2013 German-American Frontiers of Engineering Symposium, NAE April 26-28, 2013, Irvine, Overview of Materiomics: Impact on Biological and Non-Biological Systems Markus J. Buehler Laboratory for Atomistic and Molecular Mechanics Department of Civil and Environmental Engineering Massachusetts Institute of Technology E-mail: [email protected] URL: http://web.mit.edu/mbuehler/www/

Support: National Science Foundation, Department of Defense, NIH

Additive manufacturing in nature 2 Francesco Tomasinelli and Emanuele Biggi

Steel: strength ~1 GPa: strong bonds Spider silk: strength: ~1-2 GPa & 60% strain @ failure extreme toughness weak bonds; made @ room temperature via self-assembly

spider web

silk

Francesco Tomasinelli3 and Emanuele Biggi 4Source: MJB & NSF proteins Top-down vs. bottom-up A new paradigm of material design

Conventional: “Top-down approach” “bottom-up approach” – example: spider silk, self-assembled solid, - Requires many different raw materials stronger than steel - Limited structural control & flexibility spinning Dennis Kunel

Material DNA Design

Van Vliet, Yip, Buehler, Ulm et al., MRS Bulletin, 2012

New: “Bottom-up approach” - Few raw materials - Enhanced flexibility through structure (spider) silk spinning protein - Integration of material synthesis 4 ‘letters’ material/ liquid to solid 20 building blocks with manufacturing of product ACGT tissue (system perspective) (amino acids)

5 - Bioinspired M. Buehler et al., Nano Letters, 2011; Nature, 2012; Kaplan, Buehler, Wong, et al., 2012

Diverse material properties, same building block Universality-diversity paradigm – UDP

H. Waite/USCB underwater adhesive Multifunctionality actin, intermediate (mussels) (diversity) created filaments (cell) by changing structural silk fibers (spider web) arrangements of few (universal) constituents rather than inventing new collagen building blocks (tendon) Powerful paradigm for innovation - Fewer resources - More flexibility - Wider design

http://www.olympusmicro.com space

Materials composed from a library of ~20 amino acids (proteins) 7 8 M. Buehler, Nature Nanotechnology, 2010 Integration of experiment and computation Really big computers…

Anton Connecting the virtual to D.E. Shaw Research the physical world

Quantum mechanics Buehler et al., Nature Materials, 2009;. Z. Qin et al., 2010, 2012 10 Folding@Home

Computing capacity over time Molecular simulation – visualizations

A. Gautieri – collagen molecule in water

Large-scale simulation of complex biomolecules (water, solvent, reactivity…) M. Solar – molecular mechanics of amyloid fibril 11Source: TIME magazine 12 Structure prediction and functional properties

Genetics …GGLGGQGAGAA Replica Amino acid AAAAGGAGQG … Exchange sequence Simulations

Folding Validation Ensemble (experimental of final —structure results) structures

 Mechanical characterization (multiscale) Mechanics

(functionality) 14 13 NSF + Buehler et al 

hydrophilic Smaller is stronger (mix w/ water) = B detailed study: ~2-3 nm (nanocrystal)

hydrophobic, form crystals (don’t mix w/ water) = A

Smaller crystals (left) are stronger: Larger crystals (right) are fragile, crack easily

Keten, Buehler et al., Nature Materials, 2010 Coarse-grained modeling of stretching Coarse-grained modeling of stretching

Interplay of two “particles” - describe material properties of silk from “first principles” 17 Nova et al., Nano Letters, 2010 Nova et al., Nano Letters, 2010

Web mechanics: putting all scales together Mechanics of spider webs

Silk structure identified yield Constitutive behavior point using statistical methods Nanomechanical (derived from molecular (Replica Exchange MD) characterization principles: mechanisms – protein unfolding, slip of beta- sheets, failure, etc.)

Macroscale system (web)

Force beta-sheet Silk protein 31-helices – “B” nanocrystal – “A” sequence (semi amorphous) failure of Macroscopic web beta-sheets state molecular

failure mechanics deformation

linked with molecular position mechanisms Key result: Mechanical properties of web depend not only on strength and toughness of silk fibers, but are controlled by the details of the stress-strain behavior (nonlinearity), 19 S. Cranford, M. Buehler, et al., Nature, 2012 which was linked to its origin at the molecular scale Case study:

Creating designer silks based on natural building blocks

A = hydrophobic domain HBA3

B = hydrophilic domain

HAB3

21 Funding: NIH/U01 EB014976 Kaplan, Wong, Buehler et al., 2012

How sequence controls structure & mechanics Mimicking a spider’s spinning duct

Mw, Code Spider silk-like block copolymers Kaplan, Wong, Buehler et al., Advanced Da Functional Materials, 2013 M H H H H H H S S G L V P R G S G M K E T A A A K F E R Q H M D S P D L G T D D D D K A M A A S Q G G Y G G L G S Q G S G R G G L G G Q HBA3 10,068 T S G A G A A A A A G G A G T S G A G A A A A A G G A G T S G A G A Experiment: Modulus A A A A G G A G T S EAB3 = 0.16±0.03 GPa M H H H H H H S S G L V P R G S G M K E T A A A K F E R Q H M D S P D L G T D D D D K A M A A S G A G A A A A A G G A G T S Q G G Y G EBA3 = 0.44±0.1 GPa HAB3 11,967 G L G S Q G S G R G G L G G Q T S Q G G Y G G L G S Q G S G R G G L Spider’s spinning Microfluidic Spinning G G Q T S Q G G Y G G L G S Q G S G R G G L G G Q T S duct 400 μm softer

pH drop 6.9 4.8 silk solution fiber pH 6.6 mechanical shear/ elongational flow PEO solution pH 1.5

protein dope  semicrystalline fiber Enable to test small volume & to tune processing conditions

23 24 Kinahan, Wong, et al, Biomacromolecules (2011) Microscopic insight from molecular simulation DiatomDeep algae sea sponges (silica)

20 μm ., HAB3 + RSF, Homogeneous Material forms fiber, but et al Some connectivity sustains negligible tensile load

20 μm

HBA3 + RSF, Inhomogeneous Aggregates forms globular aggregates, Very poor connectivity breaks by tiny agitation

Ryu, Gronau, Kaplan, Wong, Buehler Buehler Kaplan, Wong, Ryu, Gronau, 26 25

Nanoporous silica (vs. bulk silica)

Bulk silica Bulk silica Nanoporous Nanoporous

28 Sen, Buehler, IJAM, 2010 Hierarchical composites with large toughness Systems perspective – materiomics

Biomineralized representation

, 2011 composite material – ‘biolog’ Scientific Reports Sen, Buehler, Sen, Buehler,

J-integral analysis

David Spivak (MIT )

*90% of fracture strength 29 D. Spivak, T. Giesa, L. Wood, M. Buehler, PLoS ONE, 2011

From model to physical sample

multiscale model

additive manufacturing (inkjet/UV crosslinked)

• Samples tested in tension Toughness 21× larger than • Measure force- the toughest of the two displacement building blocks • Image deformation/failure mechanisms L. Dimas & M. Buehler, et al., Advanced Functional Materials, 31 L. Dimas & M. Buehler, et al., Advanced Functional Materials, 2013 32 2013 SEM analysis of failure mode Rough at interface- No interfacial failure large shear

Distributed Failure

L. Dimas & M. Buehler, et al., Advanced Functional Materials, 2013

Tunable wettability using graphene

carbon materials (graphene family)

Mimic Lotus effect (superhydrophobicity) using graphene nanotechnology

Reversible proteins (better than nature!)

Ozkan, Buehler, Kang et al., JMR, 2013 35 Zang, Buehler, Zhao, et al., Nature Materials, 2013 Merger of structure and material

Frontier: “meso”

Need predictive tools to enable design Need effective methods to store learned data, …. 38 37Quantum to continuum Ackbarow, Buehler et al., Materials Today, 2007 Photo: Francesco Tomasinelli and Emanuele Biggi