Department of Chemical Engineering Mc Gill University Computational

Department of Chemical Engineering Mc. Gill University Computational Engineering of Cholesteric Collagen I Films: Rheological Properties, Nematodynamics and Film Formation Oscar Aguilar-Gutierrez, Pardis Rofouie Alejandro D. Rey* IMA “Liquid Crystals, Soft-matter Packing, and Active Systems: Materials and Biological Applications” University of Minnesota Minneapolis January 16, 2018 Funding: NSERC, FQNRT, COMPUTE CANADA, CLUMEQ 1

Biological Plywoods: Nature’s Fibrous Composites mm chiral fiber arrangement like a cholesteric liquid crystal bone Bouligand structure cornea 2 A. C. Neville, “Biology of Fibrous Composites”, Cambridge University

Biological Liquid Crystals I. Biological analogues (BA) II. In vitro (VT) III. In vivo (VV) -Plant cell wall -Collagen -Silk -Connective tissues in mammals -Cellulosics -Collagen in egg shell & -Exoskeleton of insects and crustaceans -Chitin glands of dog fish -Viral suspensions -DNA (sperm ) -Bone -DNA solutions acidic collagen Le/De=10 -40 Le/De=15 -45 Le/De=15 3 ADRey, Soft Matter (2010) Excluded volume

GOAL: How to Fabricate Defect Free Thin Cholesteric Collagen Films POLYDOMAIN MONODOMAIN molecular triple helix collagen Park et al. Chem Phys Chem (2014) Kirkwood & Fuller, Langmuir, 2009. h=constant 4

Generic Fabrication Approach Flow-process dilute solution into well-aligned para-nematic Convective drying and helix formation Kirkwood & Fuller. Langmuir (2009 ) Defect-free cholesteric film with nanowrinkled surface 5

Generic Fabrication Modeling Challenges 1. Melt chirality and create an isotropic phase that can be flow-structured C Need : phase diagram; 2. Flow-process to create a ordered and aligned non-equilibrium paranematic phase Need : rotational diffusivity, tumbling function, response to complex flows 3. Remove water and form chiral film with surface nanowrinkling Need : water transport and helix formation kinetic couplings, shape equation 6

Phase Diagram : C*, Lp/Deff, Gobeaux et al Langmuir (2007) Deff 50 -60 mg/ml to 80 -85 mg/ml as the acetic acid conc. of the solvent increases from 5 to 500 m. M. Lp Excluded Volume + electrostatics +flexibility p=Lp/Deff=14. 6 -43 C*=100 mg/ml Ciferri, MCLC (1990), Khokhlov et al, Macromolecules, 1984, A. D. Rey , Soft Matter (2010)

Free Energies (i) Delayed ordering (iii) Defects Ch ira lit y (P =S ) (ii) Biaxial ordering P S G. de. Luca and A. D. Rey , PRE (04) S n disclinations & dislocations

Key Non-Equilibrium Issue to Flow Process Collagen Orientation Distribution Function Ensemble of Rods Second Moment (Q-Tensor) of the Orientation Distribution Function use Effect of shear flow on Q Two possible responses > aligning tumbling < Rey, Alejandro D, MM. Denn. , Annual Review of Fluid Mechanics 34. 1 (2002): 233 -266.

Use Nematodynamics and Compare with Experiments Flow-Induced Orientation/Back-Flow Cycle Flow velocity Flow-induced orientation defects Q- velocity 4 D Parametric Space Back-flow ? 10 Marrucci and Greco (1993), Rey and Denn (2001)

Dilute Solution Flow Birefringence Experiments 50 -60 mg/ml to 80 -85 mg/ml as the acetic acid conc. increases from 5 to 500 m. M. Para Nematic Gobeaux et al Langmuir (2007) 11

Cholesteric Collagen I Properties’ Estimates from Dilute Solution SAXS Lp=220 nm, Deff=3. 96 nm aligning Lp tumbling O. F. Aguilar Gutiérrez and A. D. Rey, Langmuir, 11799– 11812, 2016. 12

Two Issues for Flow Processing : Flow Type and Flow Intensity Extension + Shear Flow What type flow? well-ordered + well aligned para-nematic weakly-ordered + weakly aligned para-nematic How much intensity ? 13

Use Taylor’s Four Roll Characterization Forest, M. G. , Wang, Q. , Zhou, R. , & Choate, E. P. (2004). Journal of nonnewtonian fluid mechanics, 118(1), 17 -31 Flow strength Flow type 14 O. F. Aguilar Gutiérrez and A. D. Rey, Langmuir, 11799– 11812, 2016.

How to Achieve Optimal PN State Flow strength Flow type good alignment and order (k=0. 2, De=1) for shear (k=1, De=0. 6) for extensional Experiments. 1 m. L/min, draw-ratio=10 15 O. F. Aguilar Gutiérrez and A. D. Rey, Langmuir, 11799– 11812, 2016.

Directed Dehydration Initial Paranematic State extension-shear mix flow-aligned Transient Evolution water flux airflow Aguilar Gutierrez & Rey, Soft Matter (2017) 16

Dehydration Microstructures P = 1 x 10 -6 P = 1 x 10 -5 P = 2 x 10 -5 0. 3 Slow water removal y y -0. 3 h = h(t) z -0. 5 0. 5 z P = 4 x 10 -5 P = 1 x 10 -4 P = 1 x 10 -3 0. 3 Fast water removal y -0. 3 -0. 5 0. 5 z Aguilar Gutierrez & Rey, Soft Matter (2017) Kirkwood & Fuller, Langmuir, (2009) 17

Dehydration of Soft Matter and Solidification of Hard Matter Removal of Heat Removal of Water Aguilar Gutierrez & Rey, Soft Matter (2017) 18

Interfacial Instability in 1 D Travelling Front Solutions Gino de Luca and AD Rey, PRE (2004)

Asyynchronous Nondirectional Dehydration: defects P = 1 x 10 -5 “Slow” “Fast” P = 1 x 10 -3 3 D Water flux S S U Aguilar Gutierrez & Rey, Soft Matter 20 (2017)

Synchronicity Principle: Defect Free Films S U S nx Aguilar Gutierrez & Rey, Soft Matter 21 (2017)

Process Operating Window Parabola defining constant P Aguilar Gutierrez & Rey, Soft Matter (2017) Line defining synchronicity 22

Nematic Shape Equations Capillary Vector X ( geometric molecular field) Rayleigh LC fiber instabilities Peristaltic Cheong AG, Rey AD. JCP ( 2002) Chiral Interfacial defect shedding Oh, S; Advanced Materials 26. 30 (2014) 23

Nano-wrinkling Elastic Mechanism Rofouie, Rey, COLCOM , 2014 Kirkwood, Langmuir 2009

Wrinkling Scaling Law Experiments Weak anchoring -0. 2<W/γ 0<-0. 001 P. Rofouie et al. , COLCOM. 2014 Chiral polymer [1] Collagen solution [2] Liquid crystalline collagen [3] Cellulosic cholesteric film [4] h(nm) λ(µm) 2. 5 100 150 5 0. 63 7. 5 8 0. 5 W/go fitted 0. 028 0. 079 0. 110 0. 059 Force microscopy of CLCs [1] [1] Terris, B. D. ; Twieg, R. J. ; Nguyen, C. ; Sigaud, G. ; Nguyen, H. T. , Europhysics Letters 1992 [2] Maeda, H. , Langmuir 1999 [3] Kirkwood, J. E. ; Fuller, G. G. , Langmuir 2009 [4] Fernandes, S. N. ; Geng, Y. ; Vignolini, S. ; Glover, B. J. ; Trindade, A. C. ; Canejo, J. P. ; Almeida, P. L. ; Brogueira, P. ; Godinho, M. H. , 25 Macromolecular Chemistry and Physics 2013

Conclusions and Outlook 1. Properties 2. Flow Process Need shear+ extension 3. Drying-Ordering Process Align water flux and helix 4. Process Operating Window Synchronize mass transfer and helix formation 26 5. Nanowrinkling