No Slide TitlePublication: J. Orlenius, O. Lyckfeldt, K.A. Kasvayee, P. Johander, “Water based...
Transcript of No Slide TitlePublication: J. Orlenius, O. Lyckfeldt, K.A. Kasvayee, P. Johander, “Water based...
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Freeze Granulation
A multi-tool for enhanced ceramic processing
PowderPro AB
Barken Storegrunds gata 1
SE-417 60 Göteborg
Sweden
Web site: http://www.powderpro.se
Swerea IVF AB
Box 104
SE-43122 Mölndal
Sweden
Web site: http://www.swereaivf.se
Ola Lyckfeldt Elis Carlström
Martin Sjöstedt Kent Rundgren
et al.
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Outline
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• Background and principle of Freeze Granulation (FG)
• Granule properties
• Applications
• Pressing
• Pre-preparation for dispersability in different applications
• Powder synthesis
• Particle preparation for different purposes
• Advantages and dis-advantages of FG
• Equipments
• Summary
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Processing of advanced ceramics
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Dry Pressing ? Colloidal processing
of fine powders
Focus in the 80s and 90s
De-agglomeration - Stabilization
Slip Casting
Tape Casting
Gel Casting
Liquid based shaping
(Current granulation methods not satisfying)
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Colloidal approach for pressing
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Idea to lock and transfer suspension homogeneity into granules
Suspension Frozen droplet Freeze-dried granule
Freeze granulation
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Review
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1988
90s
2000
2005
2017
FG started at the Swedish Ceramic Institute (SCI) with focus on pressing
Successful research and development in many projects and contracted works
Other applications
Powderpro AB was established 2000 as a spin-off company to produce and sell FG equipment
SCI was incorporated with Swerea IVF
FG, a standard processing tool in material development in a variety of applications
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Freeze granulation procedure
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Instant freezing and subsequent freeze drying homogeneity preserved
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Freeze granulation (FG) vs Spray drying (SD)
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Weak bonding
Strong bonding
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Granule properties - 1
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Granules of composite materials
Free-flowing spherical granules
Granule size is controlled by suspension rheology, feed rate and
atomizing air pressure
Diamond/Ceramic Zirconia/Alumina
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Granule Properties - 2
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Homogeneous granules with low degree of fines vs spray drying
Granule size (micron) C
um
ula
tive
ma
ss (
%)
SD FG-Air
FG-UL
No cavities and equality in composition independent of granule size
Air atomization gives wide granule size distribution, can be
fractionized and oversized is easy to recirculate
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Flow properties
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Zirconia granules Flow Energy (mJ) Bulk density (g/ml)
FG-PEG (-150 µm) 170 1.37
FG-Latex (-150 µm) 168 1.31
SD-Latex (-150 µm) 182 1.24
Powder rheology
(Flow Energy)
Measure the force to rotate
a blade down and up in a
powder bed
FG produced granules showed better flow and higher bulk density than a commercial SD version
Granule flow is
essential in automated
pressing operations
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Pressing
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Cold Isostatic Pressing and sintering of alumina specimens
FG-granules required lower CIP pressure to reach higher sintered density vs SD-granules due to homogeneity
Spray-dried (SD) Freeze-granulated (FG)
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FG-granules – Easy to re-disperse
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Powders that are difficult to deagglomerate can be dispersed at low
concentrations, freeze granulated and re-dispersed at higher concentrations
Also favourable for pre-processing of nanopowders, graphene etc
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Applications with high powder loading
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Extrusion
Injection moulding
Additive manufacturing
Freeze granulation Easy dispersing
De-agglomeration
Suspension preparation with or without additives
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Additive manufacturing (Stereolithography)
• Suspension preparation by ball milling in organic media with dispersant compatible with the photopolymer system
• Freeze granulation Easy and rapid re-dispersing into the photopolymeric resin with mild impeller stirring
• Larger batch of prepared powder can be produced and stored to be available
Components manufactured in Cerafab 7500 (Lithoz GmbH)
• Application of FG for other AM-methods are under development
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Two part gas sensor
Al2O3
Corrugated horn antenna for microwaves
Al2O3
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Material/Powder Synthesis
• Solids, salts and/or metal organic compounds are mixed
and effectively homogenized in a liquid prior to FG
• Liquid medium depends on the material, reactivity to
water requires organic solvent with suitable freezing point,
in the range of -15 to +10°C
• Due to high degree of homogeneity, solid-state synthesis
with high yield by calcination
• Further processing depends on application
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Water based synthesis and processing of LiFePO4
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Li2CO3 + 2 FeC2O4*2H2O + 2 NH4H2PO4 => 2 LiFePO4 + Bi-products Dissolved
Freeze granulation
Calcining (600-800C i reducing atm)
Evaluation
Milling and freeze granulation
Cathode manufacture
XRD
Solid
Ball milling Stirring
Solid
High degree of pure crystalline LiFePO4
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Electrochemical Performance Water vs NMP (toxic solvent) produced cathode by tape casting
Publication: J. Orlenius, O. Lyckfeldt, K.A. Kasvayee, P. Johander, “Water based processing of LiFePO4/C cathode material for Li-ion batteries utilizing freeze granulation”, Journal of Power Sources 213 (2012) 119-127
Long term charge/discharge testing Charge and discharge curve
The obtained discharge capacity at the current rate 0.1C was 141 mAh/g, corresponds to 83% of the theoretical capacity (170 mAh/g).
Excellent long term performance with maintained capacity over 400 cycles
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Particle manufacture
• FG can be utilized to produce particles (aggregates) for
– Catalytic purpose where porosity and high specific surface can be controlled
– Thermal spraying where nano/micron sized particles can be utilized for improved coating performance
• Suspension of powder mix is prepared and FG processed
• FG-produced granules are calcined or pre-sintered to certain degree to obtain specific granule porosity and/or strength
• Size fractioning for the specific process
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• Particles (90–200 μm) of metal oxides catalyse combustion of natural gas via reduction to metal – the metal particles are re-oxidised by air and the process is restarted
• A lot of powder mixes of metal oxides have been freeze granulated, sintered and evaluated regarding reactivity and granule (particle) strength
The most promising materials have been processed in a 10 kW pilot plant with excellent results
Medium for Two-Step Combustion (Department of Energy Technology, Chalmers University of Technology)
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Advantages of Freeze Granulation
• The granule density can be controlled (solid content of the slip)
• No cavities in the granules
• No migration of small particles and/or binder gives a high degree of granule homogeneity
• A mild drying procedure minimises oxidation of non-oxides and metals
• Lower specific granule density and evenly distributed pressing aids gives softer granules and ensure that all granules are broken during compaction
• Low waste of material (high yield)
• Not only larger quantities but also very small experimental batches (50–100 ml slip) can easily be processed
• The equipment is easy to clean (allows the use of latex as binder)
• Possibility of recycling organic solvents
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Disadvantages of Freeze Granulation
• Two-step process: in-freezing and batch-wise freeze-drying
• Limitation in the choice of solvent, based on the freezing properties
– a freezing point between –20 and +10 °C is recommended
• Limited scale capacity < ca100 kg granules (depends on material
density) or processing of up to 80-100 liter suspension per day
excludes processing of low-performance materials in large scale
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Laboratory Granulator LS-6
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• Impeller version (LS-6mns) for magnetic or heavy materials
• Capacity to pump feed up to 6 l powder suspension per hour – Processing of
up to 3 l suspension per hour in practice
• Easy to set up and clean – many small samples can be prepared in a day
• Freeze-dryer with suitable capacity is required
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Production granulator PS-20
Prototype developed and tested
Capacity to process up to 20 litre
suspension per hour
No manual handling of liquid nitrogen
Frozen granules collected free from
liquid nitrogen
Commercial version will be design and
equipped according to costumers
preferences
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Freeze dryer Alpha 1-4 LSC plus
Capacity to dry ca 2 litre of granules
per day, achieved from ca 1 litre
powder suspension
Heated trays for quick drying
Driers with higher capacities are
available on the market
Ordinary household freezer can be
used for storage of frozen granules
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The spread of FG
Globally, FG-equipments sold to 23 countries
Sweden Norway Denmark Polen Germany France Great Britain Netherlands Austria Hungary Slovakia Portugal Italy Greece
Canada US Mexico
India Singapore Taiwan South Korea Japan
South Africa
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• Granulation for powder pressing (ceramic and metals)
• Pre-preparation for easy mix into formulation for PIM, extrusion,
AM etc - supporting high powder loading
• Material synthesis with high yield
• Preparation of easy re-dispersible nanopowder or graphene
• Production of carrier particles for various catalysts
• Production of high performance particles for thermal spraying
• Pharmaceutical and biomaterial applications
Summary of Multi-purpose FG
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Due to the homogeneity preservation, weak bonding within the
granules, limited oxidation of sensitive materials, limited damage of
organic compounds makes the use of this technique versatile
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Thanks for your attention!
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