The moisture transfer coefficient is a key parameter for analyzing the moisture-based physical properties of materials and studying the heat–moisture coupling process within building envelopes. The liquid-water transfer coefficient, as an important aspect of this process, plays a significant role, especially under high-humidity conditions. However, the global research on liquid-water transfer coefficients is still far from complete. To further enhance the research on liquid-water transfer coefficients, this study conducted capillary water absorption experiments on seven traditional and new porous building materials, focusing on testing the moisture transfer coefficients, primarily the liquid-water transfer coefficient. A novel analysis regarding the impact of sealing materials was proposed, based on the experimental results. Based on the experimental data, the concept of a critical value related to the variation in the capillary moisture content and the liquid-water diffusion coefficient was raised, and, building upon traditional empirical models, a completely new computational model was proposed. Data processing was carried out using methods such as variability analysis, correlation analysis, and nonlinear regression for model fitting. The research findings indicate the following: (1) The capillary water absorption rate and capacity of a material are influenced by its density and porosity. (2) In terms of sealing materials, self-adhesive films performed better than non-adhesive films. (3) The concept of critical capillary moisture content was proposed, based on the rate of change in the liquid-water diffusion coefficient. For the threshold of w ≤ 80%, a new calculation model with a higher correlation coefficient was proposed which can meet the calculation requirements of the diffusion coefficient under the vast majority of relative-humidity conditions.
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