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Sorption properties of paper treated with silane-modified starch
AbstractSorption properties of paper products are important when applying paper as the packaging material. Hydrophobicity, i.e. reduced affinity of paper surface to liquid water, is of particular importance from the point of view of the direct impact on packed goods. However, hygroscopicity of the material is significant during storage of goods. The analysis of changes in the hygroscopic properties of paper products induced by the treatment with silane modified starch was presented. The results on the hygroscopicity of treated paper were related to the previously published results on the hydrophobicity. The discrete values of equilibrium moisture content allowed constructing adsorption and desorption isotherms. The three-parameter Guggenheim, Anderson, and De Boer (GAB) model, the four-parameter Generalized D’Arcy and Watt (GDW), and Yanniotis and Blahovec (Y-B) sorption isotherm models were used to quantify the hygroscopic properties for all options of untreated and modified paper samples. The effectiveness of silanes for improving hygroscopic properties was determined and compared to their impact on hydrophobicity of the studied materials. It was found that 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane was the only silane improving hydrophobic and hygroscopic properties. The analysis of the applied models of sorption isotherms depicted that the GAB model was not valid for describing water sorption isotherms in the case of the tested materials, while the GDW and Y-B models provided a much more realistic description of water sorption mechanisms. The evaluation of the results of fitting the GDW model indicated that water molecules bonding to the primary sites was the dominating mechanism of sorption.
Interlaboratory study of the operational stability of automated sorption balances
AbstractAutomated sorption balances are widely used for characterizing the interaction of water vapor with hygroscopic materials. These instruments provide an efficient way to collect sorption isotherm data and kinetic data. A typical method for defining equilibrium after a step change in relative humidity (RH) is using a particular threshold value for the rate of change in mass with time. Recent studies indicate that commonly used threshold values yield substantial errors and that further measurements are needed at extended hold times as a basis to assess the accuracy of abbreviated equilibration criteria. However, the mass measurement accuracy at extended times depends on the operational stability of the instrument. Published data on the stability of automated sorption balances are rare. An interlaboratory study was undertaken to investigate equilibration criteria for automated sorption balances. This paper focuses on the mass, temperature, and RH stability and includes data from 25 laboratories throughout the world. An initial target for instrument mass stability was met on the first attempt in many cases, but several instruments were found to have unexpectedly large instabilities. The sources of these instabilities were investigated and greatly reduced. This paper highlights the importance of verifying operational mass stability of automated sorption balances, gives a method to perform stability checks, and provides guidance on identifying and correcting common sources of mass instability.
Hydrophobic and hygroscopic properties of cellulose treated with silicone agents
AbstractThe effects of various cellulose treatments on the hydrophobic properties and sorption behavior with respect to liquid water uptake and water vapor sorption were examined within the study. Different hydrophobic agents based on silicon compounds were applied to improve the properties of cellulose-based sheets. The 1H,1H,2H,2H perfluorooctyltriethoxysilane treatment increased hydrophobicity significantly, while N-octyltriethoxysilane and inorganic sodium silicate solution treatments only slightly affected the properties. Silicone-cellulose interaction varied, influencing the fiber saturation and moisture content of the material. The swelling differences between untreated and treated cellulose and, consequently, the uncovering of new active sorption sites during a swelling process and the increase in the content of bound water were confirmed by the T2 relaxation times analysis. The GDW sorption model estimated maximum water content but lacked activation dynamics. The blocking phenomenon of active sorption sites together with silicone improved hydrophobicity had different mechanisms for applied agents. The 1H,1H,2H,2H perfluorooctyltriethoxysilane additionally cross-linked silane structure and restricted cellulose swelling.
Transient water vapor diffusion in paper treated with methyltrimethoxysilane modified starch
Abstract The interaction of cellulose paper with water is a major hindrance to its broader application. This study, which introduces a novel approach to understand water vapor diffusion in both untreated and treated paper, aims to identify the diffusion coefficient, a crucial property in improving the hydrophobicity of paper. The treatment process utilized an aqueous solution of starch or starch modified with methyltrimethoxysilane (MTMS). While the initial sorption method is frequently used to determine the diffusion coefficient, this study found that it could lead to significant errors due to the non-Fickian behavior exhibited by lignocellulosic materials. This behavior causes that the hygroscopic equilibrium is not instantly obtained by surface of paper. It also induces slowing down moisture diffusion in its final stage due to molecular relaxation. For the first time, the modified convective boundary condition was introduced into the moisture diffusion model in paper materials. The results from vapor sorption experiments demonstrated this non-Fickian behavior, particularly at high values of air relative humidity. The study also revealed that the commonly applied first kind boundary condition is not applicable, even for thin paper samples, inhibiting the use of the initial sorption method for determining the diffusion coefficient. While the treatment with starch and MTMS significantly improved the hydrophobic properties of paper, it didn’t alter substantially its hygroscopic properties, potentially due to not blocking active sorption sites of cellulose fibers. This research underscores the need for further investigation into the chemical modification of cellulose fibers to improve the hydrophobicity of paper.
Interlaboratory study of the quality of water vapor sorption data for wood from automated sorption balances
Abstract Automated sorption balances are widely used for characterizing the interaction of water vapor with hygroscopic materials. This paper is part of an interlaboratory study investigating the stability and performance of automated sorption balances. A previous paper in this study investigated the mass, temperature, and relative humidity (RH) stability of automated sorption balances by looking at the mass change of a non-hygroscopic sample over time. In this study, we examine the mass stability of wood samples held at constant RH for seven to ten days after a step change. The reason for the long hold times was to collect data to “operational equilibrium” where the change in mass is on the order of the inherent operational stability of the instrument. A total of 80 datasets were acquired from 21 laboratories covering absorption with final RH levels ranging from 10 to 95%. During these long hold times, several unusual behaviors were observed in the mass-vs-time curves. Deviations from expected sorption behavior were examined by fitting the data to an empirical sorption kinetics model and calculating the root mean square error (RMSE) between the observed and smoothed behavior. Samples that had a large RMSE relative to the median RMSE of the other datasets often had one of several types of errors: abrupt disturbances, diurnal oscillations, or long-term mass decline during an absorption step. In many cases, mass fluctuations were correlated with changes in the water reservoir temperature of the automated sorption balance. We discuss potential errors in sorption measurements on hygroscopic materials and suggest an acceptable level of RMSE for sorption data.