This protocol describes the procedure to express fresh pore solution from cementitious systems and the measurement of its ionic composition using X-ray fluorescence. The ionic composition can be used to calculate pore solution electrical resistivity, which can be used, together with concrete electrical resistivity, to determine the formation factor.
The goal of this method is to determine the chemical composition and electrical resistivity of cementitious pore solution expressed from a fresh paste sample. The pore solution is expressed from a fresh paste sample using a pressurized nitrogen gas system. The pore solution is then immediately transferred to a syringe to minimize evaporation and carbonation. After that, assembled testing containers are used for the X-ray fluorescence (XRF) measurement. These containers consist of two concentric plastic cylinders and a polypropylene film which seals one of the two open sides. The pore solution is added into the container immediately prior to the XRF measurement. The XRF is calibrated to detect the main ionic species in the pore solution, in particular, sodium (Na+), potassium (K+), calcium (Ca2+), and sulfide (S2-), to calculate sulfate (SO42-) using stoichiometry. The hydroxides (OH–) can be calculated from a charge balance. To calculate the electrical resistivity of the solution, the concentrations of the main ionic species and a model by Snyder et al. are used. The electrical resistivity of the pore solution can be used, along with the electrical resistivity of concrete, to determine the formation factor of concrete. XRF is a potential alternative to current methods to determine the composition of pore solution, which can provide benefits in terms of reduction in time and costs.
The transport properties of concrete are determined by its formation factor, which is a fundamental measure of the microstructure1. The formation factor is defined as the inverse of the product between the connectivity and the porosity of a concrete2. The formation factor can be calculated from the ratio of the electrical resistivity of concrete and the electrical resistivity of pore solution as presented in equation 13.
(1)
Here,
= electrical resistivity of bulk or concrete (Ωm);
= electrical resistivity of pore solution (Ωm).
The bulk electrical resistivity of concrete may be easily determined on hardened concrete using a resistivity meter, following approaches outlined in AASHTO PP84-17 Appendix X2 and other literature4,5. The purpose of this article is to provide instructions for expressing the pore solution from fresh paste and analysis of the solution ionic composition using X-ray fluorescence (XRF) spectroscopy. The expressed pore solution is tested in the XRF using commercially available materials (cylinders and film). The ionic composition detected by the XRF can be used for multiple concrete durability applications and can also be used to calculate the electrical resistivity of pore solution, to ultimately determine the formation factor6.
Current methods to determine the chemical composition of pore solution, such as inductively coupled plasma (ICP)7, atomic absorption spectroscopy (AAS)8, and ion chromatography (IC)9, can be costly, time-consuming, and quite laborious. Additionally, in some cases, a combination of various methods must be used in order to obtain a complete characterization of the main ionic species in pore solution10. XRF can be used as an alternative to these methods, where the composition of pore solution can be obtained at a relatively lower cost and shorter testing time compared to conventional methods.
XRF is a technique commonly used in the cement industry as it is primarily used to analyze the chemical composition of the manufactured materials for quality control and quality assurance throughout the cement manufacturing process11,12. Therefore, this method will describe how that technique can be used to enable cement manufacturers to use this tool to provide more information about the pore solution composition of different cement batches. Overall, using XRF for pore solutions could potentially extend the use of this technique for multiple applications and could be implemented in the industry relatively quickly.
1. Pore Solution Expression13
2. Assembly of the Solution Containers
3. XRF Application Development and Solution Calibration
4. XRF Analysis
5. Ionic Concentration Calculation
6. Resistivity Calculation
In this section, representative outcomes of each major step in the methodology are presented. This is done in order to obtain an idea of what is expected at the end of each step and provide useful tips to ensure a correct application of the method.
The first important step consists in the expression of the pore solution from the fresh paste sample. Figure 2 shows a pore solution that is correctly extracted and sealed in a 5-mL syringe. The pore solution in the figure was expressed from a fresh ordinary Portland cement paste with a water-to-cement ratio of 0.36. The sample was mixed 10 min before the image was taken. The pore solution is expected to be clear; however, the color can vary depending on the type of cementitious materials that were used and the age of the sample at the time of the expression.
Before the XRF measurement of the extracted pore solution, it is necessary to calibrate the instrument. In particular, each element whose ionic concentration will be measured needs to be calibrated. A representative calibration plot of the potassium (K+) ions is shown in Figure 3. The figure shows the fitting performed by the software on the intensities measured by the XRF. Note that the root mean square (RMS) error of the fitting should stay below 5%.
After calibration, it is recommended to test a solution of known ionic concentration to determine the accuracy of the machine. The measured composition of the ions using XRF is compared to the theoretical composition of both solutions. According to our experience, assuming a correct preparation of the ionic solutions, this checking step should yield a percentage of errors lower than ± 5%. Figure 4 shows the composition results for the spot-checking of the solutions. When the spot-checking yields a percentage of errors higher than ± 5%, repeat the calibration of the XRF device.
Table 2 shows a representative set of results for composition and resistivity. While the ionic concentration of the pore solution can vary widely depending on the chemical composition of the cement, the water-to-cement ratio of the system, and the presence of supplementary cementitious materials19, reference values can be obtained from the literature20 for the main ions, as shown in Table 1.
Finally, when calculating the resistivity of a sample, values for early age pore solutions are typically expected to be within 0.05 and 0.25 Ωm14. Now that the resistivity of the pore solution is known, the bulk resistivity can be obtained using other methods, like uniaxial resistivity, in order to, ultimately, calculate the formation factor, which is typically over 2,000 for good quality concrete4,5,18.
Figure 1: Assembly of the pore solution extraction system. The system consists of a main expression device, a nitrogen tank and tube with a safety pressure gauge and regulator, and a collection container. Always refer to the manufacturer's instructions and safety precautions for the specific system used. Please click here to view a larger version of this figure.
Figure 2: Correctly extracted and sealed extracted pore solution in a 5-mL syringe. The extracted pore solution should appear clear (i.e., no visible particles) and should be sealed with no air bubbles within the syringe.
Figure 3: Representative calibration plot of potassium (K+). The x-axis shows the imputed (known) concentrations in ppm, and the y-axis shows the detected (measured) intensities with XRF in cpm. The calibration line calculated from one of the correction models in the software should have the smallest RMS (%), as discussed in section 3 of the protocol. Please click here to view a larger version of this figure.
Figure 4: Sodium ion (Na+) and potassium ion (K+) verification plot. The dashed line represents a 1:1 ratio.The verification plot should show a good correlation (almost a 1:1 relationship with a high R-squared value) between the known concentrations of the sodium and potassium ions and the detected concentrations using XRF. Please click here to view a larger version of this figure.
Ionic Species (i) | Equivalent conductivity at infinite dilution (λ˚i) | Empirical conductivity coefficient |
(i) | (zλ°i) | (Gi) |
(cm2 S/mol) | (mol/L)-1/2 | |
Sodium (Na+) | 50.1 | 0.733 |
Potassium (K+) | 73.5 | 0.548 |
Calcium (Ca2+) | 59 | 0.771 |
Hydroxide (OH–) | 198 | 0.353 |
Sulfate (SO42-) | 79 | 0.877 |
Table 1: Equivalent conductivity at infinite dilution () and empirical conductivity coefficients (
) for each ionic species obtained from the literature11. These values are used in order to calculate the electrical resistivity of the pore solution.
Ionic Species | Concentration |
(i) | (mol/L) |
Sodium (Na+) | 0.16 |
Potassium (K+) | 0.39 |
Calcium (Ca2+) | 0.02 |
Hydroxide (OH–) | 0.18 |
Sulfate (SO42-) | 0.2 |
Resistivity (Ωm) | 0.156 |
Table 2: Representative results for the composition and resistivity of a cement paste with a water-to-cement ratio of 0.36 at 10 min. The values in this table are examples of the results obtained using this method.
Since this is a sensitive chemical analysis method, it is imperative to have laboratory practices that prevent contamination. For this method, it is critical that the calibration standards are specifically performed with high-purity chemicals (> 99%). When transferring the pore solution into the syringe, make sure that no visible cement grains are present in the solution to avoid any changes in the pore solution. When stored in a sealed syringe at a constant temperature of 5 ± 1 °C, the pore solution has been observed to maintain an unaltered chemical composition for up to 7 days.
One of the main limitations of this protocol is that the method of expression outlined can only be used for fresh paste specimens and is not suitable for later age samples. For later age or hardened samples, a method of expression using a high-pressure extraction die20 is needed. Another limitation is that a minimum amount of 2 g of solution is needed to test in the XRF since an amount less than 2 g does not provide a constant sample height that can cover the entire bottom face of the container. This last limitation applies to the particular set-up that was used in this study. A different set-up would probably allow a reduction in the minimum amount of pore solution required for the testing. Another limitation is that the model is not likely applicable to systems containing slag-rich cements since species such as bisulfide (HS–) may be present, as discussed by Vollpracht et al.14.
Since XRF is a commonly used technique in the cement industry, this method could potentially enable cement manufacturers to use a tool already at their disposal to provide more information about the cementitious pore solution, such as the chemical composition and resistivity for numerous applications and at a lower cost and testing time than conventional methods. For example, when comparing sample preparation and testing time between ICP (a commonly used testing method for pore solution composition), the testing time is reduced from 50 min per sample to 8 min per sample using XRF. This method could extend the applications for XRF and could potentially be implemented fairly quickly in the industry.
XRF can be used to determine the main elemental concentrations in the pore solution. This suggests the use of XRF for applications such as (i) determining the composition of pore solutions to study the dissolution kinetics of cementitious phases21 or (ii) determining the effect of chemical admixtures22. Early age pore solution and concrete resistivity measurements could be used as a measure of the water-to-cement ratio of concrete, which could potentially be used in quality control.
The authors have nothing to disclose.
The authors would like to acknowledge partial financial support from the Kiewit Transportation Institute and the Federal Highway Administration (FHWA) through DTFH61-12-H-00010. All of the laboratory work presented herein was performed at the Kiewit Transportation Institute at Oregon State University.
Energy Disperssive X-Ray Fluorescence Benchtop Spectrometer | Malvern PANalytical | Epsilon 3XLE or Epsilon 4 | |
35 mm Sample Cups for Liquids | Malvern PANalytical | 9425 888 00024 | Panalytical Consumables Catalogue 2016 for XRF Accessories and Consumables Catalog |
4 micron Polypropylene Film | Malvern PANalytical | 9425 888 00029 | Panalytical Consumables Catalogue 2016 for XRF Accessories and Consumables Catalog |
Syringe, 5 mL | VWR | 53548-005 | HSW Norm-Ject Sterile Luer-Slip syringes, Air-Tite |
Needle, 16Gx1'' | VWR | 89219-334 | Premium Veterinary Hypodermic Needles, Sterile, Air-Tite |
Container | VWR | 15704-092 | VWR Specimen containers, Polypropylene with Polyethylene Caps |
Pressurized Filter Holder | EMD Millipore | XX4004700 | 100 mL capacity, 47 mm filter diameter |
MCE Membrane Filter | PALL | 63069 | 47 mm diameter, 0.45 μm pore size |
Silicone Funnell | SpiceLuxe | SLP-122513-F1 | Top opening 2 1/2″, Bottom opening 3/4″, Height 2 3/4″ |