This is a self-archived preprint version of the Journal of the American Ceramic Society article that appears in volume 96,

issue 3, pages 885-891. doi: 10.1111/jace.12175

Modeling Rehydration/Rehydroxylation Mass Gain Curves from Davenport Ceramics Patrick K. Bowen1, Jaroslaw Drelich1, and Timothy J. Scarlett2
1

Department of Materials Science and Engineering; 2 Department of Social Sciences Michigan Technological University, Houghton, MI 49931, USA

Abstract Rehydroxylation ceramic dating, a new technique that has shown promise as an archaeometric breakthrough, was applied to XIX-century samples of Davenport ceramics from Parowan, Utah in the United States. The samples were dried at 500C to remove both physically and chemically bonded water and then exposed to a 20% relative humidity air to record the progression of rehydration/rehydroxylation over a period of 40 days. Both time1/4 and time1/n analyses were applied to the experimental mass gain vs. time results in an attempt to find the most appropriate treatment for the data. The time1/4 analysis yielded poor reproducibility and non-ideal fitting results to the Stage II mass gain, in which water reacts with meta-clays. Application of the time1/n model, where n is the rehydroxylation exponent, improved the apparent linearity of Stage II mass gain in small samples. However, the time1/n treatment still provided a poor fit to data from larger specimens, indicating that some secondary effects related to sample size and water transport may exist. To examine the effects of porosity and macrostructure on rehydration/rehydroxylation processes, a pulverized sample of the same material was analyzed, resulting in improved sample-to-sample agreement in time1/n irrespective of mass variations. These findings have implications on the application of rehydroxylation ceramic dating. Keywords: rehydroxylation; kinetics; modeling; fired clay ceramic Corresponding authors: P. K. Bowen pkbowen@mtu.edu, J. Drelich jwdrelic@mtu.edu

1.

Introduction

An archaeological ceramic sample may be returned to its original, as-fired state of hydration by reheating it to remove all physically bonded and chemically bonded (hydroxyl) water. Over time, such refired ceramic samples regain both types of water through rehydration and rehydroxylation processes, respectively. These phenomena were expounded on in a recent review of fired-clay ceramic hygral activity by Hamilton and Hall.1 In addition, Clegg et al. demonstrated that the water lost from archaeological samples during reheating was replaced after exposure to humid air.2 The water vapor present in the atmosphere is sufficient to drive the rehydration/rehydroxylation process, which can be divided into the initial gain of physically bonded (i.e. adsorbed) water and the reaction of water with meta-clays in the sample. It is has been observed that both processes proceed concurrently at early times, thus comprising Stage I behavior. At longer times, mass gain due to rehydroxylation (the chemical reaction step) is dominant after the mass of physically bonded water has reached a state of dynamic equilibrium; this gives rise to Stage II behavior. Wilson et al. determined that volume expansion and mass gain in Stage II were governed by a time1/4 power law.3; 4; 5; 6 They described this behavior using the following empirical equation:

( )

(Eq. 1)

Here, the mass (m) as a function of time (t) at constant temperature (T) and humidity (H) is controlled by the rehydroxylation rate constant (). The rehydroxylation rate constant was shown to be thermally activated according to an Arrhenius law.7 The (time)1/4 power law allows one to calculate a calendar date for ceramic manufacture if used in conjunction with: (1) the asreceived sample mass, including all waters of rehydration and rehydroxylation at the

experimental humidity; (2) the mass of an artifact measured after reheating and subsequent dehydroxylation; and (3) the mean lifetime environmental temperature. Originally, the technique required truncation at the data at a point where the data appeared linear with time1/4, or the beginning of the steady state. In the original work of Wilson et al. it was argued that steady-state data could be selected while retaining extrapolative integrity,7 but previous experimental observations for the Davenport (Utah) ceramic failed to support this assertion.8 The authors proposed a more complete, two-stage empirical equationpresented as Equation 2that expands upon the power law of Wilson et al. and attempts to incorporate the acquisition of physically bonded water.

( )

))

(Eq. 2)

Here, the mass is broken into three terms: the first is a term that describes the early pickup of physically bonded water, the second is a term that relies on a generalized version of Wilson et al.s power law to describe the kinetics of rehydroxylation mass gain, and the third is the nominal mass of the sample (). The totality of physically bonded water acquired by the sample () is gradually collected at a rate determined by the Lagergren equations kinetic term ().9 While the first term does not work to separate and quantify all the various kinetic processes taking place during Stage I, it does serve as a reasonable approximation for the aggregate physical mass gain as evidenced by a high precision of fit in previous work8 and data presented herein. The rate of hydroxyl water pickup is dictated by a rehydroxylation rate constant () in addition to a rehydroxylation exponent (n). Wilson et al. effectively posited that the rehydroxylation exponent is universally equal to four,3; 4 while the authors previous

work with the Davenport ceramic has identified an apparent dependence of n on temperature.8 When fractional mass gain is discussed, the nominal sample mass () term is 0 g/g. In this study, sherds of XIX-century Davenport fired clay ceramics from Parowan, Utah (Utah State Site Number 42IN2737) were examined.10; 11 These fragments of unglazed kiln wasters are byproducts of ceramic vessel production. The depositional feature from which these fragments were retrieved is believed to contain kiln wasters from a single, catastrophic firing accident. While updraft kiln firing can create chaotic conditions, these samples exhibit identical hardness, composition, color, and texture. Thus, the firing temperature should be constant from sherd-tosherd. The Davenport ceramics were previously shown by the authors8 to contain myriad mineralogical components, including the minerals albite, anorthite, sanidine, biotite, rutile, and quartz. The clay mineral illite was also tentatively identified. Thermal reaction products included diopside and mullite, which indicate relatively high firing temperatures. Firing at high temperatures could have played a role in establishing the rate of rehydroxylation by promoting consumption of meta-claysthe agents of rehydroxylationby secondary reactions.12 Calcite was identified as a product of weathering and mineralogical reconstruction13 in the calcareous sample. Thermogravimetric analysis revealed that a large decrease in mass occurred at approximately 600C, likely responding to both rapid final dehydroxylation and concurrent thermal decomposition of calcite. Drebushchak et al. defined the upper bound of the dehydroxylation temperature range to be approximately 600C in a recent thermogravimetric study.14 This contribution focuses on fitting high precision, well-controlled rehydroxylation mass gain data to both the time1/4 power law (Equation 1) as well as the time1/n empirical model of rehydration/rehydroxylation mass gain (Equation 2). The previous report by the authors

examined the effects of temperature and humidity fluctuations.8 The influence of sample size and morphology is of particular interest in this work, as these issues have not been addressed in other published reports. Also of concern is the overall consistency of such fitting results and effect on an extrapolated date of manufacture. 2. 2.1. Materials and Methods Davenport ceramic artifacts

After their recovery during excavation, the Davenport ceramic sherds were initially washed with tap water in the field to remove sediment before study and storage. Samples selected for analysis were then washed again with warm tap water and a soft brush to remove all loose debris and chips that could become detached during the experiments. The samples were dabbed dry to remove surface water and then left to equilibrate in the laboratory environment for several months before the start of rehydration/rehydroxylation mass-gain experiments. Five sherds were selected for concurrent evaluation. Because of the original manufacture process and depositional situation, these sherds are as geochemically similar as practically possible for fired-clay ceramic artifacts, but samples had differing nominal masses in the range 0.91.8 g. Photographs of the ceramic fragments are presented with scales in Figure 1. After the initial experiments, another set of Davenport samples were powdered to evaluate the effect of sample morphology and macroporosity upon rehydration/rehydroxylation kinetics. Large, unglazed sherds of ceramic that had not been previously dehydroxylated were selected for crushing. After being cleaned as previously described and left to dry, the large sherds were pulverized to < 100 m in an impact mill, which operated well below dehydroxylation temperatures. Under a scanning electron microscope, typical particle diameters were

approximately 315 m, though some particles were as large as 50100 m. Two samples of the resulting powder were monitored for mass gain and had nominal masses in the range of 0.51 g.

2.2.

Rehydration/rehydroxylation experiments and analysis

The samples were first dried to remove physically bonded and capillary water (corresponding to dehydration) at approximately 110 5C for 30 to 50 hours and then weighed using a Citizens CM-11 microbalance (Citizen Scale Inc.) with 1 g precision. Chemically bonded water was removed (corresponding to dehydroxylation) in a furnace by heating the samples to 500C for 45 hours. After heat treatment, samples were allowed to cool in the low-humidity environment of a desiccator until almost reaching room temperature. The powdered ceramic samples were placed in aluminum boats to minimize any static interactions with the microbalance. When the samples had reached rehydration temperatures (< 100C) and could be safely handled, they were placed in a constant-humidity glove box (Coy Laboratory Products; Grass Lake, MI) in which the microbalance was operated (Figure 2). The glove box was equipped with dehumidification systems (both a desiccation circuit and dry N2 injection), a heating fan, and a humidification apparatus; only the dehumidification systems were used during the experiments reported here. The samples remained in the glove boxs controlled environment for the duration of the experiment. The mass of each sample was measured and recorded periodically for 40 days (for both intact and powder samples) at the highest possible precision (1 g). To enhance fitting accuracy, multiple data points were recorded on the first day of experimentation. All data reported in this contribution were limited to the room temperature of 22 1C and a humidity set point of 20% RH (working values of 18.320.3% RH). All samples were subjected equally to any systematic, daily drifts in air temperature.

Fitting to the aforementioned time1/n empirical model (Equation 2) was performed with a MATLAB script that fit the time-dependent, normalized mass gain data (m/m0, where m is the mass gain relative to m0, and m0 is the mass after drying at 500C) in a least squares fashion using the nlinfit function. Fitting parameters and their corresponding 95% confidence intervals were retrieved and tabulated. Fits were only made to the complete data set (that is, only from t = 0 to test completion). 3. 3.1. Results & Discussion Intact Davenport sherds

3.1.1. Conventional time1/4 analysis The time1/4 correlation was first used to evaluate the mass gain data collected from the intact ceramic sherds, keeping with the methodology of Wilson et al. 7 To preclude data from Stage I from influencing the kinetic measurements, the first eight points were eliminated from the regression analysis. The rehydration/rehydroxylation mass gain data and second stage regression lines are presented in Figure 3. The rehydroxylation rate constants (Stage II slopes) for these intact specimens are organized in Table 1. The most apparent differences between samples analyzed in time1/4 (Figure 3 and Table 1) are the sherds relative rehydroxylation rate constants. The spread in Stage II slope is incredibly wide, ranging from 195 to 661 /hr1/4; the maximum rate is more than three times the minimum. While these values are generally similar to other reported rate constants for pottery sherds,15 this spread should not be observed, as rehydroxylation behavior should theoretically be constant over this set of identical samples. Random error cannot explain this behavior per se; all samples had essentially the same mineralogical composition and the testing was identical sample-to-sample 7

with respect to humidity, temperature, and time. Furthermore, there appears to be no range in the several weeks of Stage II behavior over which the rehydroxylation rate constants could possibly match between samples at the extremes, indicating that modifying the data truncation to achieve uniform Stage II linearity would be futile. Another feature of the time1/4 analysis in Figure 3 that is worth noting is the apparent curvature of each data set with respect to the linear trend line. Every sample appears to curve with respect to the best-fit line: the data begin below the line but peak above the trend line at ~4 hr1/4 only to return and terminate below the best fit line. This indicates consistent concave-down curvature with respect to time1/4. The nonlinearity is especially pronounced in the larger sherds, but all samples exhibit this behavior to some degree. It is worth noting that curvature would not be observed if the reported data extended to only ~44.5 hr1/4. Because the curvature resulted in an unsatisfactory fit when analyzed in time1/4, a generalized power law analysis was conducted. 3.1.2. Generalized power law (time1/n) analysis When the mass gain data were analyzed with the MATLAB fitting script, lines of best fit were commonly seen to have n values of around four. Convergence was not observed at n values very different from four unless the parameter was negative. This would imply that samples lost adsorbed water mass post-heating, which, of course, is highly unlikely. Convergence with a > 0 criterion was consistent over a wide range of initial parameters and resulted in the fitting parameters presented in Table 2. The sample that experienced the lowest mass gain, which had an initial mass of 1.175746 g, did not converge on a sensible solution due to having little Stage I mass gain. Therefore, only the four other samples are discussed in this analysis and presented in Figure 4. The average n value of 3.92 0.23 (standard deviation) is in good agreement with the authors previously published results for the same class of artifacts.8 8

The first, and probably most pronounced, sample-to-sample difference seen in the Table 2 data is that the fit to Stage II data becomes increasingly degenerate as the nominal sample mass increases. The confidence interval, indicative of the precision of the fit in Stage II, becomes progressively wider with increasing nominal mass as seen in Table 2 for both and n. The values of and n for this set of samples and their associated errors corresponding to the 95% confidence interval are presented in Figure 5 for visual comparison. It should be noted that the large error in the time1/n analysis is largely a result of allowing four separate variables to be fit, as opposed to only two in the time1/4 analysis. As mentioned above, the data sets for all four were subjected to identical sources of error. Hence, the increasingly poor fits result exclusively from real variations in sample behavior. Visual examination of the time1/n mass-gain plots contained in Figure 4 reveal that there is a clear departure from linearity in the Stage II region with increasing sample mass. The observed nonlinearity is in good agreement with the confidence interval trend previously discussed. The lightest sample, at ~1 g nominal mass, exhibits Stage II behavior that is well-described well by a time1/n model and follow, to a first approximation, a time1/4 correlation. Some minor curvature may be observed, but it appears to be reduced relative to the time1/4 fit. As the sample mass approaches ~2 g (i.e. Davenport sherd 4), however, the Stage II data still depart drastically from the time1/n line. It is clear from these best-fit lines that allowing n to vary does not eliminate curvature in all cases. Variation of the initial fitting parameters failed to produce a linear form in Stage II without irrational results for Stage I (i.e. < 0 or >> 1). The departure from Stage II linearity is, again, characterized by a concave-down curvature. It follows that when the nominal sample mass is small, Stage II behavior converges to approximately time1/n behavior, where n is approximately four at ambient temperature and moderate (20%) relative humidity.

However, when the sample mass is large, Davenport ceramic Stage II behavior apparently diverges from a general time1/n law. It could be argued that slow penetration of physically bonded water in the larger samples is responsible for these deviations. To evaluate this hypothesis, the times to 99% complete rehydration, t0.99, may be calculated from the parameter via Equation 3.
( )

(Eq. 3)

In this equation, the value of is obtained by fitting mass-gain data to Equation 2, and is related to adsorption kinetics as described by the Lagergren rate equation.9 The resulting values for t0.99 are presented in Table 3. It is seen from these values that the near-totality of physically bonded water appears to be present at about 5 hours for the smallest sample and 16 hours for the largest. A larger sample mass implies a larger internal surface area and, arguably, the total adsorbed water would therefore take longer to reach all internal pore surfaces. Indeed, there does appear to be some correlation of estimated adsorption time with the nominal sample mass, as shown in Figure 6 (with error bars representing standard deviation). From these calculated data, slow penetration by water vapor does not appear to be a viable explanation for this kinetic deviation based on the times to complete adsorption. Even if the error in the t0.99 calculations were as much as 100%, this socalled adsorption lag would still only affect the mass-gain to a maximum time of ~3035 hours (~2.32.5 hr1/4). The major concave-down curvature lasts from approximately 100 hours to 1000 hours (~3.15.7 hr1/4); hence, it is not likely that slow vapor penetration is responsible for these kinetic deviations.

10

The combined effects of Stage II departure from linearity and widely varying parameters (see Table 2 and Figure 5) make chronometric dating exceedingly difficult. These four samples represent a highly idealized case: four nearly identical, unglazed samples with similar geometries that vary from ~0.9 to ~1.7 g in mass with virtually identical geochemistries and depositional histories, in addition to concurrent data collection under identical lab processes and conditions. Even with these excessive control protocols in place, the kinetics of rehydroxylation for Davenport samples was measured to be very different from sample-to-sample both in apparent functional form and in magnitude. These findings cast serious doubt on the reproducibility of rehydroxylation mass gain measurements from sample-to-sample if minor variations in sherd mass have such drastic consequences. Because of these experiments, more work was required to determine whether size effects were unique to the porous solid ceramic. Geometric effects were eliminated by performing rehydroxylation experimentation on powdered Davenport ceramic samples. 3.2. Davenport powder curve fitting results

The long-term mass gain of the pulverized Davenport ceramic samples exhibited good agreement between samples. The pair of samples analyzed yielded consistent, strongly convergent fits to the time1/n power law, as shown in Figure 7. This figure shows the mass gain plots in both linear time and in time1/n. It should be noted that the apparent sample-to-sample disagreement in time1/n is strictly a result of different values of n; the intent of this presentation is to show the good linearity of the data with respect to the fitting line. The individual fitting parameters corresponding to the time1/n best fit lines are presented in Table 4. It is seen from these data that both samples fit best to a time1/n law (Equation 2) when the mean n was significantly less than four. The rehydroxylation exponents were not significantly different from one another. The

11

presentation of the data in time1/n (Figure 7 inset) shows that these data exhibited outstanding linearity in comparison to the time1/n fits performed on intact sherd data in Figure 4. The mean parameters for both powder samples are larger than was observed for their intact counterparts (Table 4), indicating relatively rapid adsorption of atmospheric water. The time to 99% adsorption (t0.99) was calculated to be 2.4 0.9 hours for the smaller sample (0.545349 g) and 2.8 0.8 hours for the larger sample (0.926432 g) using Equation 3. Powdering may have partially opened the meso- and micropore networks, allowing for relatively rapid penetration of atmospheric water. The observed similarity between rehydroxylation rate constants () is outstanding for the powder relative to intact sherds. The powdered samples had dissimilar masses, different by 70%, so some variation in the observed kinetics were expected based on the previous results comprising samples of differing masses (Figure 3). Instead, the two powdered samples showed quite similar rate constants; the constants differed by a statistically insignificant amount. In contrast, intact sherds of comparable mass difference (0.990702 and 1.710195 ga 73% mass difference) exhibited best-fit rehydroxylation rate constants that were dissimilar to 95% confidence in both the time1/n and time1/4 regimes. These powder results indicate that reproducibility in mass-gain experimentation may be improved by modifying the samples form to a uniform shape and size, such as a powder. This is analogous to what Wilson et al. have done in using a water-cooled saw to prepare samples of uniform geometry and, presumably, quite consistent nominal mass.15 The question of using rehydration/rehydroxylation analysis of a powdered sample to perform chronometric dating of the original consolidated porous ceramic sample will need to be answered in future research. The authors suspect that fundamental kinetic differences will preclude this approach.

12

3.3.

Archaeometric implications

These outcomes have direct implications related to the widespread application of rehydroxylation ceramic dating. First, this technique is apparently destructive if the results obtained are to be reproducible. It is apparent from the Figure 3 results that ceramic samples of nonuniform shape and size do not produce comparable mass gain data. It is acknowledged that data collection for 40 days may not be sufficient to quantify the rehydroxylation behavior to high precision. Nevertheless, the scatter in observed rehydroxylation rates is likely too large to be attributed to errors in extrapolation. Hence, any ceramics evaluated in future tests may have to be physically modified (i.e. cut into uniform sections) prior to experimentation. The relative firing temperatures and thermal phases present in the same family of artifacts, while not applicable directly to this study, also appear to be factors worthy of consideration in any future work. The physical restrictions that apply to modification of artifacts are not well established. For example, whether a cut sample should retain at least one critical dimension (i.e. thickness) is unclear from the work performed heretofore. It is evident that large samples exhibit some secondary effects on mass gain that produce undesirable curvature in the Stage II region. The curvature apparently lasts up to (and possibly beyond) a time of ~40 days in Davenport ceramics. At this time, the origin of the observed curvature is unclear. It is now apparent, however, that a power law (time1/n or time1/4) approach in its current form may not be entirely suitable for modeling the behavior of samples above some threshold size, at least for these Davenport ceramics. Small fired clay ceramic sherds and powder samples, it seems, do not suffer from this problem. These morphological requirementssmall, consistent sample size or powdering to achieve consistencyhave implications for the application of rehydroxylation ceramic dating to 13

collections of antiquities and archaeological artifacts. Curators at museums that hold collections of intact ceramic vessels must be aware that any dating using the rehydroxylation process will require a small sample be extracted from an object. These requirements would likely make application of this technique unpalatable for institutional collections of antiquities. For archaeological collections, however, these parameters could easily be built into research designs, fieldwork practice, and curatorial agreements. The second implication of these findings is that the mean chronometric date may be somewhat different based on the fitting technique used. If one assumes a universal n value of four, a different chronometric date will be obtained than if one allows n to vary. An example of this may be constructed by using data from the 0.990702 g Davenport sherd. This sample exhibited relatively good linearity in the time1/n analysis (Figure 4) and had a best-fit rehydroxylation exponent not significantly different from four. (Note that the mean n is almost precisely four for the 1.646445 g sherd, but the Stage II linearity in Figure 4 was comparatively poor.) Extrapolation to the fractional mass gain corresponding to the as-received specimen is illustrated in Figure 8. Extrapolation of the best-fit lines using parameters in Table 1 and Table 2 yielded mean extrapolated age measurements of 436 days and 407 days in the time1/4 and time1/n regimes, respectively. The disagreement between extrapolation methods is greater than 7%. These extrapolated dates are not chronometrically accurate because experiments were not carried out at the mean temperature for Parowan, Utah, and the samples were not properly equilibrated with respect to humidity before rehydration/rehydroxylation tests. Nevertheless, the two treatments are suitable for direct comparison. It should be noted that use of an accurate ambient temperature would lower the slope of both Stage II lines, thus magnifying the extrapolative mismatch (all else being equal).16 This disagreement is cause for concern; research teams

14

working on rehydroxylation dating should consider comparative testing of the different power law treatments. 4. Conclusions

Mass-gain data corresponding to rehydration/rehydroxylation from intact sherds and pulverized samples of Davenport ceramic were collected and analyzed. A conventional time1/4 analysis revealed drastically different rehydroxylation rate constants for the intact Davenport sherds. Undesirable curvature was apparent in the Stage II region relative to the line of best fit in time1/4. By comparison, a fit using an empirical time1/n model was performed which resulted in an improvement in Stage II linearity in smaller sherds. However, data collected from larger samples still did not conform to a generalized power law. In an effort to eliminate any internal structure- and size-related effects, powdered samples of Davenport ceramic were tested. A time1/n analysis on powder samples with dissimilar masses revealed comparable rehydroxylation kinetics. Thus, forcing the samples to assume a consistent form appears to enhance reproducibility. Implications related to the application of rehydroxylation ceramic dating were discussed, including (1) the apparent destructive nature of the technique and (2) the wide variation in extrapolated age that may be observed between time1/4 and time1/n treatments. Work on other sample types and by other groups is necessary to examine the universality of n=4 and to address the apparent variation in rate constant and/or extrapolated chronometric date that appears to affect the Davenport ceramic samples. 5. Acknowledgements

The authors acknowledge funding for instrumentation by the Archaeology and Archaeometry program in the Division of Behavioral and Cognitive Sciences of the National Science

15

Foundation (award no. 1112327). The DeVlieg Foundation is also acknowledged for providing support for PKB. The authors thank Emily Shearier for her assistance editing this document. Finally, thanks are due to the 2009 archeological field team; Steve and Mark Matheson; Todd Prince, Park Manager, Frontier Homestead State Park Museum; and Karen Krieger, Deputy Director Administration, Utah State Parks, Department of Natural Resources for their assistance in obtaining the Davenport ceramic samples in Parowan, Utah. 6.
1

References

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F. Clegg, C. Breen, M. A. Carter, C. Ince, S. D. Savage, M. A. Wilson, and W. Lee, "Dehydroxylation and rehydroxylation mechanisms in fired clay ceramic: a TG-MS and DRIFTS investigation," J Am Ceram Soc, 95[1] 416-22 (2012).

M. A. Wilson, W. D. Hoff, C. Hall, B. McKay, and A. Hiley, "Kinetics of moisture expansion in fired clay ceramics: a (time)(1/4) law," Phys Rev Lett, 90[12] 125503 (2003).

S. D. Savage, M. A. Wilson, M. A. Carter, W. D. Hoff, C. Hall, and B. Mckay, "Moisture expansion and mass gain in fired clay ceramics: a two-stage (time)(1/4) process," J Phys D Appl Phys, 41[5] 055402 (2008).

S. D. Savage, M. A. Wilson, M. A. Carter, B. Mckay, W. D. Hoff, and C. Hall, "Mass Gain due to the Chemical Recombination of Water in Fired Clay Brick," J Am Ceram Soc, 91[10] 3396-98 (2008).

C. Hall, M. A. Wilson, and W. D. Hoff, "Kinetics of Long-Term Moisture Expansion in FiredClay Brick," J Am Ceram Soc, 94[11] 3651-54 (2011).

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M. A. Wilson, M. A. Carter, C. Hall, W. D. Hoff, C. Ince, S. D. Savage, B. Mckay, and I. M. Betts, "Dating fired-clay ceramics using long-term power law rehydroxylation kinetics," Proc R Soc A, 465[2108] 2407-15 (2009).

P. K. Bowen, H. J. Ranck, T. J. Scarlett, and J. W. Drelich, "Rehydration/Rehydroxylation Kinetics of Reheated XIX-Century Davenport (Utah) Ceramic," J Am Ceram Soc, 94[8] 2585-91 (2011).

S. Y. Lagergren, "Zur Theorie der sogenannten Adsorption gelster Stoffe," K Sven Vetenskapsakad Handl, 24[4] 1-39 (1898).

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T. J. Scarlett, R. J. Speakman, and M. D. Glascock, "Pottery in the Mormon economy: An historical, archaeological, and archaeometric study," Hist Archaeol, 41[4] 72-97 (2007).

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J. F. Montcalm, "A Burning Question: Archaeology at the Davenport Pottery and Technological Adaptation in the Mormon Domain." MS Thesis, Department of Social Sciences, Michigan Technological University, Houghton, MI, 2010.

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S. Shoval, E. Yadin, and G. Panczer, "Analysis of thermal phases in calcareous Iron Age pottery using FT-IR and Raman spectroscopy," J Therm Anal Calorim, 104[2] 515-25 (2011).

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S. Shoval, P. Beck, Y. Kirsh, D. Levy, M. Gaft, and E. Yadin, "Rehydroxyiation of clay minerals and hydration in ancient pottery from the Land of Geshur," J Therm Anal, 37[7] 1579-92 (1991).

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V. A. Drebushchak, L. N. Mylnikova, and T. N. Drebushchak, "The mass-loss diagram for the ancient ceramics," J Therm Anal Calorim, 104[2] 459-66 (2011).

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M. A. Wilson, A. Hamilton, C. Ince, M. A. Carter, and C. Hall, "Rehydroxylation (RHX) dating of archaeological pottery," Proc R Soc A, 468[2147] 3476-93 (2012).

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C. Hall, A. Hamilton, and M. A. Wilson, "The influence of temperature on rehydroxylation [RHX] kinetics in archaeological pottery," J Archaeol Sci, 40[1] 305-12 (2013).

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Figure 1 Photographs of the Davenport sherds labeled with their respective nominal masses.

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Figure 2 Glove box with microbalance used in rehydration/rehydroxylation experiments.

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Figure 3 Time1/4 presentation of Davenport rehydration/rehydroxylation data with trend lines corresponding to Stage II mass gain. The inset directly compares the Stage II slopes in time1/4.

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Figure 4 Compiled fitting results for intact Davenport sherds in time1/n.

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Figure 5 Visual presentation of rehydroxylation exponent (left, dotted line at n=4) and the rehydroxylation rate constant (right) for the Davenport sherds. Observe that the error bars, representing the 95% confidence interval, increase with increasing sample mass.

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Figure 6 Visual presentation of the characteristic adsorption times for Davenport ceramic as a function of nominal sample mass. Error bars correspond to one standard deviation.

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Figure 7 Mass-gain plots from pulverized Davenport ceramic with time1/n lines of best fit, presented in linear time and in time1/n (inset).

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Figure 8 Extrapolation to the as-received mass using the time1/4 and time1/n lines of best fit.

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Table 1 Time1/4 rehydroxylation rate constants for Davenport sherds Nominal Mass (g) (10-6/hr1/4) 0.990702 1.175746 1.498214 1.646445 1.710195 661 10. 195 7 524 8 496 11 293 11

Table 2 Time1/n equation fitting parameters for Davenport sherds Nominal Mass (g) (10-3/hr) (g/g) (10-6/hr1/n) 0.990702 1.498214 1.646445 1.710195 872 441 447 279 942 1210 970. 430. n

570. 91 3.77 0.25 430. 86 3.68 0.30 522 125 4.08 0.43 324 128 4.15 0.72

Table 3 Characteristic water adsorption completion times for Davenport sherds; errors are standard deviation Nominal Mass (g) 0.990702 1.498214 1.646445 1.710195 t0.99 (hr) 5.3 1.0 10.4 0.6 10.3 1.0 16.5 3.7 t0.991/n (hr) 1.6 1.9 1.8 2.0

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Table 4 - Time1/n equation fitting parameters for Davenport powder Nominal Mass (g) (10-3/hr) (g/g) (10-6/hr1/n) 0.545349 0.926432 2372 2817 735. 755. n

325 66 3.03 0.23 425 72 3.42 0.24

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