Cellulose nanocrystals (CNCs) are ideal reinforcing agents for polymer nanocomposites because they are lightweight and nano‐sized with a large aspect ratio and high elastic modulus. To overcome the poor compatibility of hydrophilic CNCs in non‐polar composite matrices, we grafted poly(methyl methacrylate) (PMMA) from the surface of CNCs using an aqueous, one‐pot, free radical polymerization method with ceric ammonium nitrate as the initiator. The hybrid nanoparticles were characterized by CP/MAS NMR, X‐ray photoelectron spectroscopy, infrared spectroscopy, contact angle, thermogravimetric analysis, X‐ray diffraction, and atomic force microscopy. Spectroscopy demonstrates that 0.11 g/g (11 wt %) PMMA is grafted from the CNC surface, giving PMMA‐g‐CNCs, which are similar in size and crystallinity to unmodified CNCs but have an onset of thermal degradation 45 °C lower. Nanocomposites were prepared by compounding unmodified CNCs and PMMA‐g‐CNCs (0.0025–0.02 g/g (0.25–2 wt %) loading) with PMMA using melt mixing and wet ball milling. CNCs improved the performance of melt‐mixed nanocomposites at 0.02 g/g (2 wt %) loading compared to the PMMA control, while lower loadings of CNCs and all loadings of PMMA‐g‐CNCs did not. The difference in Young's modulus between unmodified CNC and polymer‐grafted CNC composites was generally insignificant. Overall, ball‐milled composites had inferior mechanical and rheological properties compared to melt‐mixed composites. Scanning electron microscopy showed aggregation in the samples with CNCs, but more pronounced aggregation with PMMA‐g‐CNCs. Despite improving interfacial compatibility between the nanoparticles and the matrix, the effect of PMMA‐g‐CNC aggregation and decreased thermal stability dominated the composite performance.
A new, unique system for the continuous dyeing of cellulose is reported. It requires dyes containing phosphorus acid subgroups which are believed to condense with the active hydrogen on the cellulose to join the chromophore through the phosphorus atom. This takes place in the presence of cyanamide-type compounds and heat. The dyes are applied at pH 5 to 6, and so are suitable for co-application with disperse dyes. This process lowers the cost of continuous dyeing of cotton in polyester blends compared to disperse-vat dye systems, while retaining the wet colorfastness typical of reactive systems. A full range of shades can be obtained, and the difference between dyeings on mercerized and un mercized cloth is slight. Both the dyeing and printing processes have been shown in full-scale production to be readily suitable for use in existing plants without the need for new equipment, and are applicable to typical commercial fabrics.
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