Evaluation of Carbonate Aggregate Using X-Ray Analysis, HR-266, 1989

Iowa has more than 13,000 miles of portland cement concrete (PCC) pavement. Some pavements have performed well for over 50 years, while others have been removed or overlaid due to the premature deterioration of joints and cracks. Some of the premature deterioration is classical D-cracking, which is attributed to a critically saturated aggregate pore system (freeze-thaw damage). However, some of the premature deterioration is related to adverse chemical reactivity involving carbonate coarse aggregate. The objective of this paper is to demonstrate the value of a chemical analysis of carbonate aggregate using X-ray equipment to identify good or poor quality. At least 1.5% dolomite is necessary in a carbonate aggregate to produce a discernible dolomite peak. The shift of the maximum-intensity X-ray diffraction dolomite d-spacing can be used to predict poor performance of a carbonate aggregate in PCC. A limestone aggregate with a low percentage of strontium (less than 0.013) and phosphorus (less than 0.010) would be expected to give good performance in PCC pavement. Poor performance in PCC pavement is expected from limestone aggregates with higher percentages (above 0.05) of strontium.

Thermogravimetric Analysis of Carbonate Aggregate, HR-336, 1994

Research has shown that one of the major contributing factors in early joint deterioration of portland cement concrete (PCC) pavement is the quality of the coarse aggregate. Conventional physical and freeze/thaw tests are slow and not satisfactory in evaluating aggregate quality. In the last ten years the Iowa DOT has been evaluating X-ray analysis and other new technologies to predict aggregate durability in PCC pavement. The objective of this research is to evaluate thermogravimetric analysis (TGA) of carbonate aggregate. The TGA testing has been conducted with a TA 2950 Thermogravimetric Analyzer. The equipment is controlled by an IBM compatible computer. A "TA Hi-RES" (trademark) software package allows for rapid testing while retaining high resolution. The carbon dioxide is driven off the dolomite fraction between 705 deg C and 745 deg C and off the calcite fraction between 905 deg C and 940 deg C. The graphical plot of the temperature and weight loss using the same sample size and test procedure demonstrates that the test is very accurate and repeatable. A substantial number of both dolomites and limestones (calcites) have been subjected to TGA testing. The slopes of the weight loss plot prior to the dolomite and calcite transitions does correlate with field performance. The noncarbonate fraction, which correlates to the acid insolubles, can be determined by TGA for most calcites and some dolomites. TGA has provided information that can be used to help predict the quality of carbonate aggregate.

Compositional and Mechanical Properties of Carbonate Rocks, HR-110, 1967

The research project, HR-110, was begun in the fall of 1964 to further investigate the compositional and mechanical properties of some of the carbonate rocks used as aggregate in portland cement concrete. Samples were taken only from those portions of the quarries that are used as aggregate in portland cement concrete by the Iowa State Highway Commission except where designated by commission personnel for purposes of evaluation of potential aggregate sources. Where practical, the samples were taken from each bed recognized by the Highway Commission geologists, and in most instances, the thicker beds were sampled at the top, middle, and bottom to detect any lithologic changes that escaped megascopic observation.

Behavior of Carbonate Rocks as Concrete Aggregates, HR-15, 1962

The problem of determining the suitability of carbonate rocks as concrete aggregates is extremely complex and calls for more new data than has been available or obtainable from usual methods. Since 1955 the approach which has served as a primary basis for the project has been to gather as much new information as possible to apply to the problem. New information obtained by new and different techniques provides better understanding. This approach was decided on since, in all prior studies, a standard petrographic and petrologic approach correlated in many instances with standard engineering tests did not provide the answer in Iowa or elsewhere. One can theorize that concrete fails (excluding external causes such as traffic, foundation failure, etc.) because of stresses of internal origin. The stresses can be of a physical nature, such as frost action, or result from chemical activity such as the alkali aggregate reaction. If, as service records show, the aggregate is considered the cause of distress in concrete, it will without doubt be the manner in which an aggregate can create or contribute to stress of internal origin by physical or chemical means. Therefore the main emphasis was placed on studying physical and chemical properties of aggregates as well as the behavior of carbonate rocks in concrete environments. Although standard geologic and engineering methods were also utilized, the approach adopted required considerable effort in devising new techniques and methods. This report is intended to be a detailed summary of the research performed. Whenever possible, the work accomplished will be summarized and all pertinent data will be included. For further details, reference to the various theses and publications transmitted with this report or at previous times will be made wherever possible.

Compositional and Mechanical Properties of Carbonate Rocks, Progress Report, HR-110, 1965

This report briefly describes the progress of HR-110 of the Iowa Highway Research Board.

Chemical Reactions Involving Aggregates, HR-15, 1960

The discussion presented below concerns the section on "Unidentified Cement-Aggregate Reactions" in which mention is made of concrete deterioration related to argillaceous dolomitic limestone aggregates. A considerable amount of research has been conducted on carbonate aggregate-cement reactions as part of the general study on the suitability of carbonate rocks as concrete aggregate which inadvertently did not reach the authors in time to be incorporated in their paper. These reactions which occur in response to the alkaline environment of concrete are not typical alkali-aggregate reactions associated with siliceous aggregates such as opaline cherts, volcanic glasses and etc. The reactions are associated with certain carbonate aggregates whose service records indicate deleterious performance in concrete has occurred. It is my purpose to review briefly carbonate aggregate research conducted at Iowa State University and present some new data on the problem of carbonate aggregate-cement paste reactions.

Relationship of Carbonate Aggregates to Concrete Aging, HR-116, 1967

HR-116 is concerned with the relationship of carbonate aggregate to aging of highway concrete. The ultimate purpose of the research is to provide the Materials Department with better criteria for selection of carbonate aggregates for use in highway concrete. The research stems from the problem in Iowa which relates durability of highway concrete to use of certain aggregates. Service records of certain highways have shown that concrete deterioration is related to the source of coarse carbonate aggregate. Research on this problem in projects HR-15 and HR-86 helped define three broad areas of the problem in more detail: 1. The problem of evaluation of rocks which pass current specifications but have poor service records 2. The basic problem of how rocks contribute to distress in concrete 3. The problem of how concrete ages or weathers.

The Relationship of Ferroan Dolomite Aggregate to Rapid Concrete Deterioration, HR-266, 1987

Some of Iowa's 13,200 miles of portland cement concrete (pcc) pavement have remained structurally sound for over 50 years while others have suffered premature deterioration. Research has shown that the type of coarse aggregate used in the pcc is the major cause of this premature deterioration. Some coarse aggregates for concrete exhibit a nonuniform performance history. They contribute to premature deterioration on heavily salted primary roadways while providing long maintenance-free life on unsalted secondary pavements. This inconsistency supports the premise that there are at least two mechanisms that contribute to the deterioration. Previous research has shown that one of these mechanisms is a bad pore system. The other is apparently a chemical reaction. The objective of this research is to develop simple rapid test methods to predict the durability of carbonate aggregate in pcc pavement. X-ray diffraction analyses of aggregate samples have been conducted on various beds from numerous quarries producing diffraction plots for more than 200 samples of dolomitic or dolomite aggregates. The crystalline structures of these dolomitic aggregates show maximum-intensity dolomite/ankerite peaks ranging from a d-spacing of 2.884 angstroms for good aggregates to a d-spacing of 2.914 angstroms for nondurable aggregates. If coarse aggregates with known bad pore systems are removed from this summary, the d-spacing values of the remaining aggregates correlate very well with expected service life. This may indicate that the iron substitution for magnesium in the dolomite crystal is associated with the instability of the ferroan dolomite aggregates in pcc pavement.

Investigation of Rapid Thermal Analysis Procedures for Prediction of the Service Life of PCCP Carbonate Coarse Aggregate, HR-337, 1993

The major objective of this research project was to use thermal analysis techniques in conjunction with x-ray analysis methods to identify and explain chemical reactions that promote aggregate related deterioration in portland cement concrete. Twenty-two different carbonate aggregate samples were subjected to a chemical testing scheme that included: • bulk chemistry (major, minor and selected trace elements) • bulk mineralogy (minor phases concentrated by acid extraction) • solid-solution in the major carbonate phases • crystallite size determinations for the major carbonate phases • a salt treatment study to evaluate the impact of deicer salts Test results from these different studies were then compared to information that had been obtained using thermogravimetric analysis techniques. Since many of the limestones and dolomites that were used in the study had extensive field service records it was possible to correlate many of the variables with service life. The results of this study have indicated that thermogravimetric analysis can play an important role in categorizing carbonate aggregates. In fact, with modern automated thermal analysis systems it should be possible to utilize such methods on a quality control basis. Strong correlations were found between several of the variables that were monitored in this study. In fact, several of the variables exhibited significant correlations to concrete service life. When the full data set was utilized (n = 18), the significant correlations to service life can be summarized as follows ( a = 5% level): • Correlation coefficient, r, = -0.73 for premature TG loss versus service life. • Correlation coefficient, r, = 0.74 for relative crystallite size versus service life. • Correlation coefficient, r, = 0.53 for ASTM C666 durability factor versus service life. • Correlation coefficient, r, = -0.52 for acid-insoluble residue versus service life. Separation of the carbonate aggregates into their mineralogical categories (i.e., calcites and dolomites) tended to increase the correlation coefficients for some specific variables (r sometimes approached 0.90); however, the reliability of such correlations was questionable because of the small number of samples that were present in this study.

Carbonate Rock Pore Size Distribution Determination through Iowa Pore Index Testing, MLR-15-01, 2015

The Iowa Pore Index (IPI) measures the pore system of carbonate (limestone and dolomite) rocks using pressurized water to infiltrate the pore system. This technique provides quantitative results for the primary and capillary (secondary) pores in carbonate rocks. These results are used in conjunction with chemical and mineralogical test results to calculate a quality number, which is used as a predictor of aggregate performance in Portland cement concrete (PCC) leading to the durability classification of the aggregate. This study had two main objectives: to determine the effect different aggregate size has on IPI test results and to establish the precision of IPI test and test apparatus. It was found that smaller aggregate size fractions could be correlated to the standard 1/2”-3/4” size sample. Generally, a particle size decrease was accompanied by a slight decrease in IPI values. The IPI testing also showed fairly good agreement of the secondary pore index number between the 1/2”-3/4”and the 3/8”-1/2” fraction. The #4-3/8” showed a greater difference of the secondary number from the 1/2”-3/4” fraction. The precision of the IPI test was established as a standard deviation (Sr) of 2.85 (Primary) and 0.87 (Secondary) with a repeatability limit (%r) of 8.5% and 14.9% for the primary and secondary values, respectively.

Investigation of Rapid Thermal Analysis Procedures for Prediction of the Service Life of PCCP Carbonate Coarse Aggregate: Phase I, Progress Report, HR-337, 1992

The major objective of this research project is to utilize thermal analysis techniques in conjunction with x-ray analysis methods to identify and explain chemical reactions that promote aggregate related deterioration in Portland cement concrete. The first year of this project has been spent obtaining and analyzing limestone and dolomite samples that exhibit a wide range of field service performance. Most of the samples chosen for the study also had laboratory durability test information (ASTM C 666, method B) that was readily available. Preliminary test results indicate that a strong relationship exists between the average crystallite size of the limestone (calcite) specimens and their apparent decomposition temperatures as measured by thermogravimetric analysis. Also, premature weight loss in the thermogravimetric analysis tests appeared to be related to the apparent decomposition temperature of the various calcite test specimens.