Effect of the graft density of cellulose diacetate-modified layered perovskite nanosheets on mechanical properties of the transparent organic–inorganic hybrids bearing covalent bonds at the interface

Abstract

Transparent organic–inorganic hybrids with a whitish colour were prepared from cellulose diacetate (CDA) nanosheets derived from Dion–Jacobson-type ion-exchangeable layered perovskite HLaNb₂O₇·xH₂O (HLaNb) to prepare CDA-based hybrids bearing covalent bonds between HLaNb nanosheets and CDA matrices for improved mechanical properties. An n-decoxy derivative of HLaNb (C10_HLaNb) was exfoliated in acetonitrile by ultrasonication. TEM and AFM images revealed that C10_HLaNb was exfoliated into individual nanosheets. In order to explore the local environment around HLaNb nanosheets, a very small amount of CDA was reacted with a C10_HLaNb nanosheet dispersion [molar ratio COH:(NbOH + NbOC₁₀H₂₁) = 4:1] at 80 °C, and solid-state ¹³C NMR with cross polarization and magic angle spinning techniques showed that an alcohol-exchange-type reaction was proceeded to graft the CDA chains to the HLaNb nanosheets via new Nb–O–C covalent linkages. The CDA-based hybrids were prepared by dispersing 5 mass% of HLaNb nanosheets in CDA and subsequent heating at 80 °C for 1–7 days to cause a grafting reaction, and the product prepared by a 1-day grafting reaction exhibited improved mechanical properties compared to neat CDA; the Young’s modulus, tensile strength and toughness increased by 18, 34 and 78%, respectively. The mechanical properties deteriorated with further extension of the reaction period, however. In addition, a hybrid film prepared by mixing CDA and a C10_HLaNb nanosheet dispersion exhibited only a slight improvement in mechanical properties. These results clearly indicate that formation of an appropriate number of Nb–O–C bonds at the nanosheet/CDA interfaces is effective for improving mechanical properties.