IntroductionPaper-based products have occupied much public attention as eco-friendly, convenient, and multi-purpose materials having a wide range of applications [1][2][3]. A paper sheet fundamentally has a layered, porous micronetwork architecture consisting of hydrophilic cellulosic pulp fibers. That structure results in excellent liquid absorptive properties, especially for water. The wetting characteristics of solid material surfaces are of great importance from a practical viewpoint. In the case of paper materials, adequate water-repellency, the so-called sizing effect, has been required for improvement of printing quality by ink-bleeding control, runability of coating operation, durability of liquid containers, and other surface characteristics [4]. Thus, sizing phenomena and mechanisms are of great interest for fundamental research and for functional design of cellulosic fiberbased materials.Paper sizing treatments provide a controllable slowdown of water penetration into the porous fiber network of hydrophilic paper sheets. Control is achieved by using small amounts of sizing agents with proper retention aids, through internal additive addition or surface coating systems. In particular, sizing systems with rosin acids and aluminum sulfate (alum) have long been widely applied in the industrial papermaking process, because they are highly effective, have good cost performance, and are easily used. Rosin acids as a sizing agent are a mixture of amphipathic diterpenes comprising hydrophobic rings and a hydrophilic carboxyl group. Alum, a typical retention aid of rosin sizes, plays key roles in size retention and sizing appearance both in internal and surface sizing treatments [4].Effective rosin-alum sizing systems have attracted much attention as surface modification processes for cellulosic fiber-based materials. For that reason a great deal of effort has been directed toward such unique sizing systems. Those systems have been discussed on the basis of the chemical reaction between rosin acids and aluminum components [5][6][7][8][9], and the size retention [10-13] and distribution on paper sheets [14][15][16][17][18][19]. In our previous report involving emulsion rosin sizing with alum, it was shown that free size acids in their original form directly contributed to effective sizing appearance of paper sheets, while the aluminum salts of size components were either absent or were minor components [7][8][9]. Elemental analysis revealed that the aluminum species in alum-added paper sheets were present as oxidized compounds [20,21]. Consequently, an Department of Forest and Forest Products Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan ( Present address:Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan)Abstract: The attractive force acting at a carboxyl group of a fatty acid/oxidized aluminum interface was precisely determined by atomic force microscopy (AFM). The correlation of the att...