The Role of Magnesium in Concrete Deterioration, HR-355, Appendix, 1994

In the main report concerning the role that magnesium may have in highway concrete aggregate, over 20,000 electron microprobe data were obtained, primarily from automated scans, or traverses, across dolomite aggregate grains and the adjacent cement paste. Representative traverses were shown in figures and averages of the data were presented in Table II. In this Appendix, detailed representative and selected analyses of carbonate aggregate only are presented. These analyses were not presented in the main report because they would be interesting to only a few specialists in dolomite· rocks. In this Appendix, individual point analyses of mineral compositions in the paste have been omitted along with dolomite compositions at grain boundaries and cracks. Clay minerals and quartz inclusions in the aggregate are also not included. In the analyses, the first three column headings from left to right show line number, x-axis, and y-axis (Line number is an artifact of the computer print-out for each new traverse. Consecutive line numbers indicate a continuous traverse with distances between each point of 1.5 to a few μ-m. X-axis and y-axis are coordinates on the electron microscope stage). The next columns present weight percent oxide content of FeO, K20, CaO, Si02, Al203, MgO, SrO, BaO, MnO, Na20, and C02 (calculated assuming the number of moles of C02 is equal to the sum of moles of oxides, chiefly CaO and MgO), TOTAL (the sum of all oxides), and total (sum of all oxides excluding COi). In many of the analyses total is omitted.

Deterioration of Iowa Highway Concrete Pavements: A Petrographic Study, HR-1065, 1999

Major highway concrete pavements in Iowa have exhibited premature deterioration attributed to effects of ettringite formation, alkali-silica expansive reactions, and to frost attack, or some combination of them. These pavements were constructed in the mid- 1980s as non-reinforced, dual-lane, roads ranging in thickness between 200 mm and 300 mm, with skewed joints reinforced with dowels. Deterioration was initially recognized with a darkening of joint regions, which occurred for some pavements as soon as four years after construction. Pavement condition ranges from severe damage to none, and there appeared to be no unequivocal materials or processing variables correlated with failure. Based upon visual examinations, petrographic evaluation, and application of materials models, the deterioration of concrete highway pavements in Iowa appear related to a freeze-thaw failure of the coarse aggregate and the mortar. Crack patterns sub-parallel to the concrete surface transecting the mortar fraction and the coarse aggregate are indicative of freeze-thaw damage of both the mortar and aggregate. The entrained air void system was marginal to substandard, and filling of some of the finer-sized voids by ettringite appears to have further degraded the air void system. The formation of secondary ettringite within the entrained air voids probably reflects a relatively high degree of concrete saturation causing the smaller voids to be filled with pore solution when the concrete freezes. Alkali-silica reaction (ASR) affects some quartz and shale in the fine aggregate, but is not considered to be a significant cause of the deterioration. Delayed ettringite formation was not deemed likely as no evidence of a uniform paste expansion was observed. The lack of field-observed expansion is also evidence against the ASR and DEF modes of deterioration. The utilization of fly ash does not appear to have affected the deterioration as all pavements with or without fly ash exhibiting substantial damage also exhibit significant filling of the entrained air void system, and specimens containing fly ash from sound pavements do not have significant filling. The influence of the mixture design, mixing, and placing must be evaluated with respect to development of an adequate entrained air void system, concrete homogeneity, longterm drying shrinkage, and microcracking. A high-sand mix may have contributed to the difficult mixture characteristics noted upon placement and exacerbate concrete heterogeneity problems, difficulty in developing an adequate entrained air void system, poor consolidation potential, and increased drying shrinkage and cracking. Finally, the availability of moisture must also be considered, as the secondary precipitation of ettringite in entrained air voids indicates they were at least partially filled with pore solution at times. Water availability at the base of the slabs, in joints, and cracks may have provided a means for absorbing water to a point of critical saturation.

Improving Portland Cement Concrete Mix Consistency and Production Rate through Two-Stage Mixing, TR-505, 2007

A two-stage mixing process for concrete involves mixing a slurry of cementitious materials and water, then adding the slurry to coarse and fine aggregate to form concrete. Some research has indicated that this process might facilitate dispersion of cementitious materials and improve cement hydration, the characteristics of the interfacial transition zone (ITZ) between aggregate and paste, and concrete homogeneity. The goal of the study was to find optimal mixing procedures for production of a homogeneous and workable mixture and quality concrete using a two-stage mixing operation. The specific objectives of the study are as follows: (1) To achieve optimal mixing energy and time for a homogeneous cementitious material, (2) To characterize the homogeneity and flow property of the pastes, (3) To investigate effective methods for coating aggregate particles with cement slurry, (4) To study the effect of the two-stage mixing procedure on concrete properties, (5) To obtain the improved production rates. Parameters measured for Phase I included: heat of hydration, maturity, and rheology tests were performed on the fresh paste samples, and compressive strength, degree of hydration, and scanning electron microscope (SEM) imaging tests were conducted on the cured specimens. For Phases II and III tests included slump and air content on fresh concrete and compressive and tensile strengths, rapid air void analysis, and rapid chloride permeability on hardened concrete.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, TR-480, Implementation Guide, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, TR-480, Executive Summary, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, Literature Review, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, Technical Appendices, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.