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Developing Nano clay Nanocellulose
Composites for Barrier Applications
Via Spray Coating
S.Kirubanandan
Ph.D. Student
8th June 2018, BAMI Industrial Chapter, Bioprocessing Resource Institute of Australia,
Department of Chemical Engineering, Monash University
Maisha Maliha
Ph.D. Student
Introduction and Background of the research
Research Objective
Methods
Results
Conclusion
Outline
2
Background
3
Introduction
Isogai et al. Nanoscale,2011,3, 71-85
4
Nanocellulose
Aerogels/foam
Packaging
Solar Panels Air FiltrationFlexible Electronics
Oil and water separation Water Filtration
5
Barrier materials
Wax
Aluminium
Plastics
Limitation:
Poor barrier
properties
6
Nanocellulose – Potential Barrier
• Bio degradable
• Non toxic
• Extreme High Surface Area
• Crystallinity
• Tuneable surface for
functionalization
Martin Hubbe et al, Nano cellulose in Packaging: A Review, Bio Resources 12(1), 2143-2233.
7
Overview of Barrier Materials
Aulin and Lindström, Biopolymer Coatings for Paper and Paperboard, John Wiley & Sons, Ltd, 2011, pp. 255-276
8
Effect of Inorganics Addition
Müller, Kerstin (2017). Nanomaterials. 7. 47. 10.3390/nano7040074.U.M. Garusinghe et al, Colloids and Surfaces A,540, 2018,233-241.
9
Nanocomposite films preparation techniques
1. Casting and Solvent evaporation
2. Vacuum filtration
Filtration Separation Drying
Processing time – 3 - 72 hrs
Drying time -10 mins
10
Processing and Drying time – 72 hrs
Laboratory scale
Rapid Preparation of NC films
11
Preparation of Nanocomposite via spraying
Nano clay Solution and
Nanocellulose
Preparation
Nanocellulose
Nano clay –
Nanocellulose (Raw
Diacel KY 100S)
Composites
Nano clay –
Nanocellulose
(Homogenised 2 passes)
Composites
Without Homogenization
With Homogenization
Disintegrator Spray Coating
NC- Closite Na++ (MMT)
Suspension
2 Pass
˜ 800-1000 Bar
12
Spray Coated Nanocomposite
Closite Na++ ( Natural Bentonite MMT)-
Nanocellulose Nanocomposite
Closite Ca++ (MMT)- Nanocellulose
Nanocomposite
Closite 116 (MMT)- Nanocellulose
Nanocomposite
13
Apparent Density
750
800
850
900
950
1000
1050
1100
1150
0 10 20 30 40 50 60 70
DensityKg/m3
Nanoclay Content
Closite Na
Vaccum Filtration-Closite Na
Cloasite Na Homoginized NC
14
SEM Micrograph of spray coated
nanocomposites
15
SEM MICROGRAPHS
Spray Coated NC film (unhomo)
Spray Coated 10 % MMT –NC (Homo) Composite
Spray Coated 10 % MMT –NC (unhomo) Composite
Spray Coated NC film (Homo)
16
SEM MICROGRAPHS
Spray Coated NC film (Homo) Spray Coated 30 % MMT –NC (Homo) Composites
Spray Coated 30 % MMT –NC (unhomo) CompositesSpray Coated NC film (unhomo)
17
EDX
18
Energy –Dispersive X-Ray (EDX) Spectrum of 10% MMT Nanocellulose (Unhomo) Nanocomposite
C
O
Na Mg Al Si
Barrier Properties of Nanocomposites
19
Air Permeance
All Spray Coated Nanocomposites
< 0.003 µm/Pa.S
20
Effect of Nano clay addition on WVP
R² = 0.9722
R² = 0.956
R² = 0.9684
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70 80
Watervaporpermeabilityx1011(g/Pa.s.m)
Nanoclay Loading (%)
Closite Ca2+
Closite Na+
Closite 116
21
Effect of Homogenization
22
Effect of Nano clay addition on WVP ( After Homogenization)
R² = 0.8283
R² = 0.9988
R² = 0.9975
R² = 0.9772
0
0.5
1
1.5
2
2.5
3
3.5
4
0 5 10 15 20 25 30 35
Watervaporpermeabilityx1011(g/Pa.s.m)
Nanoclay Loading (%)
Closite Na+
Nanocomposite Na via Vaccum Filtration
Nanocomposite Na via Vaccum Filtration after Homo
Nanocomposite via spraying after Homo
23
Comparison with Synthetic Polymers
VF NC Film
SC NC Film
CNF
Acetylated CNF
PVC
Aluminium Foil
LDPE
HDPE
VF Nanocomposite
SC Nanocomposite
VF Nanocomposite (Homo)
SC Nanocomposite (Homo)
0 1 2 3 4 5 6 7 8
Water Vapour Permeability (g/m.s.Pa) *10^ -11
24
Works to be performed
• XRD Analysis of Nanocomposites
• Cross-section analysis of Nanocomposites
• Optical Profilometry
• Mechanical Strength
25
Conclusion
• An optimized and rapid technique to prepare
nanocellulose/montmorillonite (MMT) was
developed.
• Low permeance of air and water vapour
• Platform for sustainability to replace synthetic
packaging
26
Acknowledgement
• Assoc Prof. Warren Batchelor and Prof. Gil Garnier
• Dr. Swambabu Varanasi
• Student friends and Staff members at BioPRIA
27
Thank you very much

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Nanocomposites via spray coating

  • 1. Developing Nano clay Nanocellulose Composites for Barrier Applications Via Spray Coating S.Kirubanandan Ph.D. Student 8th June 2018, BAMI Industrial Chapter, Bioprocessing Resource Institute of Australia, Department of Chemical Engineering, Monash University Maisha Maliha Ph.D. Student
  • 2. Introduction and Background of the research Research Objective Methods Results Conclusion Outline 2
  • 4. Introduction Isogai et al. Nanoscale,2011,3, 71-85 4
  • 5. Nanocellulose Aerogels/foam Packaging Solar Panels Air FiltrationFlexible Electronics Oil and water separation Water Filtration 5
  • 7. Nanocellulose – Potential Barrier • Bio degradable • Non toxic • Extreme High Surface Area • Crystallinity • Tuneable surface for functionalization Martin Hubbe et al, Nano cellulose in Packaging: A Review, Bio Resources 12(1), 2143-2233. 7
  • 8. Overview of Barrier Materials Aulin and Lindström, Biopolymer Coatings for Paper and Paperboard, John Wiley & Sons, Ltd, 2011, pp. 255-276 8
  • 9. Effect of Inorganics Addition Müller, Kerstin (2017). Nanomaterials. 7. 47. 10.3390/nano7040074.U.M. Garusinghe et al, Colloids and Surfaces A,540, 2018,233-241. 9
  • 10. Nanocomposite films preparation techniques 1. Casting and Solvent evaporation 2. Vacuum filtration Filtration Separation Drying Processing time – 3 - 72 hrs Drying time -10 mins 10 Processing and Drying time – 72 hrs Laboratory scale
  • 11. Rapid Preparation of NC films 11
  • 12. Preparation of Nanocomposite via spraying Nano clay Solution and Nanocellulose Preparation Nanocellulose Nano clay – Nanocellulose (Raw Diacel KY 100S) Composites Nano clay – Nanocellulose (Homogenised 2 passes) Composites Without Homogenization With Homogenization Disintegrator Spray Coating NC- Closite Na++ (MMT) Suspension 2 Pass ˜ 800-1000 Bar 12
  • 13. Spray Coated Nanocomposite Closite Na++ ( Natural Bentonite MMT)- Nanocellulose Nanocomposite Closite Ca++ (MMT)- Nanocellulose Nanocomposite Closite 116 (MMT)- Nanocellulose Nanocomposite 13
  • 14. Apparent Density 750 800 850 900 950 1000 1050 1100 1150 0 10 20 30 40 50 60 70 DensityKg/m3 Nanoclay Content Closite Na Vaccum Filtration-Closite Na Cloasite Na Homoginized NC 14
  • 15. SEM Micrograph of spray coated nanocomposites 15
  • 16. SEM MICROGRAPHS Spray Coated NC film (unhomo) Spray Coated 10 % MMT –NC (Homo) Composite Spray Coated 10 % MMT –NC (unhomo) Composite Spray Coated NC film (Homo) 16
  • 17. SEM MICROGRAPHS Spray Coated NC film (Homo) Spray Coated 30 % MMT –NC (Homo) Composites Spray Coated 30 % MMT –NC (unhomo) CompositesSpray Coated NC film (unhomo) 17
  • 18. EDX 18 Energy –Dispersive X-Ray (EDX) Spectrum of 10% MMT Nanocellulose (Unhomo) Nanocomposite C O Na Mg Al Si
  • 19. Barrier Properties of Nanocomposites 19
  • 20. Air Permeance All Spray Coated Nanocomposites < 0.003 µm/Pa.S 20
  • 21. Effect of Nano clay addition on WVP R² = 0.9722 R² = 0.956 R² = 0.9684 0 5 10 15 20 25 30 35 0 10 20 30 40 50 60 70 80 Watervaporpermeabilityx1011(g/Pa.s.m) Nanoclay Loading (%) Closite Ca2+ Closite Na+ Closite 116 21
  • 23. Effect of Nano clay addition on WVP ( After Homogenization) R² = 0.8283 R² = 0.9988 R² = 0.9975 R² = 0.9772 0 0.5 1 1.5 2 2.5 3 3.5 4 0 5 10 15 20 25 30 35 Watervaporpermeabilityx1011(g/Pa.s.m) Nanoclay Loading (%) Closite Na+ Nanocomposite Na via Vaccum Filtration Nanocomposite Na via Vaccum Filtration after Homo Nanocomposite via spraying after Homo 23
  • 24. Comparison with Synthetic Polymers VF NC Film SC NC Film CNF Acetylated CNF PVC Aluminium Foil LDPE HDPE VF Nanocomposite SC Nanocomposite VF Nanocomposite (Homo) SC Nanocomposite (Homo) 0 1 2 3 4 5 6 7 8 Water Vapour Permeability (g/m.s.Pa) *10^ -11 24
  • 25. Works to be performed • XRD Analysis of Nanocomposites • Cross-section analysis of Nanocomposites • Optical Profilometry • Mechanical Strength 25
  • 26. Conclusion • An optimized and rapid technique to prepare nanocellulose/montmorillonite (MMT) was developed. • Low permeance of air and water vapour • Platform for sustainability to replace synthetic packaging 26
  • 27. Acknowledgement • Assoc Prof. Warren Batchelor and Prof. Gil Garnier • Dr. Swambabu Varanasi • Student friends and Staff members at BioPRIA 27

Editor's Notes

  1. Good Morning everyone, Thanks for attending my presentation on nanocellulose as barrier materials , Thanks Prof Warren for introducing me to Audience , I am working on the research topic on nanocellulose sheet and its composites as high performance barrier materials and developing these materials using spray coating, an alternative for vacuum filtration.
  2. In technical seminor, I would like to talk about Introduction and Background of the research, Research aims , Preliminary research and Proposed research Conclusion of this research work I have previously presented the development of nanocellulose film via spray coating and its barrier performance and compared with the sheet prepared from vaccum filtration. I need to high light the performance of spray coating The spraying of nanocellulose on the polished metal surface to create a unique surface such as rough surface on the atmosphere side and smooth surface on the metal side The operation time for sheet formation is less than 1 min and comparable uniformity and thickness of the sheet with vaccum filtration The properties of the sheet can be tailored by simple adjusting the suspensison concentration and other process parameters in experimental configuration such as velocity and nozzle type When I see the barrier properties of nanocellusose filme is quite good compared with sheet from vaccum filtration. In this presentation, I had like to talk about the development of nanocellulose based composites via spraying and evaluate its barrier performance and compared with the nanocomposties prepared via vaccum filtration that previously reported.
  3. Cellulose is the most abundant biopolymer on the earth. Wood fibers are composed of 40–45% cellulose, which is produced in nature via photosynthesis and ubiquitously used in the everyday life.56 The cell wall of natural wood bers has a 3 dimensional (3D) hierarchical structure designed for the metabolic ion transportation and to possess mechanical stability, The microbril bundles are composed of microbril cellulose (MFC) and nanobril cellulose (NFC). MFC is delaminated from wood pulp through mechanical treatments before and/or aer enzymatic or chemical pretreatment, which has a diameter of 5– 60 nm with a length of several micrometers. It has specific characteristics to make many functional sustainable materials Due to its biodegradability, it has good alternative for synthetic polymers It has potential of recyclable It is non –toxic material Due to its biocompatibility, it can be used as base substrate for development of tissue engineering scaffolds It is eco –friendly material
  4. Nowdays Nanocellulos is a potential biomaterials and applying in many fields Our research group focus on nanocellulose based packaging
  5. Cellulose based products such as paper and boards are good packaging materials however it is poor barrier properties due to its wide pores Its barrier performance enhanced by coating with wax or laminated with aluminium or plastics , however these coating and extrusion is not recyclable and not biodegradable The challenge is to develop recyclable and sustainable packaging materials
  6. Nanocellulose is potential barrier material and its minute pores in the web like structure delays and decrease the transfer of water vapour and air The reduction of fibres leaded to reduction of pore size and resulting better barrier properties.
  7. This graph concludes nanocellulose has good oxygen barrier and poor water vapour due to its hydrophilicity Due to high polarity of nanocellulose, water vapour affects the fibre –fibre bonds. Also this material characteristic weakens the original strong bonds holding the dry 2D structure, decreasing water permeability and deterioarating material stability The water vapour permeability of nanocellulose should be improved and to bring to synthetic polymer range.
  8. Effect of Inorganics Addition in the nanocellulose: In the design of sustainable packaging material , controlling water vapour transmission rate is more critical to extend the shelf life of moisture sentitive foods. To enhance the barrier properties of nanocellulose sheets, inorganic nanomaterials are introducted to the fibre matrix result the formation of nanocomposites . Recently, Uthpala developed nanocomposite with montmorillonite (MMT) and nanocellulose via vaccum filtration and confirmed low water vapour permeabilyt and oxygen transfer rate. The mechnisism of low permeance of water vapour and air is creatiin of tortuous path when MMT arranged orthogonally in fibre matrix and results low op and wvp.
  9. There are few methods available for nanocellulose films for various functionality. Casting of the nanocellulose suspension is the most common technique at laboratory scale and it requires longest drying time for evaporation of solvent in the suspension. Vacuum filtration is the most method for making the films. It requires processing time from 10 mins to 4 hours in the nanocellulose film and in the case of nanocomposite, it requires 24 hrs s for dewatering in the filateration process 3. Spray coating is recently reported to replace the filtration process , however after coating , the same filteration is used to removed the excess water formed sheet and it required time which is not reported in the literatue. Therefore, these methods have problem in the scale up , it requires alternative process for fabrication nanocellulose film
  10. Spray coating is a contactless coating and provides contour coating and possible to coat tear sensitive material and easy to control the coating material. In this coating method, the topography of the substrate has no influence on the coating weight. For example, on uneven surfaces a contour coat can be applied. This could result in a reduction of cost and an improvement of quality. Atomization is the integral part of spray coating , this process is highly governed by the physical property of coating fluid such as density , surface tension and viscosity. Contactless Contour coating Coating of tear sensitive material Controlling the coating material
  11. I have attempted to prepared the nanocellulose composite via spray coating. Nanoclay is added with respect to fibre content in suspension and disintegrated at 15000 revoultions and sprayed on the stainless steel at a specified conditions. I have performed experiments with two catagories With homoginization of fibres Without homoginization of Diacel MFC
  12. I have prepared the nanocomposite with three typers of nanoclay Closite Na Closite Ca Closite 116 I have focused only Closite Na and prepared the nanocomposite with homoginzed nanocellulose witj claosie Na++ The nanocellulose –montmorillonite (MMT) compsites were preared via spraying and engineered its barrier performace by varying the MMT loading ( from 5 to 75% of nanoclay into the nanocellulose suspension) All composites are flexible and foldable. For example The composites prepared from clostie Na yellowshed as the MMT conten increased Similarly The composites preared from clostie Ca reddished as the MMT content increased
  13. From the plot of Density vs Nanoclay content, The appratent detnsity of nanocomposite from homoginized via spray coating are similar the sheets from vaccum filtration. Concluding that its higly compact structure than that of the nanocomposite prepared from unhomogenized cellulose via spraying
  14. SEM investigation of surface of nanocomposite confirms the distribution of nanoclay in the fibrious matrix based content of MMT in suspension
  15. When comparing the plain nanocellulose film with nanocomposite, the nanoclay distributed widely on the surface confirming the spray coating is a good method to prepare nanocompostie
  16. EDX spectr of the nanocomposite along surface of the nanocomposite confirms the distribution of nanoclay on the composite and Carbon and Oxygen from chemical structure of nanocellulose and other elecments are present in the strure of MMT.
  17. The air permeability of the nanocomposite was less than 0.003 μm/Pa.S, which is the detection limit of the instrument, confirming the film is highly impermeable for packaging application.
  18. WVP of nanocomposite increased with MMT content increased due to agglomeration of nanoclay in composite at high loading of MMT and not created a tortuous path for permeating water molecules. I need to investigate the structure of nanocomposite via XRD studies Generally, The water vapour permeability of the nanocomposites is affected by many parameters such as type and structure of MMT, its dispersion and content in the nanocellulose matrix.
  19. After Homoginization of Nanocellulose with nanoclay, WVP decreased for nanocomposite via spraying upto 20% loading and increased due to small aggregation after 30% and values bit higher than that of nanocomposite via vaccum filtration This might be the arrangement of MMT Platelet’s largest dimension perpendicular to the diffusion pathway producing a tortuous path reducting WVP.
  20. When nanocomposite compare with synthetic polymers, its has significant WVP to be sustainable packaging materials
  21. A rapid and commercially scalable, economically feasible method for preparing nanocellulose sheet is developed to produce high basis weight and quality nanofiber sheet and to replace the standard method of vacuum filtration. The basis weight is controlled by the spraying time and nanocellulose concentration in the suspension. The processing time for producing the sheet is less than 1 min and the quality of the spray coated sheet is confirmed by the uniformity in thickness of the sheet.
  22. I would like to thank my supervisor for guiding this work successfully.