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

Freeze-linked gels

Erlandsson et al., Applied Materials Today, 5:246–254, 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

Reference Most modified

Non-pressed Pressed Non-pressed Pressed

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:

BiMaC Innovation

Thank you for yourkind attention!