Structure-Property Relationships Governing Species Dependent Response in Alkali-Assisted Chemical-Mechanical Pulping of Hardwoods

The efficient utilization of hardwood lignocellulosic biomass has attracted increasing attention as a sustainable strategy for the high-value conversion of renewable resources. Chemical-mechanical pulping (CMP) is a promising route for hardwood utilization; however, its performance is strongly influenced by species-dependent differences in chemical composition, macromolecular structure, and physical accessibility. In this study, four representative hardwood species (poplar, sycamore, eucalyptus, and acacia) were selected as model feedstocks to investigate the relationships between structural characteristics and CMP performance in alkali-assisted systems. The chemical composition and structural features of cellulose, hemicellulose, lignin, and lignin-carbohydrate complexes were characterized, together with key physical parameters including density, porosity, and fiber morphology. The effects of alkali charge on fiber softening, fibrillation development, and paper properties were then evaluated. The results revealed pronounced species-dependent differences in alkali response, which were closely correlated with variations in cellulose supramolecular organization, hemicellulose substitution characteristics, lignin structural features, lignin-carbohydrate associations, and wood microstructure. This study provides a comprehensive qualitative comparative analysis of the relationships between wood structural features and CMP performance. Hardwoods with lower density and higher porosity exhibited more efficient alkali penetration and superior performance under mild conditions, whereas denser species such as sycamore and eucalyptus required higher alkali charge. This work provides important insights into the structure-performance relationships governing alkali-assisted CMP behavior, and offers useful guidance for the efficient utilization of lignocellulosic biomass in pulp and paper applications.