Sustainable Development and Concrete Technology, May 2004

For a variety of reasons, the concrete construction industry is not sustainable. First, it consumes huge quantities of virgin materials. Second, the principal binder in concrete is portland cement, the production of which is a major contributor to greenhouse gas emissions that are implicated in global warming and climate change. Third, many concrete structures suffer from lack of durability which has an adverse effect on the resource productivity of the industry. Because the high-volume fly ash concrete system addresses all three sustainability issues, its adoption will enable the concrete construction industry to become more sustainable. In this paper, a brief review is presented of the theory and construction practice with concrete mixtures containing more than 50% fly ash by mass of the cementitious material. Mechanisms are discussed by which the incorporation of high volume of fly ash in concrete reduces the water demand, improves the workability, minimizes cracking due to thermal and drying shrinkage, and enhances durability to reinforcement corrosion, sulfate attack, and alkali-silica expansion. For countries like China and India, this technology can play an important role in meeting the huge demand for infrastructure in a sustainable manner.

Development of Performance Properties of Ternary Mixes: Scoping Study, June 2005

Pozzolans and slag extend the market for concrete products by improving specific properties of the products, which allows the products to be constructed with materials or placed in environments that would have precluded the use of portland cement alone. In properly formulated concrete mixes, pozzolans and slag have been shown to enhance long-term strength, decrease permeability, increase durability, reduce thermal cracking of mass concrete, minimize or eliminate cracking related to alkali-silica reaction (ASR), and minimize or eliminate cracking related to sulfate attack. The purpose of this research project was to conduct a scoping study that could be used to evaluate the need for additional research in the area of supplementary cementitious materials (SCMs) that are used in concrete for highway applications. Special emphasis was given to the concept of using two or more SCMs in a single concrete mixture. The scope of the study was limited to a literature survey and panel discussions concerning issues relevant to the project. No laboratory work was conducted for this project. A problem statement with research plan was created that could be used to guide a pooled fund project.

Materials and Mix Optimization Procedures for PCC Pavements, March 2006

Severe environmental conditions, coupled with the routine use of deicing chemicals and increasing traffic volume, tend to place extreme demands on portland cement concrete (PCC) pavements. In most instances, engineers have been able to specify and build PCC pavements that met these challenges. However, there have also been reports of premature deterioration that could not be specifically attributed to a single cause. Modern concrete mixtures have evolved to become very complex chemical systems. The complexity can be attributed to both the number of ingredients used in any given mixture and the various types and sources of the ingredients supplied to any given project. Local environmental conditions can also influence the outcome of paving projects. This research project investigated important variables that impact the homogeneity and rheology of concrete mixtures. The project consisted of a field study and a laboratory study. The field study collected information from six different projects in Iowa. The information that was collected during the field study documented cementitious material properties, plastic concrete properties, and hardened concrete properties. The laboratory study was used to develop baseline mixture variability information for the field study. It also investigated plastic concrete properties using various new devices to evaluate rheology and mixing efficiency. In addition, the lab study evaluated a strategy for the optimization of mortar and concrete mixtures containing supplementary cementitious materials. The results of the field studies indicated that the quality management concrete (QMC) mixtures being placed in the state generally exhibited good uniformity and good to excellent workability. Hardened concrete properties (compressive strength and hardened air content) were also satisfactory. The uniformity of the raw cementitious materials that were used on the projects could not be monitored as closely as was desired by the investigators; however, the information that was gathered indicated that the bulk chemical composition of most materials streams was reasonably uniform. Specific minerals phases in the cementitious materials were less uniform than the bulk chemical composition. The results of the laboratory study indicated that ternary mixtures show significant promise for improving the performance of concrete mixtures. The lab study also verified the results from prior projects that have indicated that bassanite is typically the major sulfate phase that is present in Iowa cements. This causes the cements to exhibit premature stiffening problems (false set) in laboratory testing. Fly ash helps to reduce the impact of premature stiffening because it behaves like a low-range water reducer in most instances. The premature stiffening problem can also be alleviated by increasing the water–cement ratio of the mixture and providing a remix cycle for the mixture.

Evaluation of Microcracking and Chemical Deterioration in Concrete Pavements, October 31, 1995

The major objective of this research project was to investigate the chemistry and morphology of portland cement concrete pavements in Iowa. The integrity of the various pavements was evaluated qualitatively, based on the presence or absence of microcracks, the presence or absence of sulfate minerals, and the presence or absence of alkali-silica gel(s). Major equipment delays and subsequent equipment replacements resulted in significant delays over the course of this research project. However, all these details were resolved and the equipment is currently in place and fully operational. The equipment that was purchased for this project included: (I) a LECO VP 50, 12-inch diameter, variable speed grinder/polisher: (2) a Hitachi S-2460N variable pressure scanning electron microscope; and (3) a OXFORD Instruments Link ISIS microanalysis system with a GEM (high-purity germanium) X-ray detector. This study has indicated that many of the concrete pavements contained evidence of multiple deterioration mechanisms: and hence, the identification of a single reason for the distress that was observed in any given pavement typically had to be based on opinion rather than empirical evidence.

Evaluation of Microcracking and Chemical Deterioration in Concrete Pavements Final Report, October 31, 1995

The major objective of this research project was to investigate the chemistry and morphology of portland cement concrete pavements in Iowa. The integrity of the various pavements was evaluated qualitatively, based on the presence or absence of microcracks, the presence or absence of sulfate minerals, and the presence or absence of alkali-silica gel(s). Major equipment delays and subsequent equipment replacements resulted in significant delays over the course of this research project. However, all these details were resolved and the equipment is currently in place and fully operational. The equipment that was purchased for this project included: ( I ) a LECO VP 50, 12-inch diameter, variable speed grinder/polisher: (2) a Hitachi S-2460N variable pressure scanning electron microscope; and (3) a OXFORD Instruments Link ISIS microanalysis system with a GEM (high-purity germanium) X-ray detector. This study has indicated that many of the concrete pavements contained evidence of multiple deterioration mechanisms: and hence, the identification of a single reason for the distress that was observed in any given pavement typically had to be based on opinion rather than empirical evidence.

Reduction of Concrete Deterioration by Ettringite Using Crystal Growth Inhibition Techniques, TR-431, 2001

Many researchers have concluded that secondary or delayed ettringite is responsible for serious premature deterioration of concrete highways. In some poorly performing Iowa concretes, ettringite is the most common secondary mineral but its role in premature deterioration is uncertain since some researchers still maintain that secondary ettringite does not itself cause deterioration. The current research project was designed to determine experimentally if it is possible to reduce secondary ettringite formation in concrete by treating the concrete with commercial crystallization inhibitor chemicals. The hypothesis is such that if the amount of ettringite is reduced, there will also be a concomitant reduction of concrete expansion and cracking. If both ettringite formation and deterioration are simultaneously reduced, then the case for ettringite induced expansion/cracking is strengthened. The experiment used four commercial inhibitors - two phosphonates, a polyacrylic acid, and a phosphate ester. Concrete blocks were subjected to continuous immersion, wet/dry and freeze/thaw cycling in sodium sulfate solutions and in sulfate solutions containing an inhibitor. The two phosphonate inhibitors, Dequest 2060 and Dequest 2010, manufactured by Monsanto Co., were effective in reducing ettringite nucleation and growth in concrete. Two other inhibitors, Good-rite K752 and Wayhib S were somewhat effective, but less so than the two phosphonates. Rapid experiments with solution growth inhibition of ettringite without the presence of concrete phases were used to explore the mechanisms of inhibition of this mineral. Reduction of new ettringite formation in concrete blocks also reduced expansion and cracking of the blocks. This relationship clearly links concrete expansion with this mineral - a conclusion that some research workers have disputed despite theoretical arguments for such a relationship and despite numerous observations of ettringite mineralization in prematurely deteriorated concrete highways. Secondary ettringite nucleation and growth must cause concrete expansion because the only known effect of the inhibitor chemicals is to reduce crystal nucleation and growth, and the inhibitors cannot in any other way be responsible for the reduction in expansion. The mechanism of operation of the inhibitors on ettringite reduction is not entirely clear but the solution growth experiments show that they prevent crystallization of a soluble ettringite precursor gel. The present study shows that ettringite growth alone is not responsible for expansion cracking because the experiments showed that most expansion occurs under wet/dry cycling, less under freeze/thaw cycling, and least under continuous soaking conditions. It was concluded from the different amounts of damage that water absorption by newly-formed, minute ettringite crystals is responsible for part of the observed expansion under wet/dry conditions, and that reduction of freeze resistance by ettringite filling of air-entrainment voids is also important in freeze/thaw environments.

Development of a Rational Characterization Method for Iowa Fly Ash, HR-286, 1988

This research project was conducted in an attempt to determine the cause of paste strength variability in Iowa fly ashes and to develop test methods to more adequately reflect fly ash physical and chemical characteristics. An extensive three year sampling and testing program was developed and initiated which incorporated fly ash from several Iowa power plants. Power plant design and operating data were collected. The variability was directly linked to power plant maintenance schedules and to sodium carbonate coal pretreatment. Fly ash physical and chemical properties can change drastically immediately before and after a maintenance outage. The concentrations of sulfate bearing minerals in the fly ash increases sharply during shutdown. Chemical, mineralogical, and physical testing indicated that the sodium, sulfate bearing minerals, lime and tricalcium aluminate contents of the fly ashes play important roles in the development of hydration reaction products in fly ash pastes. The weak pastes always contained ettringite as the major reaction product. The strong pastes contained straetlingite and monosulfoaluminate as the major reaction products along with minor amounts of ettringite. Recommendations for testing procedure changes and suggested interim test methods are presented.

Effects of Deicing Salt Trace Compounds on Deterioration of Portland Cement Concrete, HR-271, 1987

A study was made of the detrimental effects of trace amounts of calcium sulfate (occurring naturally in halite deposits used for deicing) on portland cement concrete pavements. It was found that sulfate introduced as gypsum with sodium chloride in deicing brines can have detrimental effects on portland cement mortar. Concentrations of sulfate as low as 0.5% of the solute rendered the brine destructive. Conditions of brine application were critical to specimen durability. The mechanisms of deterioration were found to be due to pore filling resulting from compound formation and deposition. A field evaluation of deteriorating joints suggests that the sulfate phenomena demonstrated in the laboratory also operates in the field. A preliminary evaluation was made of remedies: limits on sulfates, fly ash admixtures, treatment of existing pavement, and salt treatments. This report gives details of the research objectives, experimental design, field testing, and possible solutions. Recommendations for further study are presented.

Evaluation of the Chemical Durability of Iowa Fly Ash Concretes, HR-327, 1993

The major objective of this research project was to investigate how Iowa fly ashes influenced the chemical durability of portland cement based materials. Chemical durability has become an area of uncertainty because of the winter application of deicer salts (rock salts) that contain a significant amount of sulfate impurities. The sulfate durability testing program consisted of monitoring portland cement-fly ash paste, mortar and concrete test specimens that had been subjected to aqueous solutions containing various concentrations of salts (both sulfate and chloride). The paste and mortar specimens were monitored for length as a function of time. The concrete test specimens were monitored for length, relative dynamic modulus and mass as a function of time. The alkali-aggregate reactivity testing program consisted of monitoring the expansion of ASTM C311 mortar bar specimens that contained three different aggregates (Pyrex glass, Oreapolis and standard Ottawa sand). The results of the sulfate durability study indicated that the paste and concrete test specimens tended to exhibit surface spalling but only very slow expansive tendencies. This suggested that the permeability of the test specimens was controlling the rate of deterioration. Concrete specimens are still being monitored because the majority of the test specimens have expanded less than 0.05%; hence, this makes it difficult to estimate the service life of the concrete test specimens or to quantify the performance of the different fly ashes that were used in the study. The results of the mortar bar studies indicated that the chemical composition of the various fly ashes did have an influence on their sulfate resistance. Typically, Clinton and Louisa fly ashes performed the best, followed by the Ottumwa, Neal 4 and then Council Bluffs fly ashes. Council Bluffs fly ash was the only fly ash that consistently reduced the sulfate resistance of the many different mortar specimens that were investigated during this study. None of the trends that were observed in the mortar bar studies have yet become evident in the concrete phase of this project. The results of the alkali-aggregate study indicated that the Oreapolis aggregate is not very sensitive to alkali attack. Two of the fly ashes, Council Bluffs and Ottumwa, tended to increase the expansion of mortar bar specimens that contained the Oreapolis aggregate. However, it was not clear if the additional expansion was due to the alkali content of the fly ash, the periclase content of the fly ash or the cristobalite content of the fly ash, since all three of these factors have been found to influence the test results.

Control of Concrete Deterioration Due to Trace Compounds in Deicers, HR-299 Phase I, 1988

This report presents the results of research on the influence of trace compounds from rock salt deicers on portland cement mortar and concrete. An evaluation of the deicers in stock throughout the state showed that about ninety-five percent contained enough sulfate to cause accelerated deterioration of concrete. Of the impurities found in rock salts, sulfate compounds of calcium and magnesium were found to be equally deleterious. Magnesium chloride was found to be innocuous. Introduction of fly ash eliminated the damage to portland cement mortar caused by sulfates. When used with frost resistant Alden aggregate in fly ash concrete and exposed to a variety of deicer brine compositions, the concrete did not deteriorate after exposure. With the exception of a high calcium brine, the behavior of the frost-prone Garrison aggregate was independent of deicer treatment; the high calcium brine reduced frost damage with this aggregate. Two approaches to reducing sulfate deterioration from deicers are suggested as (1) limiting the amount of sulfate to about 0.28 percent, and (2) making concrete sulfate-resistant by using fly ash. Techniques for making existing concrete deicer-sulfate-resistant are essential to a practical solution.

Control of Concrete Deterioration Due to Trace Compounds in Deicers, Phase II, HR-299, 1989

This report presents results of research on ways to reduce the detrimental effects of sulfate-tainted rock salt deicers on portland cement concrete used for highway pavements. Repetitious experiments on the influence of fly ash on the mortar phase of concrete showed significant improvement in resistance to deicing brines is possible. Fifteen to twenty percent by weight of fly ash replacement for portland cement was found to provide optimum improvement. Fly ashes from five sources were evaluated and all were found to be equally beneficial. Preliminary results indicate the type of coarse aggregate also plays an important role in terms of concrete resistance to freeze-thaw in deicing brines. This was particularly true for a porous ferroan dolomite thought to be capable of reaction with the brine. In this case fly ash improved the concrete, but not enough for satisfactory performance. An intermediate response was with a porous limestone where undesirable results were observed without fly ash and adequate performance was realized when 15% fly ash was added. The best combination for making deicer-resistant concrete was found to be with a non-porous limestone. Performance in brines was found to be adequate without fly ash, but better when fly ash was included. Consideration was given to treating existing hardened concrete made with poor aggregate and no fly ash to extend pavement life in the presence of deicers, particularly at joints. Sodium silicate was found to improve freeze-thaw resistance of mortar and is a good candidate for field usage because of its low cost and ease of handling.

Pooled Fund Study of Premature Concrete Pavement Deterioration, HR-1063, Supplementary Study, 1997

Recently, a number of roads have begun to exhibit the onset of deterioration at relatively early ages. Since this deterioration appears to be the result of materials issues, data concerning raw materials, design, and paving conditions have been collected and analyzed for correlation between independent variables and deterioration. This analysis shows that there is a positive and statistically significant correlation between deterioration and the following variables: alkali and sulfate content of the cementitious materials, impermeable base course, paving temperature, and the presence of fly ash. This study also concludes that there is a significant need for improvement in data collection and maintenance by many organizations responsible for the production of concrete.

Deicing Salt Corrosion with and without Inhibitors, MLR-87-8, 1989

Chloride ion penetration through concrete to reinforcing steel is causing the premature deterioration of numerous bridge decks in Iowa. The purpose of the research reported in this paper was to determine whether any of several additives or alternative deicing chemicals could inhibit corrosion of reinforcing steel. The deicers tested were calcium magnesium acetate (CMA), CMA plus NaCl (NaCl: sodium chloride), Quicksalt plus PCI, and CG-90, a polyphosphate solution being developed by Cargill. Two tests were established. First, steel coupons were placed in a 15% solution of a deicer and distilled water to determine which alternative deicer would cause the least amount of corrosion in solution. The coupons were weighed periodically to determine each coupon's weight loss from corrosion. The second test involved ponding a 15% solution of each material on reinforced concrete blocks. Weekly copper-copper sulfate electrical half-cell (CSE) potential readings were taken on each block to determine whether corrosive activity was occurring at the steel surface. When the ponding research was concluded, concrete samples were taken from one of the three blocks ponded with each deicer. The samples were used to determine the chloride ion content at the level of the steel. Results show that all the deicers were less corrosive than NaCl. Only pure CMA, however, significantly inhibited the corrosion of steel embedded in concrete.

Evaluation of Photoacoustic Spectroscopy for Quality Control of Cement, TR-409, 1998

This report discusses the feasibility of using infrared photoacoustic spectroscopy (PAS) as a viable technique that can quickly provide information on cement composition prior to use. The PAS technique is of interest because the cost is much lower than for other types of instrumentation used for mineral analysis, it requires virtually no sample preparation, and it can perform multi-component analysis in a matter of minutes. Feasibility of the technique was based on the ability of PAS to identify and quantify sulfate species and major cement matrix components. Strengths and limitations of the technique are presented.

Freeze-Thaw Durability of Concretes with Infilling of Ettringite in Voids, Phase 2, MLR-94-9, 1997

Examination of field portland cement concrete cores, from Iowa pavements with premature deterioration, reveals extensive infilling of calcium sulfate aluminum (CSA) compound in their air voids. A previous study (Phase I) has shown some evidence of the correlation between freeze-thaw durability of concretes and ettringite infilling. To further verify the previous observation, a more extensive experimental program was conducted in this Phase 2 study. A total of 101 concrete mixes were examined. Seven cements, six fly ashes, two water reducers and three coarse aggregates were used in the concrete mixes. Specimens were under moist curing for up to 223 days before being subjected to the freeze-thaw cycling. An environmental treatment consisting of three consecutive wet [70 deg F (21 deg C) in distilled water]/dry [120 deg F (49 deg C) in oven] cycles was applied to some specimens. Immediately prior to the freeze-thaw cycling, most specimens were examined by a low-vacuum scanning electron microscope (SEM) for their microstructure. The results obtained further demonstrate the correlation between concrete freeze-thaw response and CSA compound infilling in the air voids. The extent of the infilling depends on the period of moist curing as well as the wet/dry treatment. The extent of the infilling also relates to materials used. Concrete mixes with extensive infilling are more vulnerable to the freeze-thaw attack. Based on the obtained results, material criteria on cements and fly ashes for mainline paving were proposed for minimizing potential infilling of CSA compound in concrete.