Application of Cellulose and Cellulose Nanofibers in Oil ...
Nanocomposites based on cellulose nanofibers:...
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Nanocomposites based on cellulose nanofibers: preparation
methodologies and applications
Carmen S. R. Freire
CICECO
macromolecularlignocellulosic
materialsCICECO-UAveiro
and
macromolecularlignocellulosic
materialsCICECO-UAveiro
and
CENTRE FOR RESEARCH IN CERAMICS AND COMPOSITE MATERIALS CICECO main lines of expertise are: - Nano- and Micro-Structured Materials for Information and Communication Technology - Materials for Energy and Industrial Applications
- Sustainability and Biomaterials Biorefineries, Biobased Materials and Recycling
CICECO
New materials from biomass residues (e.g bio-based PU foams from cork powder and other agro-forest residues, etc.)
High value extractives from biomass residues, fruits and algae: - Lipophilic extractives - Phenolics
New polymeric materials from renewable resources : - 2,5-Difurancarboxylic acid - Vegetable oils derivatives
New (nano)omposite materials from biopolymers: - Polysacharides, proteins, etc. - Other polymers - Inorganic nanophases
Outline
Hybrids with metal/ metal oxide
NPs
Surface functionalization/
modification
Transparent (Nano)
composites
Nano-structured materials
(in situ polymerization)
Outline
Hybrids with metal/ metal oxide
NPs
Surface functionalization/
modification
Transparent (Nano)
composites
Nano-structured materials
(in situ polymerization)
Hybrid materials with metal /metal oxide nanoparticles
NFC nanocomposites with Ag and ZnO NPs for antibacterial paper products
NFC nanocomposites with Ag and ZnO NPs for antibacterial paper products:
(1) Assembly of NFC and ZnO or Ag NPs using polyelectrolytes (PDDA, PSS) as macrolinkers
LBL assembly Paper coating
NFC 2.3 % solid content
2) Application of the obtained NFC/ZnO or NFC/Ag nanofillers in paper coating starch based formulations (16 % solid content)
Hybrid materials with metal /metal oxide nanoparticles
NFC nanocomposites with Ag and ZnO NPs for antibacterial paper products:
Hybrid materials with metal /metal oxide nanoparticles
Applications: functional packaging, bioactive coatings, etc.
S. aureus
ZnO <0.03% (w/w) Ag 4.5x10-5 % (w/w)
BC composites with Cu nanostructures (NPs and nanowires)
Hybrid materials with metal /metal oxide nanoparticles
BC composites with Cu nanostructures (NPs and nanowires)
(1) Cu NPs; in situ synthesis (2) Cu nanowires; ex situ synthesis
+
Dispersion
Hybrid materials with metal /metal oxide nanoparticles
BC composites with Cu nanostructures (NPs and nanowires)
- The use of Cu nanowires and BC has shown improved chemical stability against oxidation when exposed to normal ambient conditions
- The nanocomposites were stable for
periods of time (30 days) that makes the production of Cu-based products more attractive for emerging technologic applications as electronic nanopaper
Hybrid materials with metal /metal oxide nanoparticles
3 days
5 months
BC composites with Cu nanostructures (NPs and nanowires)
Cu nanocomposites showed antibacterial action against both bacteria, however with a more marked effect in respect to K. pneumoniae
For both bacteria studied, BC/Cu nanowires nanocomposite present an antibacterial activity significantly lower (more than 2 log bacterial growth) in relation to the nanocomposite with copper NPs with similar copper amount (BC/Cu NPs2)
Hybrid materials with metal /metal oxide nanoparticles
Outline
Hybrids with metal/ metal oxide
NPs
Surface functionalization/
modification
Transparent (Nano)
composites
Nano-structured materials
(in situ polymerization)
Transparent nanocomposite films based on nanocellulose fibers and polysacharides
starch chitosan pullulan
Transparent nanocomposite films
Transparent nanocomposites based on NFC (or BC) and chitosan
Transparent nanocomposite films
A fully green process
Casting 30ºC ventilated oven 16 h
Degassing
Dispersion Ultra-Turrax 20 500 rpm 30 min.
NFC or BC (up to 40%)
LCH - WSLCH HCH - WSHCH 1.5% (v/w)
HCH HCHBC10
Transparent nanocomposites based on NFC (or BNC) and chitosan
Transparent nanocomposite films
SEM images show the good dispersion of the NFC nanofibres at the surface of chitosan films
The good dispersion together with the good interfacial adhesion of CH and cellulose gave rise to nanocomposites with improved mechanical properties
CH
40 % 10 %
5%
Transparent nanocomposites based on NFC (or BNC) and chitosan
Transparent nanocomposite films
Multipolysaccharide (starch, nanocellulose fibers, chitosan) based nanocomposite films
Mechanical properties
(NFC or BC)
Thermal stability (starch)
Tranparency and
antimicrobial activity
(chitosan)
Transparent nanocomposite films
Transparent nanocomposites based on NFC (or BC) and pullulan
Transparent nanocomposite films
Improved thermal stability and mechanical properties
Transparent nanocomposite films
Transparent nanocomposites based on NFC (or BC) and pullulan
Applications of transparent thin nanocomposite films: functional packaging, biomedical applications (bioactive films/coatings, wound healing films, drug delivery systems, etc.) organic electronics…
Work in progress: “Self-standing chitosan based films as dielectrics in organic thin-film transistors” (eXPRESS Polymer letters 7, 2013, 960-965 “Nanocellulose as substrates for inkjet printing of organic thin film transistors”
Transparent nanocomposite films
Nanocellulose blends for paper coating Improved printability (gamut area, intercolour bleeding, etc.) and surface properties Aqueous coating compositions for use in surface treatment of cellulosic substrates WO 2011012934 A2
Transparent nanocomposite films
Outline Hybrids with metal/ metal oxide
NPs
Surface functionalization/
modification
Transparent (Nano)
composites
Nano-structured materials
(in situ polymerization)
Outline
Surface functionalization/modification
Antimicrobial and biocompatible BC membranes obtained by surface functionalization with aminoalkyl groups
NH2
Si OCH3
OCH3
H3CO
Immersion of BC membranein the solution
OH
OH
OH
OH
OH
Thermal Treatment
Acetone
2 hT=110 °C
Orbital stirring5h at 25 °C
Si
NH2
O
O
O
Si
NH2
O O
OSi
NH2
O OH
O
Si
O
O
BC
BC-NH2
0123456789
10
log
CFU
T24
S. aureus
Inoculated Broth + 5% NB
BC
BC-NH2
0
1
2
3
4
5
6
7
8
9
log
CFU
T24
E. coli
Inoculated Broth + 5% NB
BC
BC-NH2
Antimicrobial and biocompatible BC membranes obtained by surface functionalization with aminoalkyl groups
In addition, the bioactive nanostructured BC-NH2 membranes also present improved mechanical and thermal properties. Applications wound healing membranes, bioactive scaffolds, etc.
Surface functionalization/modification
(Si 7.3%, N 3.4 % (w/w))
Surface hydrophobization of nanocellulose fibers using ILs as solvent media and catalysts
OH
O
H
RO
H
HORH O
OR
+ ? The use of cellulose fibers in the development of (nano)composites with thermoplastic matrices requires its preliminary surface chemical modification
Surface functionalization/modification
Modification Reaction time
Acetic Anhydride 6 hours
Butyric Anhydride 4 days
Hexanoic Anhydride 11 days
Alkenyl succinic anhydrides 15 days
Hexanoyl chloride 24 hours
NN
FF
F
SO
O
N S
O
O
F
FF
catalyst
OOHO
OHO O
OH
O
OH
OH
OOHO
OHO O
OH
O
RO
HO
R
O
+
R O
O
R
O
or
P
F
FF
SO
O
N S
O
O
F
FF
solvent
80 ºC
O
R Cl
H2SO4 as catalyst
Surface hydrophobization of nanocellulose fibers using ILs as solvent media and catalysts
Surface functionalization/modification
The modification reactions involved essentially the OH groups at the surface and the amorphous regions of the nanofibers (DS= 0.002-0.41)
Surface hydrophobization of nanocellulose fibers using ILs as solvent media and catalysts
Surface functionalization/modification
Transparent nanocomposites based on bacterial nanocellulose and polylactic acid (PLA)
Surface functionalization/modification
Transparent nanocomposites based on bacterial nanocellulose and PLA
Melting mixing
Acetylated BC (DS = 0.02)
PLA
- Higher homogeneity
- Thermal stability and
- Mechanical performance
- Low water up-take
Applications: packaging, biomedical products and devices, electronic devices etc.
Surface functionalization/modification
(1, 3, 6 % (w/w))
Nanocellulose fibers/acrylic resins nanocomposites: comercial aqueous acrylic emulsions
Surface functionalization/modification
Nanocellulose fibers/acrylic resins nanocomposites: comercial aqueous acrylic emulsions
Dispersion of BC into the acrylic emulsions
Solvent casting
Surface functionalization/modification
Nanocellulose fibers/acrylic resins nanocomposites: comercial aqueous acrylic emulsions
0 100 200 300 400 500 600 700 8000,0
0,2
0,4
0,6
0,8
1,0DTGATGA
320 340 360 380 400 420 4400,0
0,2
0,4
0,6
0,8
1,0 414oC380oC
m/m
i
Temp (oC)
AC AC-BC1 AC-BC2.5 AC-BC5 AC-BC10
Improved thermal and mechanical properties
The good compatibility between unmodified fibers and the matrix is due in this case to the presence of surfactants used in the acrylic resin emulsion
Surface functionalization/modification
Outline
Hybrids with metal/ metal oxide
NPs
Surface functionalization/
modification
Transparent (Nano)
composites
Nano-structured materials
(in situ polymerization)
Nanostructured materials
Nanostructured cellulose composites prepared by in situ polymerization techniques: ATRP
Step 1- BC functionalization with the ATRP initiator Step 2- ATRP grafting from the BC macroinitiator
Nanostructured cellulose composites prepared by in situ polymerization : ATRP
Nanostructured materials
The grafting of the polymers from BC macroinitiator was confirmed by FTIR and 13C CP-MAS solid state
Nanostructured cellulose composites prepared by in situ polymerization : ATRP
Nanostructured materials
The characteristic tridimensional network of nano and microfibrils of BC is clearly visible on the surface and cross-section of grafted BC-membranes. After grafting an increment of the diameter of the cellulose fibrils is observed which is obviously associated with the chemical sleeving by the PMMA or PBA polymeric chains.
Nanostructured cellulose composites prepared by in situ polymerization : ATRP
Nanostructured materials
Grafting PMMA or PBA yielded highly hydrophobic membranes.
The values of the elastic moduli across the whole temperature range are lower than that of the ungrafted BC membrane Because acrylate polymers are more flexible than the BC nanofibrillar network
Nanostructured cellulose composites prepared by in situ polymerization : ATRP
Nanostructured materials
Nanostructured cellulose composites prepared by in situ polymerization : Radical polymerization
Nanostructured materials
Nanostructured cellulose composites prepared by in situ radical polymerization
Nanostructured materials
The success of the polymerization reaction inside BC membranes was confirmed by FTIR and NMR analysis
Nanostructured cellulose composites prepared by in situ radical polymerization Nanostructured materials
The cross-section micrographs of the nanocomposite films displayed the typical lamellar morphology of BC completely impregnated with PHEMA
BC/PHEMA/PEGDA (1:3:0)
BC/PHEMA/PEGDA (1:3:0)
BC/PHEMA/PEGDA (1:3:0.5)
BC/PHEMA/PEGDA (1:3:0.5)
The nanocomposites without cross-linker displayed a less homogenous morphology, with several unfilled parts, suggesting a considerable surface lixiviation of PHEMA during the washing step.
Nanostructured cellulose composites prepared by in situ radical polymerization Nanostructured materials
BC/PHEMA/PEGDA (1:3:0.5)
The nanocomposites present distinct degradation profiles and the considerable increments on the Ti and Tdmax a when compared with BC and PHEMA
Nanostructured cellulose composites prepared by in situ radical polymerization Nanostructured materials
BC/PHEMA/PEGDA (1:3:0.5)
BC/PHEMA nanocomposite films showed a considerably higher swelling ratio than BC membranes
Nanostructured materials Nanostructured cellulose composites prepared by in situ radical polymerization
BC/PHEMA/PEGDA (1:3:0.5)
BC/PHEMA/PEGDA (1:3:0.05) are not cytotoxic for ADSCs and seem to be ideal for harboring cell growth Can be seen as a promising materials for several biomedical applications, including the design of 3D matrices to maintain a cellular niche for stem cell-mediated tissue regeneration
Nanostructured materials Nanostructured cellulose composites prepared by in situ radical polymerization
BC/PHEMA/PEGDA (1:3:0.5)
Nanostructured materials
Nanostructured cellulose composites prepared by in situ radical polymerization
Nanostructured materials Nanostructured cellulose composites prepared by in situ radical polymerization
The homogeneous distribution of PSSA through the entire membrane thickness is supportive that electrical percolation can be attained
Nanostructured materials Nanostructured cellulose composites prepared by in situ radical polymerization
The excellent mechanical behavior of pure BC is reflected on the composites both on magnitude of E´ (at least 20 times higher than that of Nafion) and on the thermomechanical stability
Nanostructured materials Nanostructured cellulose composites prepared by in situ radical polymerization
Drug delivery systems
Nanocellulose as new biopolymer systems for transdermal drug delivery (lidocaine, ibuprofen, caffeine, diclofenac)
drug – Glycerol Solution, 1h
Wet BC membrane
Oven dried (30ºC)
No drug agglomerates
Good dispersion
Nanocellulose as a new biopolymer system for transdermal drug delivery (lidocaine, ibuprofen, caffeine, diclofenac)
SEM
Lidocaine Ibuprofen
Drug delivery systems
Nanocellulose as a new biopolymer system for transdermal drug delivery (lidocaine, ibuprofen, caffeine, diclofenac)
In vitro permeation tests
- BC membrane with drugs
- Drugs solutions
- Commercial gels or patches
Human skin Franz cell
8h, 37ºC, PBS (phosphate buffer) drug determination: UV-Vis
Pharmaceutical Forms
Drug delivery systems
- The permeation rate of drugs in nanocellulose membranes depends strongly on its nature. - This methodology can be successfully applied for the dermal administration of several drugs, regarding the release profile and ease of application.
Drug delivery systems
Conlusions
NanoCellulose fibers… A unique biomacromolecular material Multiple opportunities …Sustainable Development
Thanks for you attention….
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