Complex Fluids Design Consortium (CFDC)

www.mrl.ucsb.edu/cfdcOverview and Update

University of California at Santa Barbara

January 23, 2007

CFDC Annual Meeting Agenda –1/23/2007 – Morning Session

9:00-9:30 Welcome and Update (Glenn Fredrickson, Director, CFDC)9:30-10:00 Rapid Mass Transport in Mixed Matrix Nanotube/Polymer Membranes (Andrei Gusev, ETH)10:00-10:30 Coffee Break10:30-11:00 A software platform for field-theoretic simulations (Eric Cochran, Iowa State U.)11:00-11:30 Progress on a force-bias algorithm in hybrid particle/field simulations (Dominik Duechs, UCSB)11:30-12:00 Inhomogeneous polymers with reversible intermolecular bonding (Won bo Lee and Richard Elliott, UCSB)12:00-1:30 Lunch

CFDC Annual Meeting Agenda – 1/23/07 –Afternoon Session

1:30-2:00 Layering transitions in thin copolymer films (Eric Cochran, Iowa State U.)2:00-2:30 Self-assembly on the sphere: a route to functional colloids(Tanya Chantawansri, UCSB)2:30-3:00 Polyelectrolyte complexation: analytical and field-theoretic simulation studies (Jonghoon Lee and Yuri Popov, UCSB)3:00-3:30 Coffee Break3:30-4:00 Thermodynamic integration: probing phase behavior beyond the mean field (Erin Lennon, UCSB)4:00-4:30 Study of nanostructuring in epoxies with SCFT (FolushoOyerokun, UCSB)4:30-5:00 Pathways to crystal nucleation and growth (Andrea Robben, UCSB)5:00-5:15 Wrap-up, Adjourn CFDC Meeting5:15-6:00 CFDC Steering Committee Meeting (Members Only, Rm 3117D MRL)

CFDC Dinner – 7pm XXX —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 at equilibrium, including polymer alloys and complex fluid formulationsAnalyzing the coupled flow, microstructure, and processing behavior of multiphase complex fluids

UCSB ParticipantsGlenn 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)Edward J. Kramer, Materials & Chem. Engr. (Polymer physics experiment, diffusion, interfaces, mechanical properties)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)

Eric Cochran, Chemical Engineering, Iowa StateSCFT theory, algorithms, and softwareExperimental polymer physics

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)Kraton Polymers (Full)*Accelyrs (Sustaining)*

*New for 2007

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 complex 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 member (shared project)As a full member (dedicated project)

CFDC Steering Committee 1/07Jun Endou (Mitsubishi)Chris Roger (Arkema)Magali Charlot (Rhodia)Azar Alizadeh (GE)Raffaele Mezzenga (Nestle)Valeriy Ginzburg (Dow)Dale Handlin (Kraton)Stephen Todd (Accelrys)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 06-07 to support a post-doc working in extending SCFT to polyelectrolytes

PD – SCFT for Polyelectrolytes (Jonghoon Lee)IGERT Program of the NSF in Computational Science and Engineering

The UCSB PIs participated in a successful proposal for graduate training that commenced Spring 2003

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

Center for Functional Engineered NanoscaleArchitectures (FENA) at UCLA

Fredrickson and Carcia-Cervera are co-PIs on a new program in block copolymer lithography

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

Several of the PIs participate in MRL programs and have access to MRL computational facilities. The MRL was renewed for 2006-2012 at $20.5MThe MRL computing facility is undergoing a major upgrade this year by 128+ processorsA pool of matching funds for unrestricted industrial gifts is available MRSEC match on first $100K of CFDC gift funds

Field-Theoretic Computer Simulations

Atomistic simulations of nano-and meso-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

G. H. Fredrickson, The Equilibrium Theory of Inhomogeneous Polymers (Oxford, 2006)

From Particles to FieldsExample: diblock copolymers

s

rA

rB

A

B

Hubbard-Stratonovich transformation

Q = single-chain partition function

A

B

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)

Scientific UpdateParallel SCFT Code – F90 and C++ versions (Scott Sides & Eric Cochran)Hybrid particle-field simulations of nano-particle/block copolymer composites (Scott Sides, Dominik Duechs/GE & MRL)SCFT in complex geometries and defect annealing strategies (August Bosse, Scott Sides, Kirill Katsov, Carlos Garcia-Cervera, Hector Ceniceros, Tanya Chantawansri/FENA & NSF)Supramolecular polymers (Ed Feng, Won bo Lee, Richard Elliott/Dow)Field-theoretic simulations at large N and numerical RG (Kirill Katsov & Michael Villet/NSF & ACS)Coupling SCFT with hydrodynamics (Turab Lookman, David Hall, SanjoyBanerjee/LANL)Beyond mean-field theory (Erin Lennon, Kirill Katsov, Hector Ceniceros, Carlos Garcia-Cervera/IGERT & NSF)Semi-flexible polymers (Tanya Chantawansri, Hector Ceniceros, Carlos Garcia-Cervera/NSF IGERT)Polyelectrolyte complexes (Jonghoon Lee/ICB & Yuri Popov/Rhodia & MCC)Nanostructured epoxies (Folusho Oyerokun/Arkema)Cubic phases in food grade polymers (Won bo Lee/Nestle)Graphoepitaxy of thin copolymer films (Su-mi Hur/FENA)Soft thermoplastic elastomers (Folusho Oyerokun/Kraton)

Licensing to Accelyrs

UCSB and Accelyrs have nearly completed an agreement to provide Accelyrs an exclusive license to market and sell our CFDC code (Cochran C++ code) as part of its Materials Studio productCFDC members of good standing will continue to receive royalty-free software distributions from the centerMembers can also directly purchase the Accelyrsproduct, if they desire the improved user interface and integrated features of Materials StudioWe expect that the partnership will help us to professionally manage our software assets

The resources provided by Accelyrs as sustaining member will be applied for this purpose

High-Resolution SCFT(Eric Cochran)

Our pseudo-spectral methods scale as O(M log M), so we can address problems with M~106-107 spatial basis functions

The gyroid structure at right has 8 unit cells computed with 1923 ~ 7x106 modes

We have corrected the Matsen-Schick calculations to show stability of gyroid (Ia3d) at strong segregation

Eric will describe the structure and workings of his code, and an application to copolymer films

B. J. Kim 2005

Fp

BicontinuousStructure

0.50

Macrophaseseparation

100 nm

Lamellar

0 0.10 0.20 0.30 0.40

Bicontinuous Transition Driven by Nanoparticle SurfactantsB. J. Kim (2006)

A Hybrid Particle-Field Simulation ApproachS. W. Sides et. al. PRL 96, 250601 (2006)

Combine a field-based description of a polymeric fluid with a particle-baseddescription of the nanoparticlesThe particles are described as cavitiesin the fluid. They can:

Be of arbitrary size, shape, and aspect ratioHave a surface treatment to attract or repel any fluid componentHave grafted polymers of any architecture on their surfaces

The fluid field equations are solved even inside the cavities for computational efficiencyThe forces on the particles can computed in a single sweep of the fluid fieldA variety of MC and BD update schemes can be applied

Block Copolymer Morphology Change Induced by Nanoparticles

SW Sides, BJ Kim, EJ Kramer, GHF, PRL 96, 250601 (2006)

By adding PS coated nanoparticles

Hybrid FTS PS-b-P2VP 58k-57k/ Au-PSLow particle conc. Low particle conc.

High particle conc. High particle conc.

Lamellar

Hexagonal

Structured nanoparticles and colloidsT. Chantawansri et. al., PRE (submitted)

Heterogeneous SupramolecularPolymers

Most supramolecular systems to date link chemically similar polymers to create compositionally homogeneous networksGreater opportunities for unique property sets should arise from linking dissimilar polymers to create block and graft copolymers or inhomogeneous networks In such systems, macrophasesand microphases can compete, and reaction equilibria plays into the self-assembly

J Ruokolainen et al. Science 1998, 280, p.1601

A theory for inhomogeneous systems(for equilibrium assembly)

Group of ten Brinke has shown how to impose mass action laws on RPA to address weakly inhomogeneous systems A more complete theory should allow for:

Exact chemical reaction equilibriumArbitrary strength inhomogeneitiesMean-field or beyond

Flexible framework based on grand canonical ensemblewith activities zA and zB of reactive chains

+

+

+

Supra diblock

Supra triblock

Triblock Phase Diagram(2NA=NB, h/χN=0.627) W.B. Lee and R. Elliott

Polyelectrolyte Complexation: CoascervatesJ. Lee and Y. Popov

Ion correlations in simple electrolytes can produce a liquid-liquid phase separation at low T that remains poorly understood (Percus, Fisher, …)A similar complexation occurs in mixtures of polyanions and polycations at low charge densities and room temperature (coascervation)Homogeneous phases have been studied at the Debye-Hückel(one-loop) level by Joanny, Olvera de la Cruz, and othersWe can conduct direct simulations of a relevant field theory model (no salt)

σ: charge fraction

lB =e2 /ε kBT: Bjerrum length

+ +

+

+

- -

--

CFDC Annual Meeting Agenda –1/23/2007 – Morning Session

9:00-9:30 Welcome and Update (Glenn Fredrickson, Director, CFDC)9:30-10:00 Rapid Mass Transport in Mixed Matrix Nanotube/Polymer Membranes (Andrei Gusev, ETH)10:00-10:30 Coffee Break10:30-11:00 A software platform for field-theoretic simulations (Eric Cochran, Iowa State U.)11:00-11:30 Progress on a force-bias algorithm in hybrid particle/field simulations (Dominik Duechs, UCSB)11:30-12:00 Inhomogeneous polymers with reversible intermolecular bonding (Won bo Lee and Richard Elliott, UCSB)12:00-1:30 Lunch

CFDC Annual Meeting Agenda – 1/23/07 –Afternoon Session

1:30-2:00 Layering transitions in thin copolymer films (Eric Cochran, Iowa State U.)2:00-2:30 Self-assembly on the sphere: a route to functional colloids(Tanya Chantawansri, UCSB)2:30-3:00 Polyelectrolyte complexation: analytical and field-theoretic simulation studies (Jonghoon Lee and Yuri Popov, UCSB)3:00-3:30 Coffee Break3:30-4:00 Thermodynamic integration: probing phase behavior beyond the mean field (Erin Lennon, UCSB)4:00-4:30 Study of nanostructuring in epoxies with SCFT (FolushoOyerokun, UCSB)4:30-5:00 Pathways to crystal nucleation and growth (Andrea Robben, UCSB)5:00-5:15 Wrap-up, Adjourn CFDC Meeting5:15-6:00 CFDC Steering Committee Meeting (Members Only, Rm 3117D MRL)

CFDC Dinner – 7pm Spice Avenue —sign up at break

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 AgreementUnrestricted Gift

No formal research contractNo UCSB overhead Eligible for NSF-MRSEC matching fundsSponsor can participate in definition and execution of project

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

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”

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