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BiMaC Innovation
O
OH
HO OH
O
PeriodateWhen
met
Cellulose……a “love story” of both scientific and commercial interest
BiMaC Innovation
Who am I?
Per Larsson
• Became member of the BiMaC Innovation family on December 5, 2011
Before that
• Postdoc at McGill University/FPInnovations,Montréal, Canada
• PhD in Pulp and Paper Chemistry and Technology, KTH Royal Institute of Technology
• Master of Science in Chemical Engineering, Chalmers University of Technology, Gothenburg, Sweden
BiMaC Innovation
Acknowledgements
All BiMaC Innovation members (former and current), at KTH and in industry
and special gratitude to my co-authors andclosest collaborators:
Lars WågbergLars BerglundLinda FogelströmJoby KochumalayilPhilip LindhTorbjörn PetterssonSören ÖstlundEric LinvillVéronica LópezNicholas CervinChristopher CarrickJohan ErlandssonFarhan AnsariHenrik HedlundRebecca HollertzGiada Lo ReTomas LarssonLennart Salmén
BiMaC Innovation
Let’s first go back in time…
… to December 7, 1854 (in Lille, France):
“…chance favours the prepared mind.” Louis Pasteur
Original quote: Dans les champs de l'observation le hasard ne favorise que les esprits préparés.
(In the fields of observation, chance favours only the prepared mind.)
BiMaC Innovation
Back to BiMaC Innovation
Extract from the BiMaC Innovation project plan (the project where I was deployed), written during the Summer/Autumn of 2011:
Task 1Manufacturing and evaluation of thin CNF [cellulose nanofibril] nanocomposites of high toughness (strain to failure >20%)
BiMaC Innovation
Fibres partly periodate oxidised (and thereby converted to dialdehyde cellulose or further
reduced to dialcohol cellulose)
Zeronian et al., Tappi 14(9):557–564, 1964
dialcohol cellulose
dialdehyde cellulose
BiMaC Innovation
Dialcohol cellulose nanofibril films
Oxygen permeability0.5 ml·µm/(m2·kPa·24 h)
at 50% RH
Larsson et al., Biomacromolecules 15(6):2218–2223, 2014
BiMaC Innovation
Periodate oxidation
Any vicinal diol
Two carbonyls
Image courtesy of www.masterorganicchemistry.com
BiMaC Innovation
Cellulose(or other poly-carbohydrate)
O
OH
HO OH
O OOH
O O
O
Dialdehyde cellulose
Periodate oxidation
Dialcohol cellulose
Implementation project!
Implementation project!
OOH
R-HN NH-R
O
Aminated cellulose
Dicarboxylated cellulose
2x
BiMaC Innovation
Hungry for all modifications?
Véronica López’s PhD thesis defence
When: Friday February 23 at 10 amWhere: Lecture hall F3, KTH, Lindstedtsvägen 26
Thesis title: Chemical modification of cellulose fibres and fibrils for design of new materials
vs
Prof. Akira Isogai, Tokyo University
BiMaC Innovation
Larsson et al.,15th Fundamental Research Symposium, Cambridge, UK, pp. 851–866, 2013Larsson et al., Green Materials 2(4):163–168, 2014
Dialdehyde nanofibrils for barrier films
Wet, no x-link
Wet, x-link
Dry, no x-link
Dry, x-link
Larsson and Wågberg., Patent WO 2015/034426 Al
BiMaC Innovation
Cross-linking CNFs for high wet strength
0 2 4 6 8 10 12 14 160
5
10
15
20
25
30
35
0 2 4 6 8 10 12 14 16
Wet
tens
ile in
dex
(Nm
/g)
Real fibril content (%)
a) No retention aid Reference Reference + pDADMAC Carboxymethylated CNF Periodate oxidised CNF Periodate oxidised CNF + pDADMAC Dopamine CNF Kraft MFC
Real fibril content (%)
b) Retention aid
(Hollertz et al., Cellulose, 24:3883–3899, 2017)
(PVAm or pDADMAC)
Fibril content (%)Fibril content (%)
BiMaC Innovation
Dialdehyde nanofibrils for foams
Tchang Cervin et al., ACS Appl. Mater. Interfaces, 8:11682−11689, 2016
BiMaC Innovation
Cellulose
O
OH
HO OH
O OOH
O O
O
Dialdehyde cellulose
Periodate oxidation
Dialcohol cellulose
Implementation project!
Implementation project!
OOH
R-HN NH-R
O
Aminated cellulose
Dicarboxylated cellulose
2x
BiMaC Innovation
Fibres partly converted to dialcoholcellulose
Zeronian et al., Tappi 14(9):557–564, 1964
Density is about 900 kg/m3
BiMaC Innovation
Dialcohol cellulose fibres
Larsson et al., Cellulose 21(1):323–333, 2014
Conventional tensile test
Zero-span tensile test
80–90% dialcohol cellulose
Kasai et al. (2014), Cellulose 21(1):769–776 = 950 kg/m3
Regenerated films
BiMaC Innovation
More extensive modification
- Higher degrees of oxidation- Beaten fibres
0 4 8 12 16 20 24
0
10
20
30
40
Deg
ree
of o
xida
tion
(%)
Oxidation time (h)
Beaten Non-beaten
5 10 15 20 25 30 35 40 45 502(°)
0% 13% 24% 40% 40% (pressed) 20% (non-beaten) 36% (non-beaten)
0 10 20 30 400
65
70
75
80
85
Crystallinity indexCry
stal
linity
inde
x (%
)
Degree of oxidation (%)
0
3.0
3.5
4.0
Crystallite widthFilled = beatenOpen = non-beaten
Cry
stal
lite
wid
th (n
m)
Larsson and Wågberg, Green Chem., 18:3324–3333, 2016
BiMaC Innovation
Dense, ductile and tough
0 10 20 30 400
20
40
60
80
100
Tens
ile s
tress
(MPa
)
Tensile strain (%)
0% 13% 24% 40% 20% non-beaten 36% non-beaten
Filled = non-pressedOpen = pressed
21 MJ/m3
CNF film(Tensile strength: 250 MPaStrain-at-break: 7%)12–15 MJ/m3
Larsson and Wågberg, Green Chem., 18:3324–3333, 2016
Density of about 1300 kg/m3
BiMaC Innovation
O2barrier
O2barrier
O2barrier
O2barrier
O2barrier
CNF based
Fibre based
Larsson and Wågberg, Green Chem., 18:3324–3333, 2016
Larsson and Wågberg., Patent WO 2017/003364 A1
BiMaC Innovation
Both thermo- and hygroplastic
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10
10
20
30
40
50
60
70
Engineering Strain ( x 100 % )
Stre
ss (M
Pa)
15.8 % and 23 oC
6.7 % and 23 oC
6.7 % and 114 oC
(mm)
Linvill et al., Materials & Design 128:231–240, 2017
BiMaC Innovation
Both thermo- and hygroplastic
Linvill et al., Materials & Design 128:231–240, 2017
Forming limit diagram
BiMaC Innovation
Extrudable dialcohol fibres
Extrusion with or without other polymer (EAA)
Heat and/or moisture
Patent filed
BiMaC Innovation
Short about implementation...
- Larger containers,- Higher concentrations and temperature,- New facilities and personnel,- …
Unexpected side reactions, lower yield, different material properties…
How do we handle and recycle the chemicals? Can we use alternative chemicals and processes?
In addition: How to form a CNF barrier? How to make a paper on existing paper machines?
...identifies technical and practical challenges by need of: