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Nanofluids:
   Advanced Flow and Heat Transfer Fluids




 Resistively Heated
 Crucible

                       Liquid
Cooling System

                                Deionized water prior to Oil prior to (left) and
                                (left) and after (r
                                                  ight)  after (ri ht) evaporation
                                                                 g
                                dispersion of Al2O3      of Cu nanoparticles
                                nanoparticles
                                       Prof. M. Kostic
                                       Mechanical Engineering
                                       NORTHERN ILLINOIS UNIVERSITY
                                                    1
Wet-Nanotechnology:

    nanofluids
      at NIU
in collaboration with ANL

                     2
First NIU Nanofluids




                   3
Dry- vs. Wet-nanotechnology
• Fluids (gases & liquids) vs. Solids
  in 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)


                                                       4
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
                                          5
Wet-Nanotechnology:
       nanofluids’ applications
Advanced, hybrid 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)


                                              6
NIU- nanofluids
Development of advanced hybrid nanofluids:
  POLY-nanofluids (Polymer-nanofluids) and
  DR-nanofluids (Drag-Reduction-nanofluids)
• Development of Heat-transfer nanofluids
  Collaboration with ANL and NSF Proposal
  Related Invention/Patent Application pending
  Coherent X-ray Scattering Dynamic Characterization
• Development of Tribological nanofluids
  Center for Tribology and Coating (CTC) Project
More at:
 www.kostic.niu.edu/DRnanofluids
Web Search>nanofluids
                                          7
Acknowledgment and Thanks:
This presentation is in part based on the above Presentation
      by Dr. Steven U.S. Choi, Energy Technology Division
                Argonne National Laboratory 8
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
                                           9
Background
• Need for Advanced Flow and Heat-Transfer
  Fluids and Other Critical Applications
• Concept of Nanofluids
• Materials for Nanoparticles and Base Fluids
• Methods for Producing
  Nanoparticles/Nanofluids
• Characterization of Nanoparticles and
  Nanofluids
• Thermo-Physical Properties
• Flow and Heat-Transfer Characterization


                                  10
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.
                                                     11
Concept of Nanofluids




                                              Thermal conductivity (W/m-K)
•   Conventional heat transfer fluids have                                   2500
    inherently poor thermal conductivity                                             1-Engine Oil
    compared to solids.                                                      2000
                                                                                     2-Ethylene Glycol
                                                                                     3-Water
•   Conventional fluids that contain mm- or                                          4-Alumina
                                                                                     5-Silicon
    µm-sized particles do not work with the
                                                                             1500
                                                                                     6-Aluminum
    emerging “miniaturized” technologies                                             7-Copper
                                                                                     8-Silver
    because they can clog the tiny channels
                                                                             1000
                                                                                     9-Carbon
    of these devices.                                                         500

•   Modern nanotechnology provides
    opportunities to produce nanoparticles.                                    0
                                                                                    0.15   0.25   0.61

                                                                                    1       2      3     4     5    6   7   8   9
•   Argonne National Lab (Dr. Choi’s team)                                                                   Material
    developed the novel concept of                                                  Thermal conductivity of typical materials
    nanofluids.
•   Nanofluids are a new class of advanced                                   Solids have thermal conductivities
    heat-transfer fluids engineered by                                       that are orders of magnitude larger
    dispersing nanoparticles smaller than                                    than those of conventional heat
    100 nm (nanometer) in diameter in                                        transfer fluids.
    conventional heat transfer fluids.
                                                                                                         12
10 m
     1m
                      Laptop Computer
  0.1 m
   1 cm
  1 mm
                      Microchannel
100 µm     Sensors
 10 µm
                             Bacteria
   1 µm
100 nm
                     Viruses/ NPs
 10 nm
    1 nm             Small molecules
 0.1 nm
                              13
Why Use Nanoparticles?
•   The basic concept of dispersing solid particles in fluids to enhance thermal
    conductivity can be traced back to Maxwell in the 19th Century.
•   Studies of thermal conductivity of suspensions have been confined to
    mm- or mm-sized particles.
•   The major challenge is the rapid settling of these particles in fluids.
•   Nanoparticles stay suspended much longer than micro-particles and, if below a
    threshold level and/or enhanced with surfactants/stabilizers, remain in suspension
    almost indefinitely.
•   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
    interior atoms of nanoparticles, is very large).
•   These properties can be utilized to develop stable suspensions with enhanced flow,
    heat-transfer, and other characteristics


                                                                     14
Materials for Nanoparticles and Base Fluids
Materials for nanoparticles and base fluids are diverse:
1. Nanoparticle materials include:
    – Oxide ceramics – Al2O3, CuO
    – Metal carbides – SiC
    – Nitrides – AlN, SiN
    – Metals – Al, Cu
    – Nonmetals – Graphite, carbon nanotubes
    – Layered – Al + Al2O3, Cu + C
    – PCM – S/S
    – Functionalized nanoparticles
2. Base fluids include:
    – Water
    – Ethylene- or tri-ethylene-glycols and other coolants
    – Oil and other lubricants
    – Bio-fluids
    – Polymer solutions
    – Other common fluids
                                                             15
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…
                                          16
Production of Copper
                          Nanofluids with copper
                                • Nanofluids
                                             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.
 Resistively Heated
 Crucible                                •   ANL produced for the first time
                                Liquid       stable suspensions of copper
Cooling System
                                             nanoparticles in fluids w/o
Schematic diagram of nanofluid               dispersants.
production system designed for
direct evaporation/condensation of       •   For some nanofluids, a small
metallic vapor into low-vapor-               amount of thioglycolic acid (<1 vol.
pressure liquids.                            %) was added to stabilize
                                             nanoparticle suspension and further
                                             improve the dispersion, flow and HT
                                             characteristics.17
Insulated and
vertically-adjustable boat-heater
                      evaporator




  Rotating drum with
moving nanofluid film




                            Nitrogen
    cooling plate with coils and fins




                                     FIG. 2: Proposed improvements for the one-step,
                                                                                   18
                                    direct-evaporation nanofluid production apparatus
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
 Bright-field TEM micrograph of Cu
                                       sedimentation occurs
 nanoparticles produced by direct      with this new and
 evaporation into ethylene glycol.     patented method.

                                                19
Dispersion Experiments




     Deionized water prior to    Oil prior to (left) and
     (left) and after (r
Dispersion experiments ight)    show thatevaporation
                                 after (ri ht) stable
                                         g
     dispersion of Al2O3         of Cu nanoparticles
  suspensions of oxide
     nanoparticles      and metallic
   nanoparticles can be achieved in common
   base fluids.

                                                     20
Multiwalled 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)
CNT nanofluids with and without
                                            nanofluids were produced by a two-
dispersant: (a) NTs quickly settle
                                            step method.
without use of a proper dispersant,
and (b) NTs are well dispersed and      •   Stable nanofluids with carbon-
suspended in the oil with succinimide       nanotubes and enhanced thermal
dispersant (5 wt.%).                        conductivity are promising for critical
                                            heat transfer applications.
                                                            21
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.     22
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.
Thermal conductivity enhancement of
copper, copper oxide, and alumina   •   A German research group has also used
particles in ethylene glycol.           metal nanoparticles (NPs) in fluids, but these
                                        NPs settled. The ANL innovation was
Appl. Phys. Lett. 78, 718, 2001.        depositing small and stable metal
                                        nanoparticles into base fluids by the one-
                                        step direct-evaporation method.
                                                             23
Nonlinear Increase in Conductivity
     with Nanotube Loadings
                                    •   Nanotubes yield by far the highest
        1.08
                                        thermal conductivity enhancement
        1.06
        1.04                            ever achieved in a liquid: a 150%
        1.02
        1.00                            increase in conductivity of oil at ~1
            0.0   0.4   0.8   1.2
                                        vol.%.
                                    •   Thermal conductivity of nanotube
                                        suspensions (solid circles) is much
                                        greater than predicted by existing
Measured and predicted thermal          models (dotted lines).
conductivity enhancement for
                                    •   The measured thermal conductivity is
nanotube-in-oil nanofluids.
                                        nonlinear with nanotube volume
Appl. Phys. Lett. 79, 2252, 2001.       fraction, while all theoretical
                                        predictions clearly show a linear
                                        relationship (inset).

                                                          24
Temperature-Dependent
                                                                  Conductivity
                                         1 .3

                                                          A l 2 O 3 (1 % )
                                                                                                  •   Das et al. (*) explored the temperature
                                        1 .2 5            A l 2 O 3 (4 % )
                                                                                                      dependence of the thermal conductivity
 Thermal conductivity ratio λ/λ water




                                                                                                      of nanofluids containing Al2O3 or CuO
                                         1 .2

                                                                                                      nanoparticles.
                                        1 .1 5

                                                                                                  •   Their data show a two- to four-fold
                                         1 .1
                                                                                                      increase in thermal conductivity
                                        1 .0 5
                                                                                                      enhancement over a small temperature
                                                                                                      range, 20°C to 50°C.
                                            1
                                                 0   10         20           30   40

                                                              T e m p e ra tu re ( )
                                                                                   C
                                                                                        50   60
                                                                                                  •   The strong temperature dependence of
Temperature dependence of thermal
                                                                                                      thermal conductivity may be due to the
conductivity enhancement for Al2O3-                                                                   motion of nanoparticles.
in-water nanofluids

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

                                                                                                                         25
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.
CHF enhancement for Al2O3-in-water         •   The nanofluid CHF enhancement
nanofluids
                                               cannot be explained with any existing
You et al., Appl. Phys. Lett., in press.       models of CHF.
                                                                 26
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.

                                       27
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.
Schematic cross section of nanofluid
structure consisting of nanoparticles,
                                         •   From this thermally bridging
bulk liquid, and nanolayers at               nanolayer idea, a structural model of
solid/liquid interface.                      nanofluids that consists of solid
                                             nanoparticles, a bulk liquid, and solid-
                                             like nanolayers is hypothesized.
                                                              28
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
Thermal conductivity enhancement
ratio as a function of particle radius       could be potentially better than
for copper-in-ethylene-glycol                adding more larger-size nano-
suspension.
                                             particles.
J. Nanoparticle Res., 5, 167, 2003.
                                                              29
Brownian motion of nanoparticles
                                                                                       •   A new model that accounts for the
 Normalized conductivity (keff/kBF)




                                      1.8                      Water + Cu                  Brownian motion of nanoparticles in
                                                               (6nm )                      nanofluids captures the
                                      1.6                                                  concentration and temperature-
                                                                                           dependent conductivity.
                                      1.4
                                                                      Water + Al 2O3   •   In contrast, conventional theories
                                      1.2                             (38.4nm )            with motionless nanoparticles fail to
                                                                                           predict this behaviour (horizontal
                                      1.0
                                                                                           dashed line).
                                            300   305    310    315     320    325
                                                        Temperature (K)                •   The model predicts that water-based
                                                                                           nanofluids containing 6-nm Cu
                                                                                           nanoparticles (curve with triangles)
Temperature-dependent thermal                                                              are much more temperature
conductivities of nanofluids at a fixed
                                                                                           sensitive than those containing 38-
concentration of 1 vol.%, normalized
to the thermal conductivity of the                                                         nm Al2O3 particles, with an increase
base fluid.                                                                                in conductivity of nearly a factor of
                                                                                           two at 325 K.
                                                                                                            30
Summary: New Applications
• Development of methods to manufacture diverse,
  hybrid nanofluids with polymer additives with
  exceptionally high thermal conductivity while at the
  same time having low viscous friction.
• High thermal conductivity and low friction are critical
  design parameters in almost every technology requiring
  heat-transfer fluids (cooling or heating). Another goal
  will be to develop hybrid nanofluids with enhanced
  lubrication properties.
• Applications range from cooling densely packed
  integrated circuits at the small scale to heat transfer in
  nuclear reactors at the large scale.

                                             31
Summary: Nature & Self-Assembly
• Nature is full of nanofluids, like blood, a complex
  biological nanofluid where different nanoparticles (at
  molecular level) accomplish different functions
• Many natural processes in biosphere and atmosphere
  include wide spectrum of mixtures of nanoscale particles
  with different fluids
• Many mining and manufacturing processes leave waste
  products which consist of mixtures of nanoscale
  particles with fluids
• A wide range of self-assembly mechanisms for
  nanoscale structures start from a suspension of
  nanoparticles in fluid

                                          32
Summary: Future Research
• Little is known about the physical and chemical surface
  interactions between the nanoparticles and base fluid
  molecules, in order to understand the mechanisms of
  enhanced flow and thermal behavior of nanofluids.
• Improved theoretical understanding of complex nanofluids will
  have an even broader impact
• Development of new experimental methods for characterizing
  (and understanding) nanofluids in the lab and in nature.
• Nanoscale structure and dynamics of the fluids: using a
  variety of scattering methods; small-angle x-ray scattering
  (SAXS), small-angle neutron scattering (SANS), x-ray photon
  correlation spectroscopy (XPCS), laser based photon
  correlation spectroscopy (PCS) and static light scattering.
• Development of computer based models of nanofluid
  phenomena including physical and chemical interactions
  between nanoparticles and base-fluid molecules.

                                             33
Summary: Beyond Coolants
• Beyond the primary goal of producing enhanced flow and heat
  transfer with nanofluids, the research should lead to important
  developments in bio-medical applications, environmental
  control and cleanup and directed self-assembly at the
  nanoscasle.
• Possible spectrum of applications include more efficient flow
  and lubrication, cooling and heating in new and critical
  applications, like electronics, nuclear and biomedical
  instrumentation and equipments, transportation and industrial
  cooling, and heat management in various critical applications,
  as well as environmental control and cleanup, bio-medical
  applications, and directed self-assembly of nanostructures,
  which usually starts from a suspension of nanoparticles in
  fluid.

                                               34
Acknowledgements:
• Argonne National Laboratory (ANL)
  Dr. S. Choi and Dr. J. Hull
• NIU’s Institute for NanoScience, Engineering
  & Technology (InSET)
  Dr. C. Kimball and Dr. L. Lurio
• NIU/CEET and Center for Tribology and
  Coatings: Dean P. Vohra
• NIU’s ME Department: Chair S. Song

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

                                   35

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Nanofluids kostic

  • 1. Nanofluids: Advanced Flow and Heat Transfer Fluids Resistively Heated Crucible Liquid Cooling System Deionized water prior to Oil prior to (left) and (left) and after (r ight) after (ri ht) evaporation g dispersion of Al2O3 of Cu nanoparticles nanoparticles Prof. M. Kostic Mechanical Engineering NORTHERN ILLINOIS UNIVERSITY 1
  • 2. Wet-Nanotechnology: nanofluids at NIU in collaboration with ANL 2
  • 4. Dry- vs. Wet-nanotechnology • Fluids (gases & liquids) vs. Solids in 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) 4
  • 5. 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 5
  • 6. Wet-Nanotechnology: nanofluids’ applications Advanced, hybrid 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) 6
  • 7. NIU- nanofluids Development of advanced hybrid nanofluids: POLY-nanofluids (Polymer-nanofluids) and DR-nanofluids (Drag-Reduction-nanofluids) • Development of Heat-transfer nanofluids Collaboration with ANL and NSF Proposal Related Invention/Patent Application pending Coherent X-ray Scattering Dynamic Characterization • Development of Tribological nanofluids Center for Tribology and Coating (CTC) Project More at: www.kostic.niu.edu/DRnanofluids Web Search>nanofluids 7
  • 8. Acknowledgment and Thanks: This presentation is in part based on the above Presentation by Dr. Steven U.S. Choi, Energy Technology Division Argonne National Laboratory 8
  • 9. 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 9
  • 10. Background • Need for Advanced Flow and Heat-Transfer Fluids and Other Critical Applications • Concept of Nanofluids • Materials for Nanoparticles and Base Fluids • Methods for Producing Nanoparticles/Nanofluids • Characterization of Nanoparticles and Nanofluids • Thermo-Physical Properties • Flow and Heat-Transfer Characterization 10
  • 11. 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. 11
  • 12. Concept of Nanofluids Thermal conductivity (W/m-K) • Conventional heat transfer fluids have 2500 inherently poor thermal conductivity 1-Engine Oil compared to solids. 2000 2-Ethylene Glycol 3-Water • Conventional fluids that contain mm- or 4-Alumina 5-Silicon µm-sized particles do not work with the 1500 6-Aluminum emerging “miniaturized” technologies 7-Copper 8-Silver because they can clog the tiny channels 1000 9-Carbon of these devices. 500 • Modern nanotechnology provides opportunities to produce nanoparticles. 0 0.15 0.25 0.61 1 2 3 4 5 6 7 8 9 • Argonne National Lab (Dr. Choi’s team) Material developed the novel concept of Thermal conductivity of typical materials nanofluids. • Nanofluids are a new class of advanced Solids have thermal conductivities heat-transfer fluids engineered by that are orders of magnitude larger dispersing nanoparticles smaller than than those of conventional heat 100 nm (nanometer) in diameter in transfer fluids. conventional heat transfer fluids. 12
  • 13. 10 m 1m Laptop Computer 0.1 m 1 cm 1 mm Microchannel 100 µm Sensors 10 µm Bacteria 1 µm 100 nm Viruses/ NPs 10 nm 1 nm Small molecules 0.1 nm 13
  • 14. Why Use Nanoparticles? • The basic concept of dispersing solid particles in fluids to enhance thermal conductivity can be traced back to Maxwell in the 19th Century. • Studies of thermal conductivity of suspensions have been confined to mm- or mm-sized particles. • The major challenge is the rapid settling of these particles in fluids. • Nanoparticles stay suspended much longer than micro-particles and, if below a threshold level and/or enhanced with surfactants/stabilizers, remain in suspension almost indefinitely. • 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 interior atoms of nanoparticles, is very large). • These properties can be utilized to develop stable suspensions with enhanced flow, heat-transfer, and other characteristics 14
  • 15. Materials for Nanoparticles and Base Fluids Materials for nanoparticles and base fluids are diverse: 1. Nanoparticle materials include: – Oxide ceramics – Al2O3, CuO – Metal carbides – SiC – Nitrides – AlN, SiN – Metals – Al, Cu – Nonmetals – Graphite, carbon nanotubes – Layered – Al + Al2O3, Cu + C – PCM – S/S – Functionalized nanoparticles 2. Base fluids include: – Water – Ethylene- or tri-ethylene-glycols and other coolants – Oil and other lubricants – Bio-fluids – Polymer solutions – Other common fluids 15
  • 16. 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… 16
  • 17. Production of Copper Nanofluids with copper • Nanofluids 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. Resistively Heated Crucible • ANL produced for the first time Liquid stable suspensions of copper Cooling System nanoparticles in fluids w/o Schematic diagram of nanofluid dispersants. production system designed for direct evaporation/condensation of • For some nanofluids, a small metallic vapor into low-vapor- amount of thioglycolic acid (<1 vol. pressure liquids. %) was added to stabilize nanoparticle suspension and further improve the dispersion, flow and HT characteristics.17
  • 18. Insulated and vertically-adjustable boat-heater evaporator Rotating drum with moving nanofluid film Nitrogen cooling plate with coils and fins FIG. 2: Proposed improvements for the one-step, 18 direct-evaporation nanofluid production apparatus
  • 19. 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 Bright-field TEM micrograph of Cu sedimentation occurs nanoparticles produced by direct with this new and evaporation into ethylene glycol. patented method. 19
  • 20. Dispersion Experiments Deionized water prior to Oil prior to (left) and (left) and after (r Dispersion experiments ight) show thatevaporation after (ri ht) stable g dispersion of Al2O3 of Cu nanoparticles suspensions of oxide nanoparticles and metallic nanoparticles can be achieved in common base fluids. 20
  • 21. Multiwalled 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) CNT nanofluids with and without nanofluids were produced by a two- dispersant: (a) NTs quickly settle step method. without use of a proper dispersant, and (b) NTs are well dispersed and • Stable nanofluids with carbon- suspended in the oil with succinimide nanotubes and enhanced thermal dispersant (5 wt.%). conductivity are promising for critical heat transfer applications. 21
  • 22. 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. 22
  • 23. 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. Thermal conductivity enhancement of copper, copper oxide, and alumina • A German research group has also used particles in ethylene glycol. metal nanoparticles (NPs) in fluids, but these NPs settled. The ANL innovation was Appl. Phys. Lett. 78, 718, 2001. depositing small and stable metal nanoparticles into base fluids by the one- step direct-evaporation method. 23
  • 24. Nonlinear Increase in Conductivity with Nanotube Loadings • Nanotubes yield by far the highest 1.08 thermal conductivity enhancement 1.06 1.04 ever achieved in a liquid: a 150% 1.02 1.00 increase in conductivity of oil at ~1 0.0 0.4 0.8 1.2 vol.%. • Thermal conductivity of nanotube suspensions (solid circles) is much greater than predicted by existing Measured and predicted thermal models (dotted lines). conductivity enhancement for • The measured thermal conductivity is nanotube-in-oil nanofluids. nonlinear with nanotube volume Appl. Phys. Lett. 79, 2252, 2001. fraction, while all theoretical predictions clearly show a linear relationship (inset). 24
  • 25. Temperature-Dependent Conductivity 1 .3 A l 2 O 3 (1 % ) • Das et al. (*) explored the temperature 1 .2 5 A l 2 O 3 (4 % ) dependence of the thermal conductivity Thermal conductivity ratio λ/λ water of nanofluids containing Al2O3 or CuO 1 .2 nanoparticles. 1 .1 5 • Their data show a two- to four-fold 1 .1 increase in thermal conductivity 1 .0 5 enhancement over a small temperature range, 20°C to 50°C. 1 0 10 20 30 40 T e m p e ra tu re ( ) C 50 60 • The strong temperature dependence of Temperature dependence of thermal thermal conductivity may be due to the conductivity enhancement for Al2O3- motion of nanoparticles. in-water nanofluids (*) J. Heat Transfer, 125, 567, 2003. 25
  • 26. 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. CHF enhancement for Al2O3-in-water • The nanofluid CHF enhancement nanofluids cannot be explained with any existing You et al., Appl. Phys. Lett., in press. models of CHF. 26
  • 27. 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. 27
  • 28. 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. Schematic cross section of nanofluid structure consisting of nanoparticles, • From this thermally bridging bulk liquid, and nanolayers at nanolayer idea, a structural model of solid/liquid interface. nanofluids that consists of solid nanoparticles, a bulk liquid, and solid- like nanolayers is hypothesized. 28
  • 29. 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 Thermal conductivity enhancement ratio as a function of particle radius could be potentially better than for copper-in-ethylene-glycol adding more larger-size nano- suspension. particles. J. Nanoparticle Res., 5, 167, 2003. 29
  • 30. Brownian motion of nanoparticles • A new model that accounts for the Normalized conductivity (keff/kBF) 1.8 Water + Cu Brownian motion of nanoparticles in (6nm ) nanofluids captures the 1.6 concentration and temperature- dependent conductivity. 1.4 Water + Al 2O3 • In contrast, conventional theories 1.2 (38.4nm ) with motionless nanoparticles fail to predict this behaviour (horizontal 1.0 dashed line). 300 305 310 315 320 325 Temperature (K) • The model predicts that water-based nanofluids containing 6-nm Cu nanoparticles (curve with triangles) Temperature-dependent thermal are much more temperature conductivities of nanofluids at a fixed sensitive than those containing 38- concentration of 1 vol.%, normalized to the thermal conductivity of the nm Al2O3 particles, with an increase base fluid. in conductivity of nearly a factor of two at 325 K. 30
  • 31. Summary: New Applications • Development of methods to manufacture diverse, hybrid nanofluids with polymer additives with exceptionally high thermal conductivity while at the same time having low viscous friction. • High thermal conductivity and low friction are critical design parameters in almost every technology requiring heat-transfer fluids (cooling or heating). Another goal will be to develop hybrid nanofluids with enhanced lubrication properties. • Applications range from cooling densely packed integrated circuits at the small scale to heat transfer in nuclear reactors at the large scale. 31
  • 32. Summary: Nature & Self-Assembly • Nature is full of nanofluids, like blood, a complex biological nanofluid where different nanoparticles (at molecular level) accomplish different functions • Many natural processes in biosphere and atmosphere include wide spectrum of mixtures of nanoscale particles with different fluids • Many mining and manufacturing processes leave waste products which consist of mixtures of nanoscale particles with fluids • A wide range of self-assembly mechanisms for nanoscale structures start from a suspension of nanoparticles in fluid 32
  • 33. Summary: Future Research • Little is known about the physical and chemical surface interactions between the nanoparticles and base fluid molecules, in order to understand the mechanisms of enhanced flow and thermal behavior of nanofluids. • Improved theoretical understanding of complex nanofluids will have an even broader impact • Development of new experimental methods for characterizing (and understanding) nanofluids in the lab and in nature. • Nanoscale structure and dynamics of the fluids: using a variety of scattering methods; small-angle x-ray scattering (SAXS), small-angle neutron scattering (SANS), x-ray photon correlation spectroscopy (XPCS), laser based photon correlation spectroscopy (PCS) and static light scattering. • Development of computer based models of nanofluid phenomena including physical and chemical interactions between nanoparticles and base-fluid molecules. 33
  • 34. Summary: Beyond Coolants • Beyond the primary goal of producing enhanced flow and heat transfer with nanofluids, the research should lead to important developments in bio-medical applications, environmental control and cleanup and directed self-assembly at the nanoscasle. • Possible spectrum of applications include more efficient flow and lubrication, cooling and heating in new and critical applications, like electronics, nuclear and biomedical instrumentation and equipments, transportation and industrial cooling, and heat management in various critical applications, as well as environmental control and cleanup, bio-medical applications, and directed self-assembly of nanostructures, which usually starts from a suspension of nanoparticles in fluid. 34
  • 35. Acknowledgements: • Argonne National Laboratory (ANL) Dr. S. Choi and Dr. J. Hull • NIU’s Institute for NanoScience, Engineering & Technology (InSET) Dr. C. Kimball and Dr. L. Lurio • NIU/CEET and Center for Tribology and Coatings: Dean P. Vohra • NIU’s ME Department: Chair S. Song More at: www.kostic.niu.edu/nanofluids 35