Complex Fluids Design Consortium (CFDC)

www.mrl.ucsb.edu/cfdcOverview and Update

University of California at Santa Barbara

February 2, 2005

CFDC Annual Meeting Agenda –2/1/05 – Morning Session

9:00-9:30 Overview and Update (Glenn Fredrickson, Director, CFDC)9:30-10:00 Direct numerical predictions for the properties of complex microstructure composite materials (Andrei Gusev, ETH)10:00-10:30 Coffee Break10:30-11:00 Progress on a spectral-filtering algorithm: increased speed in numerical SCFT simulations (Scott Sides, Tec-X Corp.)11:00-11:30 On elasticity of block-copolymer mesophases with glassy domains (Kirill Katsov, UCSB)11:30-12:00 Variable box shape SCFT (Eric Cochran, UCSB)12:00-1:30 Lunch

CFDC Annual Meeting Agenda –2/1/05 – Afternoon Session1:30-2:00 Mesoscale modeling of hybrid organic-inorganic materials at the Dow Chemical Company (Valeriy Ginzburg, Dow)2:00-2:30 Lateral confinement of block copolymer thin films in SCFT(August Bosse, Carlos Garcia-Cervera, Scott Sides, UCSB)2:30-3:00 Multiscale modeling of thermoplastic elastomers (Stephan Baeurle, UCSB)3:00-3:30 Coffee Break3:30-4:00 Modeling supramolecular polymer systems (Edward Feng, UCSB)4:00-4:30 Hydrodynamic self-consistent field theory: the continuing saga (David Hall & Sanjoy Banerjee, UCSB, Turab Lookman, LANL)4:30-4:45 Wrap-up, Adjourn CFDC Meeting5:00-6:00 CFDC Steering Committee Meeting (Members Only, Rm3014 MRL)

CFDC Dinner – 7pm Ming Dynasty—sign up at break

What is the CFDC?The Complex Fluids Design Consortium is an academic-industrial-national laboratory partnership aimed at developing computational tools for:

Designing soft materials, including polymer alloys and complex fluid formulationsAnalyzing the coupled flow, microstructure, and processing behavior of multiphase complex fluids

UCSB Participants

Glenn Fredrickson, Chem. Engr. & Materials (Polymer physics, field theory, mesoscopic simulations)Sanjoy Banerjee, Chem. Engr. & Mechan. Engr. (Turbulence modeling, multiphase flow of structured fluids)Hector Ceniceros, Mathematics (Numerical methods, multiscale PDEs, computational fluid mechanics)Carlos Garcia-Cervera, Mathematics (Numerical methods, stochastic PDEs)Others, as per interest

National Lab ParticipantsLANL

Turab Lookman (kinetics of phase transitions)Tony Redondo (multiscale materials modeling)

SNLJohn Curro (liquid state theory, PRISM)Gary Grest (MD, MC of polymers)Amalie Frischknecht (Density functional theory, PRISM)

Other Academic CollaboratorsAndrei Gusev, Materials, ETH Zurich

Finite element methodsComposite media modeling (Mechanical, transport, and optical properties)

David Morse, Chemical Engineering, U. Minnesota

SCFT theory and algorithms

David Wu, Chemistry and Chemical Engineering Depts., Colorado School of Mines

Molecular simulationsPRISM

Current Industrial Partners

Arkema Chemicals (Full)Mitsubishi Chemical (Sustaining)Rhodia (Sustaining)General Electric CR&D (Full)Dow Chemical (Full)Nestle Research Center (Full)

The Problem—Design of Polymer FormulationsPolymer formulations are complex fluids:

Multiphase plasticsSolution formulationsProcessed foods…Can exhibit complex self-assembly and phase behavior

Relationship between formulation, structure, and properties difficult to establish

Trial and error experimentation is norm

Can Theory/Simulation help?

What do we hope to accomplish?

To create a suite of models, theoretical approaches, numerical methods, and software that:

Can be shared among the members of the consortiumCan be applied to address materials design problems and fluid processing problems of collective or individual interest

Objectives -- continuedCreate a world-class center for complex fluid and soft materials modelingEnhance interactions among the academic, industrial, and national lab partners and pool funding for supporting research projects of mutual interestCreate employment opportunities for the students and post-docs of the consortium

Organization and Partnership Model

UCSB is focal point for the CFDCCFDC “Steering Committee” will guide collective research agendaAcademic partners will contribute:

Time and expertiseAccess to graduate students and postdocsFunding though group grants

National lab partners will contribute:Time and expertiseAccess to computational facilitiesFunding though group grants, and/or DOD/DOE programs

Partnership Model -- continued

Industrial partners will contribute:Staff timeComputational resourcesFunding

As a sustaining memberAs a full member

Participation Levels

Sustaining Member: $35K/yr as an unrestricted gift

Access to annual workshopAccess to shared software toolsAccess to students & postdocsRepresentation on Steering Committee and participation in group project selection

Participation Levels –Ctd.Full Member: Annual funding as unrestricted gift or research contract sufficient to support one postdoc or graduate student

Access to annual workshopAccess to shared software toolsAccess to students & postdocsRepresentation on Steering Committee and participation in group project selectionIndividually customized project to address sponsor’s R&D needs and interests

Gift Verses Research AgreementResearch Agreement

Formal research contract with IP provisionsUCSB overhead assessed at 47.5% of direct costsProject and milestones can be defined in writing

Unrestricted GiftNo formal research contractNo UCSB overhead Eligible for NSF-MRSEC matching fundsSponsor can participate in definition and execution of project

Gift Research Agreement

Student $50,000 $75,000

Postdoc $75,000 $100,000

CFDC Software Distribution PolicySoftware developed at UCSB under CFDC funding will be made available for distribution to industrial partners at no cost, provided:

Use is for non-commercial research or educational purposesRecipient acknowledges that software is provided “as is”

CFDC Steering Committee 1/05Takao Usami (Mitsubishi)Brian Edgecombe (Arkema)Magali Charlot (Rhodia)Azar Alizadeh (GE)Raffaele Mezzenga (Nestle)Valeriy Ginzburg (Dow)Turab Lookman (LANL)John Curro (SNL)Andrei Gusev (ETH)Sanjoy Banerjee (UCSB)Glenn Fredrickson (UCSB), Chair

Update--Leveraged ActivitiesInstitute for Collaborative Biotechnologies (ICB)

Our grant was renewed for 05-06 to support a post-doc working in extending SCFT to polyelectrolytes

PD – SCFT for Polyelectrolytes (Jonghoon Lee)

IGERT Program of the NSFThe UCSB PIs participated in a successful proposal for graduate training that commenced Spring 2003

GS – Time integration methods for stochastic field-based simulations (Erin Lennon)GS—Pseudo-spectral solutions of the wormlike chain Fokker-Planck equation (Tanya Chantawansri)

UCSB IGERT Program in Computational Science and Engineering

PhD programDepartments: Chemical Engineering, Computer Science, Mathematics, Mechanical and Environmental EngineeringResearch: Students will work in interdisciplinary teams. Theses will be jointly supervised.

Complex FluidsComputational Materials ScienceMicroscale Engineering

Two new courses:Atomic-Scale Computer Simulation MethodsPractical High-Performance Computing

Internship partners include: Lawrence Livermore National Laboratory, Los Alamos National Laboratory, Sandia National Laboratories, Chevron/Texaco, Avery-Dennison, Air Products and Chemicals, + CFDC members.Career development workshop, guest speakers and visitors, some travel support

Leveraged Activities – Ctd.Materials Research Laboratory (NSF MRSEC)

Several of the PIs participate in MRL programs and have access to MRL computational facilities. A pool of matching funds for unrestricted industrial gifts is available (MRSEC match on first $100K of CFDC gift funds)

DOE ProgramsWe are in discussion with SNL and LANL regarding appropriate DOE programs to apply to for longer-term funding, e.g. Office of Industrial Technology

Scientific UpdateParallel SCFT Code – Defect relaxation methods (Scott Sides/Arkema)Mechanical properties of thermoplastic elastomers (Andrei Gusev & Stephan Baeurle/MCC & Rhodia; Kirill Katsov/NSF)Nano-particle/block copolymer composites (Ellen Reister & Eric Cochran/GE CR&D)SCFT in complex geometries (August Bosse, Scott Sides, Kirill Katsov, Carlos Garcia-Cervera/NSF)Supramolecular polymers (Ed Feng/Dow)Coupling SCFT with hydrodynamics (Turab Lookman, David Hall, Sanjoy Banerjee/LANL Care)

Beyond mean-field theory (Erin Lennon, Hector Ceniceros, Carlos Garcia-Cervera/NSF Igert)Semi-flexible polymers (Tanya Chantawansri, Hector Ceniceros, Carlos Garcia-Cervera/NSF Igert)Polyelectrolytes (Jonghoon Lee/ICB)

Field-Theoretic Computer Simulations

Atomistic simulations of nano-structured polymers are not feasible

Field-theoretic simulations of field-based models provide:

Seamless connection to continuum property modeling Spatial resolution can be continuously adjusted by spectral, FD, or FE field representations Polymeric Microemulsion,

Bates et.al. 1997

≈1014 “atoms” τ>10 s

From Particles to FieldsExample: diblock copolymers

s

rA

rB

A

B

Hubbard-Stratonovich transformation

A

B

Q = single-chain partition function

Mean-Field Approximation: SCFT

• SCFT is derived by a saddle point approximation to the FT:

• The approximation is asymptotic for

• We can simulate the field theory at two levels:

• “Mean-field” approximation (SCFT): F ≈ H[w*]

• Full stochastic sampling of the complex field theory: “Field-theoretic simulations” (FTS)

+volume fraction of homopolymer-monomers

fraction of A monomers on each triblock chain fAχNh = 16.0

light

darkABA triblock + A homopolymer alloyArkema Chemicals

Nt /Nh = 2

+ lightPolymer 44 (2003) p. 5859

256 Rg

10 CPU hours16, 1.9 GHz processors1024 x 1024 lattice3000 iterations

ABC triblock 643 46,000 field iterations 50 hrs 16 processors

c.f. PI-PS-PEO materials of Bates group

χAB = χBC = 0.05

χAC= 0.20

fA = fC = 0.25fB = 0.50

A B C Contour surfaceof φA= 0.55

Simulation resultsExperiments: Acrylic BCsArkema/ESPCI (Paris)

<φΒ > = 0.35<φA > ~ 0.65

PBA

PMMA (light)

(dark)pdi =1.00

<φPMMA > ~ 0.65<φPBA > ~ 0.35

<φA > ~ 0.65 <φΒ > ~ 0.35

PDI ~ 2.0-3.0

pdi=1.225

200 nm 12 Rg ~214 nmTEM data courtesy of A.-V. Ruzette

SelfSelf--Assembly within a Cylindrical PoreAssembly within a Cylindrical Pore

dip-coating

Precursor solution:1.38g P12310g ethanol

2.7g pH=2 H2O5.2g TEOS •Aging (25oC, 65-75% RH):

--Evaporization of ethanol,H2O, HCl.

--Liquid-crystalline mesophase locks in.•Calcined at 400oC for 3hr.

hydrophilic hydrophobic hydrophilic

EO EOPO

20 70 20

500nm

* Expt. data courtesy of Stucky group at UCSB

Diblock + homopolymer in a cylindrical pore

χΑC N = 0.1 (hydrophilic)χΒCN = 15.0 (hydrophobic)χABN = 15.0VC = 0.30 fA = 0.60

* walls attract C homopolymer and repel AB diblock

BA

C

SCFT parameters:χΑCN, χΒCN, χABN – segregation strengthsVC -- vol fraction of solventNC -- length of homopolymerfA -- size of A block

S. W. Sides & K. Katsov

Yiying Wu, G. D. Stucky

31nmD-helix/no-core

18nmS-spheres

Yiying Wu, G. D. Stucky

Core-shellD-helix

52nm

40nmS-helix/core Nature Materials

3, 816 (2004)

Summary—Expt. and Theory

Constant Strain SimulationsS. Sides, J-L Barrat, S. Baeurle, K. Katsov, & GHF (2005)

Experimental buckling studies:Y. Cohen, M. Brinkmann, E.L. Thomas, JCP 114, 984 (2001)

Unit Cell Calculations (Eric Cochran)

The previous were examples of large-cell calculations, which are most useful in a discovery modeFor accurate computations of free energies and phase diagrams unit cellcalculations are preferred (Matsen & Schick)The pseudo-spectral approach can also be adapted to parallelepiped unit cells with O(Ng log Ng ) scaling Ia3d (gyroid) phase of diblock

copolymer melt, Ng=643, f=.39, χN=15

Constant Stress SimulationsJ-L Barrat, GHF, S. W. Sides, J. Phys. Chem. (in press);E. Cochran

Extension of Parrinello-Rayman-Ray formalism to field-based simulationsTransformation of a square cell at zero applied external stress to the primitive cell of the hexagonal phase, χN=20, f=0.3

Constant Stress SimulationsJ-L Barrat, GHF, S.W. Sides, J. Phys. Chem. (in press)

Transformation of a hex phase subject to uniaxial compression along the horizontal axis at χN=16, f=0.64

Work in Progress and New Capabilities

Sampling techniques for beyond mean-field theory“Sign” problemImproved numerical methods

Systems with quenched and annealed disorderPolydispersityRandom grafting and couplingSupramolecular polymers/reversible bonding

Polyelectrolytes and PE copolymersColloids, nanoparticles and polymersPolymers with intramolecular structure

LCPs – wormlike chainsFreely jointed, freely rotating, RIS models

Nonequilibrium phenomenaQuasi-static controlled stress or strain simulationsProcessing behavior, coupled flow and mesostructuralevolution

CFDC Annual Meeting Agenda –2/1/05 – Morning Session

9:00-9:30 Overview and Update (Glenn Fredrickson, Director, CFDC)9:30-10:00 Direct numerical predictions for the properties of complex microstructure composite materials (Andrei Gusev, ETH)10:00-10:30 Coffee Break10:30-11:00 Progress on a spectral-filtering algorithm: increased speed in numerical SCFT simulations (Scott Sides, Tec-X Corp.)11:00-11:30 On elasticity of block-copolymer mesophases with glassy domains (Kirill Katsov, UCSB)11:30-12:00 Variable box shape SCFT (Eric Cochran, UCSB)12:00-1:30 Lunch

CFDC Annual Meeting Agenda –2/1/05 – Afternoon Session1:30-2:00 Mesoscale modeling of hybrid organic-inorganic materials at the Dow Chemical Company (Valeriy Ginzburg, Dow)2:00-2:30 Lateral confinement of block copolymer thin films in SCFT(August Bosse, Carlos Garcia-Cervera, Scott Sides, UCSB)2:30-3:00 Multiscale modeling of thermoplastic elastomers (Stephan Baeurle, UCSB)3:00-3:30 Coffee Break3:30-4:00 Modeling supramolecular polymer systems (Edward Feng, UCSB)4:00-4:30 Hydrodynamic self-consistent field theory: the continuing saga (David Hall & Sanjoy Banerjee, UCSB, Turab Lookman, LANL)4:30-4:45 Wrap-up, Adjourn CFDC Meeting5:00-6:00 CFDC Steering Committee Meeting (Members Only, Rm3014 MRL)

CFDC Dinner – 7pm Ming Dynasty—sign up at break