Method-1

Extraction of CNF (Cotton Nano-Fiber) solution from cotton stem.

Material
1. Sulfuric acid (H2SO4, 98%)
2. Hydrogen peroxide (H2O2, 30%)
3. Dimethyl sulfoxide (DMSO, spectroscopically pure grade)
4. 2, 2, 6, 6-tetramethylpiperidine-1-oxyl radical (TEMPO, 98%)
5. Sodium hydroxide (NaOH, 97%), sodium bromide (NaBr, 99.6%)
6. Sodium hypochlorite (NaClO, 12%)
7. Sodium carbonate (Na2CO3, 99.5%)
8. Ethanol (C2H5OH)
9. Deionized water
10. Liquid Nitrogen for freezing purpose
Equipment
1. Oven
2. Grinder
3. Stirrer
4. Centrifuge
5. Mold (cylindrical)

Degumming Cotton Stalk

Estimated Time 13 to 14 hours
1. The pristine cotton stalk barks obtained from the cotton plant were treated by using a 3
mL/L H2SO4 solution (liquor ratio 1:30) at 60 ⁰C for 2.5 h to remove the mud.
2. After completely washed with the deionized water, the cotton stalk barks were heated
at 70 ⁰C in a mixture of 8 g/L NaOH and 8 mL/L H2O2 (liquor ratio 1:100) for 2 h.
3. Then the cotton stalk barks were washed with the deionized water and put into in a
mixture of 12 g/L NaOH and 12 mL/L H2O2 and heated at 80 ⁰C for 1 h (liquor ratio
1:100).
4. Then treated cotton stalk barks were dispersed in a H2SO4 solution (0.5 ml/L) for 10
minutes to neutralize the remained NaOH and dried in an oven at 70 ⁰C for 7 h
subsequently.
 After the above mentioned process, the degummed cotton stalk barks with a fiber-like were
obtained, which were denoted as DCSB-1.

Alkalization and DMSO (Dimethyl sulfoxide) Treatment

Estimated Time 56 to 60 hours
1. The DCSB-1 was grinded into particle size (with about 1 mm) and dispersed in an 8 wt. %
NaOH solution at 70 ⁰C for 4 h.
2. After been washed with deionized water and dried at 70 ⁰C for 24 h, the mass was
soaked in a DMSO (liquor ratio 1:30) solution and heated at 70 ⁰C for 4 h in a water
bath.
3. The mass was washed with a 2 wt. % Na2CO3 solution and deionized water and dried at
70 ⁰C for 24 h.
The alkali treated DCSB-1 and NaOH/DMSO successively treated DCSB-1 were named DCSB-
2 and DCSB-3, respectively.

Preparation of CNF
Estimated Time 51 to 55 hours
1. The DCSB-1 (1.0 g) or treated DCSBs (1.0 g) were dispersed in 100 mL water and then
added the NaBr (0.33 g) and TEMPO (0.033 g) into the suspension.
2. The reaction was initiated by adding the 12 wt. % NaClO solution (20.0 g) with stirring
for 2.5 h and the pH value was decreased as oxidation proceeded and adjusted between
10.6 and 10.8 by adding the 2 wt. % NaOH solution.
3. The reaction was ended by adding ethanol absolute, followed by continuously stirring
for 10 min.
4. The final product was obtained by successive centrifugations (10000 rpm for 10 min)
from the suspension and washed several times with deionized water.
5. The cellulose jelly was dispersed in deionized water by a high-speed homogenization to
obtain CNF.
6. The CNF extracted from DCSB-1, DCSB-2 and DCSB-3 was named CNF-1, CNF-2 and CNF-
3, respectively.
7. The 0.5 wt.% CNF aqueous solutions (50 mL) were prepared and poured into cylindrical
molds and quickly frozen in liquid nitrogen, then the freeze-drying process was
conducted in a freeze-drier (FD-1D-80) continuously 48 h until the frozen water in the
cellulose materials was sublimed completely from the solid phase to the gas phase.
8. The cold trap temperature was -80 ⁰C and the vacuum was 3.5 Pa during the freeze-
drying process.
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2015.09.056