Garden Gateposts (1987), as seen in Figures 1A. The structures are made of Seneca sandstone, an arkosic micaceous sandstone quarried near Washington, DC. Photographs document that deposits have increased on the relatively new gateposts over the last six years. Generally, black deposits on sandstone are attributed to solubilized silica that incorporates dark particulate material [1]. XRF analysis of a sample taken from a gatepost (Fig. 1B) and in situ analysis of deposits on the Castle instead indicate that the deposits are manganese rich, likely colored by small amounts of manganese oxide. The deposits are thus comparable to desert varnishes on sandstone, which contain mineralized manganese and sometimes iron as a result microbial action [2, 3]. Normally soiling on buildings is associated with moisture and rainwater patterns, and the seemingly random locations of the manganese-rich deposits without a clear relationship to water remain a puzzle. Manganese-rich black deposits have not been reported on other sandstone buildings in temperate climates; it is not clear to what extent they are present elsewhere and may have been incorrectly identified. Correct characterization of such deposits is important from a conservation standpoint in order to determine the most effective method of removal, if required.

Progress in Nanoscale Studies of Hydrogen Reactions in Construction Materials

Nuclear resonance reaction analysis (NRRA) has been applied to measure the nanoscale distribution of hydrogen with depth in the hydration of cementitious phases. This has provided a better understanding of the mechanisms and kinetics of cement hydration during the induction period that is critical to improved concrete technology. NRRA was also applied to measure the hydrogen depth profiles in other materials used in concrete construction such as fly ash and steel. By varying the incident beam energy one measures a profile with a depth resolution of a few nanometers. Time-resolved measurements are achieved by stopping the chemical reactions at specific times. Effects of temperature, sulfate concentration, accelerators and retarders, and superplasticizers have been investigated. Hydration of fly ashes has been studied with synthetic glass specimens whose chemical compositions are modeled on those of actual fly ashes. A combinatorial chemistry approach was used where glasses of different compositions are hydrated in various solutions for a fixed time. The resulting hydrogen depth profiles show significant differences in hydrated phases, rates of depth penetration and amount of surface etching. Hydrogen embrittlement of steel was studied on slow strain rate specimens under different corrosion potentials.

The Fractal Ratio as a Metric of Nanostructure Development in Hydrating Cement Paste

It is necessary to have appropriate metrics to quantify the development of the nanostructure in Portland cement paste. The fractal ratio, calculated from Small Angle Neutron Scattering (SANS) data, serves as such a metric. It expresses the proportion of the volume-fractal surface area of calcium-silicate-hydrate gel (C-S-H) to the surface-fractal surface area. The volume fractal develops in the scale range from ≈ 5 nm to ≈ 100 nm, and it is associated with the formation of outer product in the capillary pore space by the through-solution mechanism. The surface fractal is attributed to the surface structure formed by colloidal particles on solid substrates such as the Portland cement grains and fly ash particles. The evolution of this ratio over time provides insight into which types of hydration processes are dominant. Applied to study of the hydration of fly ash/Portland cement mixes at later ages, the fractal ratio method showed that in every case, except two, there was a reduced hydration rate due to the dilution effect. The two exceptions involved fly ash fractions with sufficient CaO to generate significant C-S-H gel by the alkali-activated reaction. In all cases the fractal ratio increased with time, indicating the production of additional C-S-H through the topochemical reaction.