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Nanofluids:Nanofluids: Advanced Flow and Heat Transfer Fluids Advanced Flow and Heat Transfer Fluids

Prof. M. KosticProf. M. KosticMechanical EngineeringNORTHERN ILLINOIS UNIVERSITY

Cooling System

Liquid

Resistively Heated Crucible

Deionized water prior to(left) and after (right)dispersion of Al2O3

nanoparticles

Oil prior to (left) andafter (right) evaporationof Cu nanoparticles

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Wet-Nanotechnology:

nanofluidsat NIU

in collaboration with ANL

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First NIU Nanofluids

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Dry- vs. Wet-nanotechnology

• Fluids (gases & liquids) vs. Solidsin Nature and (Chemical & Bio) Industry

• More degree of freedoms – more opportunities…(also more challenges)

• Nanofluids: nanoparticles in base fluids * Understanding nano-scale particle-fluid interactions

in physical-, chemical-, and bio-processes, and engineering new/enhanced functional products

• Directed self-assembly:* starts from suspension of nanoparticles in fluids* ends with advanced sensors and actuators, devices,

systems, and processes

• Synergy of dry-nanotechnology (solid-state) & wet-nanotechnology (POLY-nanofluids)

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Nanofluids: Suspensions of nanoparticles in base fluids

Size does matter: unique transport properties, different from conventional suspensions: do not settle under gravity, do not block flow, etc …

• Enhancing functions and properties by combining and controlling interactions

• Combining different nanoparticles (structure, size) in different base-fluids with additives

• Controlling interactions using different “mixing” methods and thermal-, flow-, catalyst-, and other field-conditions

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Wet-Nanotechnology:nanofluids’ applications

Advanced, Advanced, hybrid nanofluidshybrid nanofluids::• Heat-transfer nanofluids (ANL & NIU)• Tribological nanofluids (NIU)• Surfactant and Coating nanofluids• Chemical nanofluids• Process/Extraction nanofluids• Environmental (pollution cleaning) nanofluids• Bio- and Pharmaceutical-nanofluids• Medical nanofluids

(drug delivery and functional tissue-cell interaction)

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NIU- nanofluids

Development of advanced hybrid nanofluids:POLY-nanofluids (Polymer-nanofluids) and DR-nanofluids (Drag-Reduction-nanofluids)

• Development of Heat-transfer nanofluidsCollaboration with ANL and NSF Proposal Related Invention/Patent Application pendingCoherent X-ray Scattering Dynamic Characterization

• Development of Tribological nanofluidsCenter for Tribology and Coating (CTC) Project

More at:www.kostic.niu.edu/DRnanofluids

Web Search>nanofluids

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Acknowledgment and Thanks:Acknowledgment and Thanks:This presentation is in part based on the above PresentationThis presentation is in part based on the above Presentation

by Dr. Steven U.S. Choi, by Dr. Steven U.S. Choi, Energy Technology Division

Argonne National LaboratoryArgonne National Laboratory

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Inter-Institutional Collaboration:• Northern Illinois University:

– M. Kostic, Mechanical Engineering (Flow and Heat Transfer Characterization)

– L. Lurio, Physics (Structural Characterization)

– C.T. Lin, Chemistry (Interfacial/Surface Enhancers)

• ANL:– Steven U.S. Choi, Energy Technology (Nanofluid Pioneer Researcher)– John Hull, TEM Manager, Energy Technology– Wenhua Yu, Energy Technology

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Background

• Need for Advanced Flow and Heat-Transfer Need for Advanced Flow and Heat-Transfer Fluids and Other Critical ApplicationsFluids and Other Critical Applications

• Concept of NanofluidsConcept of Nanofluids• Materials for Nanoparticles and Base FluidsMaterials for Nanoparticles and Base Fluids• Methods for Producing Methods for Producing

Nanoparticles/NanofluidsNanoparticles/Nanofluids• Characterization of Nanoparticles and Characterization of Nanoparticles and

NanofluidsNanofluids• Thermo-Physical PropertiesThermo-Physical Properties• Flow and Heat-Transfer CharacterizationFlow and Heat-Transfer Characterization

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Advanced Flow and Heat-Transfer Challenges

• The heat rejection requirements are continually increasing due to trends toward faster speeds (in the multi-GHz range) and smaller features (to <100 nm) for microelectronic devices, more power output for engines, and brighter beams for optical devices.

• Cooling becomes one of the top technical challenges facing high-tech industries such as microelectronics, transportation, manufacturing, and metrology.

• Conventional method to increase heat flux rates:

– extended surfaces such as fins and micro-channels

– increasing flow rates increases pumping power.

• However, current design solutions already push available technology to its limits.

• NEW Technologies and new, advanced fluids with potential to improve flow & thermal characteristics are of critical importance.

• Nanofluids are promising to meet and enhance the challenges.

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Concept of Nanofluids• Conventional heat transfer fluids have

inherently poor thermal conductivity compared to solids.

• Conventional fluids that contain mm- or m-sized particles do not work with the emerging “miniaturized” technologies because they can clog the tiny channels of these devices.

• Modern nanotechnology provides opportunities to produce nanoparticles.

• Argonne National Lab (Dr. Choi’s team) developed the novel concept of nanofluids.

• Nanofluids are a new class of advanced heat-transfer fluids engineered by dispersing nanoparticles smaller than 100 nm (nanometer) in diameter in conventional heat transfer fluids.

0

500

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Thermal conductivity of typical materialsT

herm

al c

ondu

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W/m

-K)

Material

0.15 0.25 0.61

1-Engine Oil2-Ethylene Glycol3-Water4-Alumina5-Silicon6-Aluminum7-Copper8-Silver9-Carbon

Solids have thermal conductivitiesthat are orders of magnitude larger than those of conventional heat transfer fluids.

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10 m

1 m

0.1 m

1 cm

1 mm

100 µm

10 µm

1 µm

100 nm

10 nm

1 nm

0.1 nm

Bacteria

Small molecules

Laptop Computer

Microchannel

Viruses/ NPs

Sensors

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Why Use Nanoparticles?• The basic concept of dispersing solid particles in fluids to enhance thermal The basic concept of dispersing solid particles in fluids to enhance thermal

conductivity can be traced back to Maxwell in the 19th Century.conductivity can be traced back to Maxwell in the 19th Century.

• Studies of thermal conductivity of suspensions have been confined to Studies of thermal conductivity of suspensions have been confined to mm- or mm-sized particles. mm- or mm-sized particles.

• The major challenge is the rapid settling of these particles in fluids. The major challenge is the rapid settling of these particles in fluids.

• Nanoparticles stay suspended much longer than micro-particles and, if below a Nanoparticles stay suspended much longer than micro-particles and, if below a threshold level and/or enhanced with surfactants/stabilizers, remain in suspension threshold level and/or enhanced with surfactants/stabilizers, remain in suspension almost indefinitely.almost indefinitely.

• Furthermore, the surface area per unit volume of nanoparticles is much larger Furthermore, the surface area per unit volume of nanoparticles is much larger (million times) than that of microparticles (the number of surface atoms per unit of (million times) than that of microparticles (the number of surface atoms per unit of interior atoms of nanoparticles, is very large). interior atoms of nanoparticles, is very large).

• These properties can be utilized to develop stable suspensions with enhanced flow, These properties can be utilized to develop stable suspensions with enhanced flow, heat-transfer, and other characteristicsheat-transfer, and other characteristics

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Materials for Nanoparticles and Base FluidsMaterials for nanoparticles and base fluids are diverse:Materials for nanoparticles and base fluids are diverse:

1.1. Nanoparticle materials include:Nanoparticle materials include:

– Oxide ceramics – AlOxide ceramics – Al22OO33, CuO, CuO

– Metal carbides – SiCMetal carbides – SiC

– Nitrides – AlN, SiNNitrides – AlN, SiN

– Metals – Al, CuMetals – Al, Cu

– Nonmetals – Graphite, carbon nanotubesNonmetals – Graphite, carbon nanotubes

– Layered – Al + AlLayered – Al + Al22OO33, Cu + C, Cu + C

– PCM – S/SPCM – S/S

– Functionalized nanoparticlesFunctionalized nanoparticles

2.2. Base fluids include:Base fluids include:

– WaterWater

– Ethylene- or tri-ethylene-glycols and other coolantsEthylene- or tri-ethylene-glycols and other coolants

– Oil and other lubricantsOil and other lubricants

– Bio-fluidsBio-fluids

– Polymer solutionsPolymer solutions

– Other common fluidsOther common fluids

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Methods for Producing Nanoparticles/Nanofluids

Two nanofluid production methods has been developed in ANL to allow selection of the most appropriate nanoparticle material for a particular application.

• In two-step process for oxide nanoparticles (“Kool-Aid” method), nanoparticles are produced by evaporation and inert-gas condensation processing, and then dispersed (mixed, including mechanical agitation and sonification) in base fluid.

• A patented one-step process (see schematic) simultaneously makes and disperses nanoparticles directly into base fluid; best for metallic nanofluids.

Other methods: Chem. Vapor Evaporation; Chem. Synthesis; new methods…

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Production of Copper Nanofluids

• Nanofluids with copper nanoparticles have been produced by a one-step method.

• Copper is evaporated and condensed into nanoparticles by direct contact with a flowing and cooled (low-vapor-pressure) fluid.

• ANL produced for the first time stable suspensions of copper nanoparticles in fluids w/o dispersants.

• For some nanofluids, a small amount of thioglycolic acid (<1 vol.%) was added to stabilize nanoparticle suspension and further improve the dispersion, flow and HT characteristics.

Cooling System

Liquid

Resistively Heated Crucible

Schematic diagram of nanofluid Schematic diagram of nanofluid

production system designed for production system designed for

direct evaporation/condensation of direct evaporation/condensation of

metallic vapor into low-vapor-metallic vapor into low-vapor-

pressure liquids.pressure liquids.

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Rotating drum with moving nanofluid film

Insulated and vertically-adjustable boat-heater

evaporator

Nitrogen cooling plate with coils and fins

FIG. 2: Proposed improvements for the one-step,direct-evaporation nanofluid production apparatus

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TEM Characterization of Copper Nanoparticles

• The one-step nanofluid production method resulted in a very small copper particles (10 nm diameter order of magnitude)

• Very little agglomeration and sedimentation occurs with this new and patented method.

Bright-field TEM micrograph of Cu nanoparticles produced by direct evaporation into ethylene glycol.

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Dispersion Experiments

Dispersion experiments show that stable suspensions of

oxide and metallic nanoparticles can be achieved in

common base fluids.

Deionized water prior to(left) and after (right)dispersion of Al2O3

nanoparticles

Oil prior to (left) andafter (right) evaporationof Cu nanoparticles

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Multiwalled Carbon Nanotubes (MWNTs) in OilMultiwalled Carbon Nanotubes (MWNTs) in Oil

• Multi-wall nano-tubes (MWNTs) were produced in a chemical vapor deposition reactor, with xylene as the primary carbon source and ferrocene to provide the iron catalyst.

• MWNTs have a mean dia. of ~25 nm and a length of ~50 µm; contained an average of 30 annular layers.

• Nanotube-in-synthetic oil (PAO) nanofluids were produced by a two-step method.

• Stable nanofluids with carbon-nanotubes and enhanced thermal conductivity are promising for critical heat transfer applications.

CNT nanofluids with and without CNT nanofluids with and without

dispersant: (a) NTs quickly settle dispersant: (a) NTs quickly settle

without use of a proper dispersant, without use of a proper dispersant,

and (b) NTs are well dispersed and and (b) NTs are well dispersed and

suspended in the oil with succinimide suspended in the oil with succinimide

dispersant (5 wt.%).dispersant (5 wt.%).

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Four Characteristic Features of Nanofluids

• Pioneering nanofluids research in ANL has inspired physicists, chemists, and engineers around the world.

• Promising discoveries and potentials in the emerging field of nanofluids have been reported.

• Nanofluids have an unprecedented combination of the four characteristic features desired in energy systems (fluid and thermal systems):

– Increased thermal conductivity (TC)at low nanoparticle concentrations

– Strong temperature-dependent TC

– Non-linear increase in TC with nanoparticle concentration

– Increase in boiling critical heat flux (CHF)

• These characteristic features of nanofluids make them suitable for the next generation of flow and heat-transfer fluids.

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Enhanced Nanofluid Thermal Conductivity

• Nanofluids containing <10 nm diameter copper (Cu) nanoparticles show much higher TC enhancements than nanofluids containing metal-oxide nanoparticles of average diameter 35 nm.

• Volume fraction is reduced by one order of magnitude for Cu nanoparticles as compared with oxide nanoparticles for similar TC enhancement.

• The largest increase in conductivity (up to 40% at 0.3 vol.% Cu nanoparticles) was seen for a nanofluid that contained Cu nanoparticles coated with thioglycolic acid.

• A German research group has also used metal nanoparticles (NPs) in fluids, but these NPs settled. The ANL innovation was depositing small and stable metal nanoparticles into base fluids by the one-step direct-evaporation method.

Thermal conductivity enhancement of copper, copper oxide, and alumina particles in ethylene glycol.

Appl. Phys. Lett. 78, 718, 2001.

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Nonlinear Increase in Conductivity with Nanotube Loadings

• Nanotubes yield by far the highest thermal conductivity enhancement ever achieved in a liquid: a 150% increase in conductivity of oil at ~1 vol.%.

• Thermal conductivity of nanotube suspensions (solid circles) is much greater than predicted by existing models (dotted lines).

• The measured thermal conductivity is nonlinear with nanotube volume fraction, while all theoretical predictions clearly show a linear relationship (inset).

Measured and predicted thermal conductivity enhancement for nanotube-in-oil nanofluids.

Appl. Phys. Lett. 79, 2252, 2001.

1.001.021.041.061.08

0.0 0.4 0.8 1.2

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Temperature-Dependent Conductivity

• Das et al. (*) explored the temperature dependence of the thermal conductivity of nanofluids containing Al2O3 or CuO nanoparticles.

• Their data show a two- to four-fold increase in thermal conductivity enhancement over a small temperature range, 20°C to 50°C.

• The strong temperature dependence of thermal conductivity may be due to the motion of nanoparticles.

Temperature dependence of thermal conductivity enhancement for Al2O3-in-water nanofluids

(*) J. Heat Transfer, 125, 567, 2003.

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T e m p e ra tu re (C )

Th

erm

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rati

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w

ater

A l 2O 3 (1% )

A l 2O 3 (4% )

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Significant Increase in Critical Heat Flux

• You et al. measured the critical heat flux (CHF) in pool boiling of Al2O3-in-water nanofluids.

• Their data show unprecedented phenomenon: a three-fold increase in CHF over that of pure water.

• The average size of the departing bubbles increases and the bubble frequency decreases significantly in nanofluids compared to pure water.

• The nanofluid CHF enhancement cannot be explained with any existing models of CHF.

CHF enhancement for Al2O3-in-water nanofluids

You et al., Appl. Phys. Lett., in press.

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Limitations and Need for TC modeling:

• The discoveries of very-high thermal conductivity and critical heat flux

clearly show the fundamental limits of conventional models for solid/liquid suspensions.

• The necessity of developing new physics/models has been recognized by ANL team and others.

• Several mechanisms that could be responsible for thermal transport in nanofluids have been proposed by ANL team and others.

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Nanofluid Structure• Although liquid molecules close to a

solid surface are known to form layered structures, little is known about the interactions between this nanolayers and thermo-physical properties of these solid/liquid nano-suspensions.

• ANL team (Choi et.al.) proposed that the nanolayer acts as a thermal bridge between a solid nanoparticle and a bulk liquid and so is key to enhancing thermal conductivity.

• From this thermally bridging nanolayer idea, a structural model of nanofluids that consists of solid nanoparticles, a bulk liquid, and solid-like nanolayers is hypothesized.

Schematic cross section of nanofluid structure consisting of nanoparticles, bulk liquid, and nanolayers at solid/liquid interface.

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Nanolayer-Dependent Conductivity

• A three- to eight-fold increase in the thermal conductivity of nanofluids compared to the enhancement without considering the nanolayer occurs when nanoparticles are smaller than r = 5 nm.

• However, for large particles (r >> h), the nanolayer impact is small.

• This finding suggests that adding smaller (<10 nm diameter) particles could be potentially better than adding more larger-size nano-particles.

Thermal conductivity enhancement ratio as a function of particle radius for copper-in-ethylene-glycol suspension.

J. Nanoparticle Res., 5, 167, 2003.

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Brownian motion of nanoparticles • A new model that accounts for the

Brownian motion of nanoparticles in nanofluids captures the concentration and temperature-dependent conductivity.

• In contrast, conventional theories with motionless nanoparticles fail to predict this behaviour (horizontal dashed line).

• The model predicts that water-based nanofluids containing 6-nm Cu nanoparticles (curve with triangles) are much more temperature sensitive than those containing 38-nm Al2O3 particles, with an increase in conductivity of nearly a factor of two at 325 K.

Temperature-dependent thermal conductivities of nanofluids at a fixed concentration of 1 vol.%, normalized to the thermal conductivity of the base fluid.

3 0 0 3 0 5 3 1 0 3 1 5 3 2 0 3 2 5

1 .0

1 .2

1 .4

1 .6

1 .8

No

rmal

ized

co

nd

uct

ivit

y (

k eff/k

BF)

T e m p e r a t u r e ( K )

).( nm

OAlWater

43832

)( nm

CuWater

6

3 0 0 3 0 5 3 1 0 3 1 5 3 2 0 3 2 5

1 .0

1 .2

1 .4

1 .6

1 .8

No

rmal

ized

co

nd

uct

ivit

y (

k eff/k

BF)

T e m p e r a t u r e ( K )

).( nm

OAlWater

43832

)( nm

CuWater

6

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Summary: New Applications• Development of methods to manufacture diverse, Development of methods to manufacture diverse,

hybrid nanofluids with polymer additiveshybrid nanofluids with polymer additives with with exceptionally high thermal conductivity while at the exceptionally high thermal conductivity while at the same time having low viscous friction.same time having low viscous friction.

• High thermal conductivity and low friction are High thermal conductivity and low friction are critical critical design parametersdesign parameters in almost every technology requiring in almost every technology requiring heat-transfer fluids (cooling or heating). Another goal heat-transfer fluids (cooling or heating). Another goal will be to develop hybrid nanofluids with enhanced will be to develop hybrid nanofluids with enhanced lubrication properties.lubrication properties.

• ApplicationsApplications range from cooling densely packed range from cooling densely packed integrated circuits at the small scale to heat transfer in integrated circuits at the small scale to heat transfer in nuclear reactors at the large scale. nuclear reactors at the large scale.

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Summary: Nature & Self-Assembly

• Nature is full of nanofluidsNature is full of nanofluids, like blood, a complex , like blood, a complex biological nanofluid where different nanoparticles (at biological nanofluid where different nanoparticles (at molecular level) accomplish different functionsmolecular level) accomplish different functions

• Many Many natural processesnatural processes in biosphere and atmosphere in biosphere and atmosphere include wide spectrum of mixtures of nanoscale particles include wide spectrum of mixtures of nanoscale particles with different fluidswith different fluids

• Many Many mining and manufacturing processesmining and manufacturing processes leave waste leave waste products which consist of mixtures of nanoscale products which consist of mixtures of nanoscale particles with fluidsparticles with fluids

• A wide range of A wide range of self-assembly mechanismsself-assembly mechanisms for for nanoscale structures start from a suspension of nanoscale structures start from a suspension of nanoparticles in fluidnanoparticles in fluid

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Summary: Future Research• Little is knownLittle is known about the physical and chemical surface about the physical and chemical surface

interactions between the nanoparticles and base fluid interactions between the nanoparticles and base fluid molecules, in order to understand the mechanisms of molecules, in order to understand the mechanisms of enhanced flow and thermal behavior of nanofluids.enhanced flow and thermal behavior of nanofluids.

• Improved Improved theoretical understandingtheoretical understanding of complex nanofluids will of complex nanofluids will have an even broader impacthave an even broader impact

• Development of Development of new experimental methodsnew experimental methods for characterizing for characterizing (and understanding) nanofluids in the lab and in nature.(and understanding) nanofluids in the lab and in nature.

• Nanoscale structure and dynamics of the fluids:Nanoscale structure and dynamics of the fluids: using a using a variety of scattering methods; small-angle x-ray scattering variety of scattering methods; small-angle x-ray scattering (SAXS), small-angle neutron scattering (SANS), x-ray photon (SAXS), small-angle neutron scattering (SANS), x-ray photon correlation spectroscopy (XPCS), laser based photon correlation spectroscopy (XPCS), laser based photon correlation spectroscopy (PCS) and static light scattering.correlation spectroscopy (PCS) and static light scattering.

• Development of Development of computer based modelscomputer based models of nanofluid of nanofluid phenomena including physical and chemical interactions phenomena including physical and chemical interactions between nanoparticles and base-fluid molecules. between nanoparticles and base-fluid molecules.

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Summary: Beyond Coolants• Beyond the primary goalBeyond the primary goal of producing enhanced flow and heat of producing enhanced flow and heat

transfer with nanofluids, the research should lead to important transfer with nanofluids, the research should lead to important developments in bio-medical applications, environmental developments in bio-medical applications, environmental control and cleanup and directed self-assembly at the control and cleanup and directed self-assembly at the nanoscaslenanoscasle..

• Possible spectrum of applicationsPossible spectrum of applications include more efficient flow include more efficient flow and lubrication, cooling and heating in new and critical and lubrication, cooling and heating in new and critical applications, like electronics, nuclear and biomedical applications, like electronics, nuclear and biomedical instrumentation and equipments, transportation and industrial instrumentation and equipments, transportation and industrial cooling, and heat management in various critical applications, cooling, and heat management in various critical applications, as well as environmental control and cleanup, bio-medical as well as environmental control and cleanup, bio-medical applications, and directed self-assembly of nanostructures, applications, and directed self-assembly of nanostructures, which usually starts from a suspension of nanoparticles in which usually starts from a suspension of nanoparticles in fluid. fluid.

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Acknowledgements:• Argonne National Laboratory (Argonne National Laboratory (ANL) )

Dr. S. Choi and Dr. J. HullDr. S. Choi and Dr. J. Hull• NIU’s Institute for NanoScience, Engineering ’s Institute for NanoScience, Engineering

& Technology (& Technology (InSET) ) Dr. C. Kimball and Dr. L. LurioDr. C. Kimball and Dr. L. Lurio

• NIU/CEET and Center for Tribology and NIU/CEET and Center for Tribology and Coatings: Coatings: Dean P. VohraDean P. Vohra

• NIU’s ME Department: NIU’s ME Department: Chair S. SongChair S. Song

More at: More at: www.kostic.niu.edu/nanofluids