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V Nanocellulose

1) Nanocellulose refers to cellulose materials isolated from plant, algal, bacterial, or animal sources that have at least one dimension in the nanoscale. 2) There are two main types of nanocellulose - cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC). CNF are produced through mechanical treatment while CNC are produced through acid hydrolysis. 3) Nanocellulose has advantages like renewability, biodegradability, and good mechanical properties. It can be extracted from various natural sources and modified through different processes to tailor its properties for different applications.

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Santiago Tuesta
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261 views38 pages

V Nanocellulose

1) Nanocellulose refers to cellulose materials isolated from plant, algal, bacterial, or animal sources that have at least one dimension in the nanoscale. 2) There are two main types of nanocellulose - cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC). CNF are produced through mechanical treatment while CNC are produced through acid hydrolysis. 3) Nanocellulose has advantages like renewability, biodegradability, and good mechanical properties. It can be extracted from various natural sources and modified through different processes to tailor its properties for different applications.

Uploaded by

Santiago Tuesta
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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NANOCELLULOSE

Cellulose
A biopolymer found naturally in plant cell
Linear molecule composed of β-glucose subunits (bound at 1-
4 arrangement of glycosidic bonds )
Advantages: renewable resource, environmental friendly, low
health risk, biodegradable, low cost, low density, high reactive
surface and good mechanical property (high aspect ratio)

3 2
1
3

Polysaccharide: Cellulose vs. Starch


4

Natural cellulosic fiber: Type

Natural cellulosic fibers are the most promising resource for


the synthesis nanocellulose
Plant fiber can be classified:
5

Natural cellulosic fiber: Type (cont.)

Different sources and processes  Different structures of cellulose


6

Plant cell wall


7

Plant cell wall (cont.)


8

Natural fiber component

Basically component: Cellulose, Lignin and Hemicellulose


A few natural fibers are free of lignin and/or hemicelluloses
(i.e.; cotton fiber)
Chemical composition and cell structure are complicated
9

Natural fiber component (cont.)


10

Classification of nanocellulose (NC)

Isolated cellulosic materials with one dimension in nanoscale


Different nanocellulose:
Cellulose nanofibril (CNF)
Cellulose nanocrystal (CNC)
11

Cellulose nanofibril (CNF)


Also called cellulose microfibril (CMF)
Nanometer size in width (10-70 nm) and micrometer size in length
Containing both crystalline and amorphous part
Delaminating intermolecular H-bonding of microfibril (require
intensive mechanical treatment)

Wood pulp
12

Cellulose nanofibril (CNF): TEM

Rice straw Rubber wood

Wheat straw Oil palm


13

Cellulose nanofibril (CNF): Diameter


14

Preparation of CNF
Mechanical treatment can isolate CNFs from the primary and
secondary cell wall without severe degradation.
Mechanical isolation involves grinding, refining, high-pressure
homogenization, microfluidization and cryochrusching
Depending on source, defibrillation technique, amorphous
fraction and entangled network
 Different morphology and aspect ratio of the CNFs
A large amount of H-bonding, Lignin and Hemicellulose content
and Rehydration  Hard to isolate CNFs
To ease mechanical treatment and reduce the energy consumption
 Pre-chemical treatment (using enzyme and oxidation)
15

High-pressure homogenization

 Dilute slurries of refined cellulose fibers


 Pumped at high pressure
 Fed through a spring high-pressure loaded valve
(shearing and impact forces)
 Homogenized high degree of fibrillation
16

TEMPO oxidation Saito et al. (2006)

2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) reagent


Isolate individual NFC after TEMPO-mediated oxidation
Width of 3-4 nm and a few micron in length
Transform of cellulose hydroxyls groups to carboxyl
Reduce energy consumption compare to mechanical treatment

TEMPO-cotton
17

Cellulose nanocrystal (CNC)


Rigid rod-like crystal nanoparticles
Width of 5-70 nm and length of 100-250 nm for plant cellulose
and 100 nm to several micron for cellulose of algae, bacteria
and sea animal
Acid hydrolysis remove the amorphous region
Strong acid condition combined with sonication
 known as whiskers
CNC properties depend on type of mineral acid and its
concentration, hydrolysis temperature and time, and ultrasonic
condition used
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Acidic hydrolysis of glycosidic bond

I: Proton (from acid) rapidly interact with the glycosidic oxygen linking 2 sugar unit

II’: Protonation at the ring oxygen II: Forming a conjugate acid


III’: Ring opening III: Slow cleaving C-O bond
Non-cyclic carbonium ion  Cyclic carbonium ion

Free sugar and a proton after adding water


19

Cellulose nanocrystal (CNC): TEM

Rice straw Cotton

Bagasse Eucalyptus
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Cellulose nanocrystal (CNC): Source


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CNC: Comparison
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Crystal structure of CNC

Two crystal structures:


Iα : Triclinic unit cell (bacteria and algae)
Iβ : Monoclinic unit cell (plant cell wall and tunicates)
Both crystal structures co-exist in the same cellulose sample

Iα : (110)t , (010)t , (100)t

Iβ : (200)m , (110)m , (110)m


23

Crystal structure of CNC (cont.)


Intraplane H-bonding in Iβ ~ 70-80% of network (better distributes over
Iα)
Weaker inter H-bonding in Iα
Iα  Iβ (H-bonds in Iα thermally degrade at lower temperatures)

Iα
Not stable

Iβ
Stable
24

Hydrogen-bonded plane

(110)t (200)m
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Hydrolysis cellulose: Sulfuric acid


Most widely use strong acid  Sulfuric acid (H2SO4)
Esterification on the surface hydroxyl groups negatively
charged sulfate groups (SO3-)
 Limits the agglomeration and flocculation of CNCs in
aqueous medium (better dispersion in water)
 Thermostability of the nanocrystals

To control the acid hydrolysis, acid


concentration, reaction time, and
reaction temperature are considering
26

Preparation of CNC: H2SO4 concentration

Higher concentration
 DP
 Crystallinity (loss amorphous region)
 Crystal size
27

Bacterial cellulose (BC)


Bottom up method: fermentation of low molecular weight sugars
using bacteria from the Acetobacter species
Ribbon-shaped fibril
High degree of polymerization (up to 8000) and high degree
crystallinity (up to 85 %)  Good mechanical properties
Nanoscale in width (10-70 nm) and micrometer size in length
Very fine and pure fiber network structure
No need to eliminate lignin and hemicellulose
Applications: medical health and surgical
Disadvantages: low availability, inefficient process and high costs
 hard to commercially attractive
28

Bacterial cellulose (BC): TEM

CNF CNC
29

Sea animals celluloses


Only animals known to produce cellulose microfibrils: Tunicates
Tunicate shells  cut into small fragments  bleached by several
steps  extracting nanocellulose by acid hydrolysis
High modulus and high aspect ratio
30

Tunicate cellulose: TEM

CNC
31

Cellulose nanocrystal (CNC): Source


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Nanocellulose: Comparison
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Modified nanocellulose

Surface functionality can be categorized into 3 groups:


Surface chemistry as a result of nanocellulose extraction
Adsorption
Covalent bond
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Surface chemistry: Extraction


35

Surface chemistry: Adsorption

Electrostatic interaction

CTAB: Cetyltetramethylammoniumbromide surfactant


PEI: Polyethyleneimine
36

Surface chemistry: Covalent bond


37

Fabrication of NC based materials

Solution casting
Melt-compounding
minimize NC degradation resulting from shear stresses
and temperatures involved in the process
Electrospinning
Layer-by-layer assembly
38

Nanocellulose film
Filter paper

Touch screen
BC-Acrylic

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