•Reactive Blue P-3R, a derivative of anthraquinone, can react directly with polyamide 56.•Benzophenone tetracarboxylic acid, a photoactive derivative of benzophenone, can also react directly with polyamide 56.•Modified polyamide 56 has excellent ultraviolet protective and photochemical properties.The bio-based material polyamide 56 (PA 56) is a new kind of biopolymer. Reactive Blue P-3R, which is a derivative of anthraquinone, can react directly with the amino groups on PA 56. 3,3′,4,4′-Benzophenone tetracarboxylic acid (BPTCA), which is a photoactive derivative of benzophenone, can also react directly with the amino groups on PA 56 to form amide bonds. The modified bio-based PA 56 fabrics not only exhibited excellent ultraviolet (UV) protective property, but also exhibited important photochemical properties, such as producing reactive oxygen species, including hydroxyl radicals (HO) under UV light exposure. The hydroxyl radical-generating abilities of these materials were measured, and their photochemical reactive mechanisms were discussed. The modified PA 56 fabrics demonstrated good antimicrobial activities against both E. coli and S. aureus. Reactive Blue P-3R and BPTCA exhibited good synergistic properties. These modified biomaterials could therefore be used in medical textiles and biological materials.Download high-res image (196KB)Download full-size image

•Novel Schiff base with a chelating group was used to modify silk fibroin membrane.•The modified membrane had the selective sorption for Pb(II) and Cd(II).•The adsorption for Cd(II) was in line with the pseudo-second-order model.•The membrane has potential application for removal heavy metal ion from solutions.Water-insoluble silk fibroin (WSF) membrane was prepared by co-blending and interaction of fibroin and silane coupling agent. A novel Schiff base with a chelating group, 3,5-bis-{2-hydroxyphenyl-5- [(2-sulphate-4- sulphatoethylsulphonyl-azobenzol) methylene amino]} benzoic acid (BHSABA), was applied to modify WSF membrane. The morphological structure and surface element analysis of WSF and its modified membrane (MWSF) were investigated by scanning electron microscopy (SEM) and energy dispersive spectrometer (SEM-EDS). The sorption behavior of MWSF membrane for six metal ions, Cu(II), Co(II), Ni(II), Cr(III), Pb(II) and Cd(II), were measured. MWSF membrane had the significantly selective sorption for Pb(II) and Cd(II) metal ions and the removal percentage being 82% and 56%, respectively. The adsorption kinetics of MWSF membrane for Cd(II) was analyzed by the pseudo-first-order and pseudo-second-order equations. The adsorption removal process for Cd(II) metal ion was in line with the pseudo-second-order model. MWSF membrane as bioabsorbent has potential application for removal heavy metal ions from the aqueous solution.Download high-res image (92KB)Download full-size image

Disperse Yellow BROB is an important kind of yellow disperse dyes, being stable under the alkaline condition. Two new dispersion systems of Disperse Yellow BROB, nonionic/anionic and anionic/anionic polymer surfactants, were investigated by particle size analysis and Field Emission Scanning Electron Microscopy (FESEM). Amino-terminated polyether (nonionic surfactant L64), and sulfonated amino polyether (anionic surfactant B600), as assisting dispersing agent were applied to grind the dye powder, respectively. Crystal morphological structure of Disperse Yellow BROB was observed by FESEM. Dyeing property of the ground disperse dye under the alkaline condition was discussed. The results show that Disperse Yellow BROB formed stellate crystal in N,N-dimethyl formamide (DMF). Two new dispersion systems of the dye had excellent dispersibility and well-distributed particle sizes. The dispersed particle size with anionic/anionic surfactant was finer than that with nonionic/anionic surfactant. Compared with the traditional sodium salt of polycondensated naphthalenesulphonic acid (dispersing agent MF) dispersion system, the dyeing rate of two new dispersion systems under alkaline condition obviously increased. Nonionic/anionic and anionic/anionic surfactant dispersion systems of Disperse Yellow BROB were stable. The excellent dispersion system of disperse dyes could improve the dyeing property of poly(ethylene terephthalate) (PET) fabric.

•Cellulose was modified by reactive azo-Schiff base with huge azo conjugated system.•Multi-functional cellulose fabrics had excellent UV-protective property.•Multi-functional cellulose also exhibited moderate activity against S. aureus.A novel Schiff base containing huge azo conjugated system and reactive groups, 3,5-bis{2-hydroxyphenyl-5-[(2-sulfate-4-sulfatoethylsulfonyl-azobenzol)methylene amino]}benzoic acid (BHSABA) was applied to modify cellulose. Exhaustion and grafting reactive rate, and grafting quantity of BHSABA on cellulose were calculated. The chemical structure of the modified cellulose was characterized and thermal degradation and morphology were also investigated. The UV protection and antibacterial properties were measured. With increasing the concentration of BHSABA, grafting quantity of BHSABA on cellulose increased from 1.52 × 10−2 mmol/g to 5.08 × 10−2 mmol/g. The multi-functional cellulose fabrics had excellent UV-protective property, which possessed very high UPF value and very low ultraviolet transmittance. The UPF values exceeded 50 and the ultraviolet transmittances were all less than 1%. They also exhibited moderate activity against Staphylococcus aureus and after 10 times washing still maintained antibacterial activity. The onsets of degradation slightly decreased. With increasing the grafting quantity of BHSABA on cellulose, mass loss yields of the residues increased. The morphological structure had no noticeable change.

Cellulose hybrids containing polyhedral oligomeric silsesquioxane (POSS) were synthesized by crosslinking reaction. The chemical and morphological structures of the hybrids were characterized by elemental analysis, infrared spectrum, scanning electron microscope and atomic force microscope. The hybrids were used for adsorbing C.I. Reactive Red 250 in aqueous solution. Adsorption kinetic and equilibrium isotherm of the cellulose hybrids for the dye were investigated. The hybrids formed new adsorptive positions for dyes because of a nanometer-sized cubic core and numerous organic functional groups (-C-N-). The adsorption capacity of the hybrid materials was significantly higher than that of the control cellulose. The adsorption of the dye on the hybrids was good fit with Langmuir isotherm equation and the second-order model. The apparent activation energy of the dye on the hybrid was 14.87 kJ/mol.

Azobenzene Schiff base possesses excellent photochromic or thermochromic properties based on intermolecular proton transfer or cis-trans isomerization. The azobenzene Schiff base containing two reactive groups, N, N-bis{p-[(2′-sulphatoethyl)sulphonyl phenylazo] salicylidene}-1,2-ethylenediamine (BSPEA), was applied to modify cellulose materials. The functional cellulose fabrics containing azobenzene Schiff base groups were prepared. The chemical and morphological structures of functional cellulose fabrics were characterized by element analysis, FT-IR spectrum, and scanning electron microscopy (SEM). The UV-protection properties of the fabrics were investigated by the ultraviolet transmittance spectra and ultraviolet protection factor (UPF). The results show that the functional cellulose fabrics had excellent UV-protection properties with higher UPF value (UPF value reached 31.7) and lower ultraviolet transmittance (less than 5%). The modified cellulose fabrics had not significant influence on the physical properties. The functional cellulose fabrics based on reactive azobenzene Schiff base would have potential application in textile and functional materials.Highlights► We prepared the functional cellulose containing azobenzene Schiff base. ► The UV-protection properties of the fabrics were investigated by the UPF. ► The fabrics had excellent UV-protection properties with higher UPF value.

Cellulose fabric is dyed with Reactive Red B-3BF. Dispersion of silica nanoparticles on dyed cellulose surface is investigated. Novel color cellulose/silica surface is prepared and characterized by FT-IR, AFM and FSEM. The color data of the cellulose/silica surface are discussed by reflectance spectra, color yield (K/S). The results show that silica nanoparticles form smooth film with high degree of homogeneity on the cellulose surface. The surface color shade of the dyed cellulose can be affected by sol–gel. The K/S of two sample surfaces have noticeable increase. With increasing silica nanoparticles, the K/S of samples have further improvement. The thin film imparts low reflectance index and increases color yield.

The bleaching of cotton fabrics with hydrogen peroxide requires high temperature at a high pH value. A large amount of energy is consumed and the aggressive treatment conditions frequently damage the cellulose macromolecular chain. In this paper, novel cationic activator for H2O2 bleaching, (N-[4-triethylammoniomethyl]-benzoyl) caprolactam chloride (TBCC), was synthesized and characterized by elemental analysis, FT-IR and 1H NMR. Low temperature bleaching technique and surface morphology of cellulose fabric with TBCC were discussed. The desized and scoured cotton cellulose fabric could be bleached at low temperature 60 °C, using TBCC as active bleaching agent for H2O2. The whiteness index and wettability of the cotton fabric bleached at low temperature were similar with those of the cotton fabric bleached with the traditional high temperature method. Cotton cellulose fabric was not damaged at low temperature bleaching. It has potential application in cleaner production of cellulose materials.

The silk/silica hybrid biomaterials are synthesized by sol–gel crosslinking process. The chemical and morphological structures of silk/silica hybrids are investigated with micro-FT-IR spectra, X-ray diffraction, SEM, AFM, and DSC. The results show that the crosslinking reactions among inorganic nano-particles, fibroin and 2,4,6-tri[(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) take place during sol–gel process. The silk/silica hybrids form new molecular structures containing not only organic fibroin but also inorganic nano-silica particles. The inorganic particles are bounded to the fibroin through covalent bonds. The silk/silica hybrids can form excellent film with very even nanometer particles. The thermal properties of organic/inorganic hybrid are improved.

The crystal growth and morphological changes of C. I. Disperse Blue 79 in supercritical CO2 were investigated using scanning electron microscopy, X-ray diffraction and differential scanning calorimetry. Crystals of the undissolved dye grew in the supercritical fluid and the melting point and crystallinity of this undissolved dye increased with increasing temperature and pressure.

Cellulose fabric was chemically modified with the triazine derivatives containing the multi-cationic benzyl groups. The novel durable antibacterial cellulose biomaterial containing the multi-cationic benzyl groups was prepared. The chemical structure and thermal property of the antibacterial cellulose biomaterial were investigated with FT-IR spectra, nitrogen content analysis, and differential scanning calorimetry (DSC). The results show that the thermal stability of the novel antibacterial cellulose was slightly decreased. Physical properties of the novel antibacterial cellulose had not significant change. The novel antibacterial cellulose imparted excellent durable antibacterial properties.

The cellulose/silica hybrid (CSH) was prepared by sol–gel crosslinking process. 2,4,6-tri [(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) was used as crosslinking agent in the sol–gel process. The dyeing properties of the cellulose/silica hybrid with the traditional reactive dyes were discussed by reflectance spectra, color yield (K/S) and the colorimetric data of CIELAB. SEM analysis was used to characterize surface structure of the cellulose/silica hybrid. The results show that the cellulose/silica hybrid could be dyed with traditional reactive dyes. The dyeing process for the cellulose/silica hybrid quickly reached equilibrium. K/S of three different color dyes on cellulose/silica hybrid was much higher than those of them on the traditional cellulose. Cellulose/silica hybrid imparted excellent fastness properties. After dyeing, the reflectance spectra curves and the minimum reflectance wavelengths of the dyed cellulose/silica hybrid and cellulose fabrics had not noticeable change.

The polysiloxane modified with cationic and perfluorocarbon groups could form film on the polyester surface by macromolecular self-assembly process. The thin film on the polyester surface could affect the color shade of dyed materials. The effect of the polysiloxane film on the color shade of the dyed polyester was investigated by reflectance spectra, color yield (K/S) and the color differences (ΔE). The colorimetric data of CIELAB was discussed. The results show that the thin film of the polysiloxane modified with cationic and perfluorocarbon groups on the polyester surface had good water repellency. The effect of the polysiloxane film on the color shade of dyed polyester was noticeable. The K/S of the dyed polyester fabrics with the modified polysiloxane film obviously increased. The reflectance spectra of the dyed fabrics treated without and with the modified polysiloxane had not significant change.

Two water-soluble amphiphilic polysiloxane copolymers modified with quaternary ammonium salts (QAS) and long-carbon chain groups are synthesized by copolymerization. FTIR, 1H NMR, and 13C NMR are used to characterize the structures of the amphiphilic polysiloxane copolymers. The results show that two water-soluble amphiphilic polysiloxanes have high surface activity in the aqueous solution and excellent wettability. They can form hydrophilic films on the surface of materials to improve the wettability of materials. The whiteness of the polyester fabrics treated with the amphiphilic polysiloxanes obviously reduces. The color yields (K/S) of the dyed fabrics treated with the amphiphilic polysiloxanes slightly increase. The amphiphilic polysiloxanes have shade darkening effect on dyed polyester microfiber fabric. However, the reflectance spectra curves of the fabrics treated without and with the amphiphilic polysiloxanes undergo no significant change.

Dyeing fabrics in supercritical carbon dioxide (SCD) instead of water can save energy, reduce water use and prevent pollution. The special pilot plant was designed to test dyeing procedures in supercritical carbon dioxide and the analyses of the results indicate major benefits as compared to water based procedures. The dyeing of polyethylene terephthalate (PET) fabric in supercritical carbon dioxide using special pilot plant was investigated. Disperse dye, C.I. (color index) Disperse Blue 79, was used in this study. After dyeing, rinsing in supercritical carbon dioxide, which removes the excess dyes, was also discussed. At the same dyeing conditions, K/S (color yield) of dyed fabric significantly increased with increasing the dye concentration from 1% o.w.f. (on weight of fabric) to 5% o.w.f. Dyeing temperature and pressure had a strong influence on the color yield. When the temperature rose above 110 °C, the increase in color yield was obvious. At 20 MPa, 120–130 °C, dyeing reached equilibrium after 60 min. The excess dye of the dyed PET fabric was small. The suitable condition in supercritical carbon dioxide for removal of excess dye from the dyed fabric was 70 °C, 20 MPa. The PET fabric dyed in supercritical carbon dioxide had good fastness and physical properties.