The effect on mechanical and barrier properties upon addition of glycerol to temperature-responsive hydrophobically modified (HM) potato starch was studied on free films. The addition of glycerol lowered the glass transition temperature, the storage modulus, and the water vapor permeability (WVP) for the HM starch films. The HM starch phase separates upon cooling below an upper critical temperature into a solid and a liquid phase. Adding glycerol to the warm starch solution had an inhibiting effect on the particulate precipitation. Substrates surface sized with HM starch with various amounts of glycerol were investigated with respect to barrier properties; WVP, contact angle and Cobb values. Hydroxypropylated starch was used as a reference. Cobb values and WVP results on surface-sized substrates indicated that the film formation properties of the starches were of great importance for the final surface properties. Good film formation properties were essential for the gas barrier and water resistance while they were less important for high contact angles. The WVP decreased as the glycerol content of the sizes increased, but no sufficient water vapor barrier could be obtained. The HM starches investigated in this work provided good oxygen barrier and the contact angles indicated a hydrophobic character of the surface. The role of the precipitate was investigated, and surface sizing with the precipitate gave low WVP and high contact angles despite its poor film-forming properties under the experimental conditions. Cobb 60 values were slightly improved for HM starch with increasing glycerol content over glycerol-free sizing.

Some starches containing quaternary dimethylalkylammonium groups exhibit an unique phase behavior. A solid phase or gel phase is formed upon cooling, i.e. they are temperature‐responsive polymers. The aim of this study was to investigate the phase and gelation behavior of hydrophobically modified quaternary ammonium starch ethers in aqueous solutions. The mechanisms behind the phase behavior and hydrophobic character were investigated by light scattering (turbidity) and rheological measurements. A relatively large increase in the complex viscosity at higher concentrations was observed when the solutions were cooled to room temperature. The phase angle decreased drastically at a certain critical temperature. The decrease in the phase angle depended on the concentration of starch in solution, higher concentrations showing the greatest decrease and lower concentrations showing no significant change. Turbidity measurements indicated that a solid‐like highly concentrated phase was precipitated. The starch with zero net charge showed a larger increase in turbidity than the starch with a positive net charge, which indicates that particular precipitation is favored by a zero net charge and that the formation of a gel network is favored by charged starch molecules.

The film-forming properties of hydrophobically modified potato starch were studied to optimize coating and surface sizing formulations for improvement of barrier properties of paper and paperboard. The spontaneous fractionation of a potato starch hydrophobically modified with a quaternary dodecylammonium chloride resulted in an amylose-rich precipitate with properties differing from those of the original starch. Film formation was investigated in the presence of glycerol and poly(vinyl alcohol) plasticizers. Anti-plasticization was found to occur at low and intermediate plasticizer levels but highly flexible, continuous films were obtained when 30 parts of plasticizer were added to 100 parts of dry starch. The highest transparency and greatest flexibility were obtained with glycerol, while the hydrophobic film properties were maintained with poly(vinyl alcohol). A study of the glass transition temperatures and melting behavior of starch-plasticizer films by differential scanning calorimetry gave useful information about the crystallinity of the films.

The aim of this study was to investigate the properties of hydrophobically modified (HM) quaterna-ry ammonium starch ethers for paper sizing. These starches possess temperature-responsive properties; that is, gelation or phase separation occurs at a certain temperature upon cooling. This insolubility of the HM starches in water at room temperature improved their performance as sizing agents. The contact angles for water on sized liner were substantially larger than on unsized liner. When the application temperature was well above the critical phase-separation temperature, larger contact angles were obtained for liner independently of pH compared with those at the lower application temperature. Cobb60 values for liner decreased upon surface sizing, with a low pH and high application temperature giving lower water penetration. Contact angles on greaseproof paper decreased upon sur-face sizing as compared to unsized greaseproof paper, independently of pH and temperature. Greaseproof paper showed no great difference between unsized substrates and substrates sized with HM starch at different pH. This is probably due to the already hydrophobic nature of greaseproof paper. However, the Cobb60 values increased at low pH and low application temperature. Surfactants were added to investigate how they affect the sized surface. Addition of surfactant reduces the contact angles, in spite of indications of complex formation.

The phase behavior of temperature-responsive hydrophobically modified starches and the interaction between oxidized potato amylose and hydrophobically modified potato amylopectin have been investigated by rheology, turbidity measurements and differential scanning calorimetry. When oxidized amylose was mixed with hydrophobically modified amylopectin, a viscosity peak was observed, indicative of a guest-host interaction between the oxidized amylose and the hydrophobically modified amylopectin. A series of oxidized and hydrophobically modified potato starches were investigated in the presence of an anionic and cationic surfactant. A coil-helix transition of the investigated starches was observed in the presence of surfactant, with the exception of a cationic surfactant combined with a hydrophobically modified zwitterionic starch of high positive net charge. The destabilizing mechanism (the phase separation) of the hydrophobically modified starches was studied as well as the difference in stabilizing capacity between the investigated cationic and anionic surfactants.