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Mercury Porosimetry Advantages and Limitations. Herbert Giesche New York State College of Ceramics at Alfred University. Outline:. Introduction / Theory The Measurement Technique Tips and Tricks Precision and Accuracy What Information do we get? Hysteresis Pore-Network Models - PowerPoint PPT Presentation
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Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Mercury PorosimetryAdvantages and Limitations
Herbert Giesche
New York State College of Ceramics
at Alfred University
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Outline:
• Introduction / Theory
• The Measurement Technique– Tips and Tricks – Precision and Accuracy
• What Information do we get?
• Hysteresis
• Pore-Network Models
• Alternative Techniques
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
But first, “Where on earth is Alfred ?”
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
What type or size of pore is measured ?Closed Pores Blind Pores Cross-linked Pores Through Pores
In all cases, Hg-Porosimetry measures the largest available access to a pore,the size of the “entrance” towards a pore.
Most times this is substantially smaller than the inner pore diameter!
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Theory
cos r
2
p
= 11
=P :equation - Washburnand -Laplace Young21
lv
rr
Essentially all calculations are based on the assumption of cylinder pores.
This is a major assumption !!!
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
What are the basic parameters to be measured ?
• Pressure
• Intruded volume
• Contact angle, θ
• Surface tension, γ
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Pressure
• Pressure transducer have to cover the entire measurement range. (> 5 orders of magnitude !)
• Use several transducer with overlapping ranges.
• Avoid temperature drifts.
• Avoid accidental over-range exposure.
• Calibrate and check with “Standards”
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Volume Measurement
• The “antique” techniques: Optically Contact wire Resistance wire
• Nowadays used in essentially all instruments:Precision capacitance bridge
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Contact angle (which one ?)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Contact angle (cont.)
• Bashforth-Adams tables
• Max. Height
• Anglometer
cos = 1- g h
2 max
lg
2
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Contact angle (cont.)• Adjust θ in order to get close to N2-surface area
Hg-Porosimetry N2-Adsorption
Tungsten powder 0.11 0.10Iron powder 0.20 0.30Zinc dust 0.34 0.32Copper powder 0.34 0.49Silver iodide 0.48 0.53Aluminum dust 1.35 1.14Fluorspar 2.48 2.12Iron oxide 14.3 13.3Anatase 15.1 10.3Graphitized carbon black 15.7 12.3Boron nitride 19.6 20.0Hydroxyapatite 55.2 55.0Carbon black, Spheron-6 107.8 110.0
P
0lg
P V(P) cos
1 darea
This assumes a reversible process !
It is strongly effected by small pores, even in minor quantities !
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
The Instrument
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Sample Cell and Calibration-kit
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Tips and Tricks: Sample Preparation• Sample weight ???
• Heat treatment (?)
• Evacuation (final vacuum & time)
• Clean surfaces !
• Choice of ‘best’ penetrometer
• Filling with mercury (head-pressure)
• Use optimum switch-over between‘low’ and ‘high’ pressure port
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Tips and Tricks (cont.)
• Artificial pores due to sample positioningstainless steel wire as sample holder and as ‘separator’
• Space filler to reduce compressibility effects and amount of ‘wasted’ mercury.
• Reactive metals (e.g. Zn, Ag, Pb) coated with stearic acidwith Cu a light oxidation might be sufficient
• Watch out for compressibility of the sample:especially with highly porous sol-gel or polymer samples.
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Removing Mercury• Repeat measurements on same sample after
removing Hg at > 360°C under vacuum
• Collect spilled Hg with Cu-wire brush (activated with HNO3 and dipping in mercury)“Quecksilber Teufel”
• Or vacuum suction
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Precision and Accuracy• < 1 – 2% for “data” in repeat tests• Contact angle uncertainty:
• Surface tension value:Impurities can reduce γHg up to 20%
Temperature has only a minor effect: 2.1 10-4 N/m °C
Pressure: γ (N/m) – 2.66 104 ΔP (MPa) e.g. up to 12% at 200 MPa
• ! Temperature changes by up to 15°C during compression and expansion; volume changes
%28100 153 cos
130 cos - 153 cosor %52 100
115 cos
115 cos - 130 cos
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Kinetic Effects• Time for mercury to
move through pores
• Over-pressure is needed• Smaller pore take longer
Example: 110% injection pressure
Pore radius 0.5 to 50 μm
tl
2 4
P rp2
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Equilibration rate - example
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Equilibration rate - example
Pore Volume (cm3/g) Pore diameter (m)
• 0 seconds 0.5823 0.0081
• 2 seconds 0.5938 0.0089
• 10 seconds 0.5939 0.0095
• 30 seconds 0.6161 0.0098
• 0.001 l/g-sec 0.6210 0.0102
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Equilibration Kinetics of FCC-catalyst
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Equilibration Kinetics of FCC-catalyst (Intrusion)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Equilibration Kinetics of FCC-catalyst (Extrusion)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
What Information do we get?• Pore Size (which size ??)
• Pore Volume• Density (bulk, skeletal, or at various stages)
• Compressibility
• Surface Area
• Particle Size
• Pore Shape (?)
• Pore Connectivity (?)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Compressibility
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Compressibility (cont.)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
What Information do we get?• Pore Size (which size ??)
• Pore Volume• Density (bulk, skeletal, or at various stages)
• Compressibility
• Surface Area
• Particle Size
• Pore Shape (?)
• Pore Connectivity (?)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Particle Size (?)• We use the inter-particle pore size as an estimation of
the particle size (Mayer & Stove)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Particle Size (cont.)
• Pore size particle size (as shown)
This is highly dependent on the particle packing characteristics (particle shape, stickiness, compaction pressure, etc.)
Approximation: pore = 20% of particle size
• Alternatively we use the calculated surface area to convert this into an equivalent particle size
Rarea
3
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
What Information do we get?• Pore Size (which size ??)
• Pore Volume• Density (bulk, skeletal, or at various stages)
• Compressibility
• Surface Area
• Particle Size
• Pore Shape (?)
• Pore Connectivity (?)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Pore Shape and Pore Networks
• Intrusion describes primarily the pore opening or entrance
• Hysteresis is caused by:– Network effects– Pore shape (or pore connections)– Surface properties (contact angle effects)
• Permeability (flow through) provides additional information (check for simulations)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Hysteresis and Pore-Shape
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Hysteresis due to Surface ChemistryAlumina sample coated with Cu-sulfate
Intrusion: a) for all samples
Extrusion: b) untreated
c) 0.5% d) 2% e) 40% CuSO4
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Network modelsMercury intrusion in model porous media. By C. Tsakiroglou and A. Payatakes; Adv. Colloid Interface Sci; 75, 215-53 (1998)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Network modelsMercury retraction in model porous media.
By C. Tsakiroglou and A. Payatakes; Adv. Colloid Interface Sci; 75, 215-53 (1998)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
“Snap-off in ‘lenticular’ Throats”By C. Tsakiroglou and A. Payatakes; Adv. Colloid Interface Sci; 75, 215-53 (1998)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Pore-Connectivity / Network - EffectBy C. Tsakiroglou and A. Payatakes; Adv. Colloid Interface Sci; 75, 215-53 (1998)
Initial stage
↓Final stage
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
“Energy Barrier Model”
Length Intrusion Extrusion PI/PE
μm MPa MPa
100 0.735 0.726 1.01
10 0.735 0.650 1.13
5 0.735 0.566 1.31
2 0.735 0.309 2.78
1.5 0.735 0.166 7.58
1.4 0.735 0.050 14.66
Conical-Cylinder PoreCylindrical Pore1 μm diameter; Θ = 140°; γ = 0.48 N/m
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Pore-Cor Simulation Model
sandstone sample: showing mercury intrusion (grey), after injection by polymer (blue). Yellow volumes are empty.
Generates a 3-D representation of the pore space using information derived directly from mercury intrusion data.
PoreCor data reduction shows:
• porosity • pore connectivity • pore throat correlation • pore tortuosity • absolute gas permeability (gas diffusion through a dry sample) • trapping of non-wetting fluids
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Complimentary Porosity Characterization Techniques• Microscopy
• Permeability measurements
• Infiltration tests:– Wood’s metal– Water or other liquids
• CT (computer tomography)
• NMR studies of relaxation times
• Light Scattering, SAXS (and SANS)
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Conclusions
• Hg-Porosimetry uniqueness; it covers 5 orders of magnitude; from mm to nm.
• Safety and Environmental concerns; manageable.• Remember: Intrusion = Pore Entrance• Hysteresis may lead to understanding of pore shape
and connectivity.• Work on model pore structures is needed to gain
more understanding.• New simulation software offers great possibilities;
but use with caution !!
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Thanks for your interest and
thanks to the organizer for the opportunity to be here!
Literature• H. Giesche; Chapter 2.7 in ‘Handbook of Porous Solids’,
Wiley (2002) Overview article
• H. Giesche, et.al.; Colloid & Surfaces, 37, 93-113 (1989) Ordered silica sphere structures
• C. Tsakiroglou et.al.; Adv. Colloid Interface Sci; 75 215-53 (1998) 2-D model pore structures; experiments & simulations
Others not specifically referenced in this presentation:
• Sean Rigby; numerous publications over the last 5 yearsNetwork models for hysteresis effects; experiments and interpretation
• Peter Matthew; numerous publications over the last 10 years‘Pore Core’ simulation model
• Geoffrey Mason; numerous publications over the last 20 yearsSurface curvature; intrusion and extrusion in simple rod-plate structures
• Powder Technology, Vol. 29 (1981), special issue Hg-porosimetry
Porotec Workshop 15 & 16th Nov. 2004NYSCC Alfred University
Literature• H. Giesche; Chapter 2.7 in ‘Handbook of Porous Solids’,
Wiley (2002) Overview article
• H. Giesche, et.al.; Colloid & Surfaces, 37, 93-113 (1989) Ordered silica sphere structures
• C. Tsakiroglou et.al.; Adv. Colloid Interface Sci; 75 215-53 (1998) 2-D model pore structures; experiments & simulations
Others not specifically referenced in this presentation:
• Sean Rigby; numerous publications over the last 5 yearsNetwork models for hysteresis effects; experiments and interpretation
• Peter Matthew; numerous publications over the last 10 years‘Pore Core’ simulation model
• Geoffrey Mason; numerous publications over the last 20 yearsSurface curvature; intrusion and extrusion in simple rod-plate structures
• Powder Technology, Vol. 29 (1981), special issue Hg-porosimetry
Literature
Thanks for your interest and
thanks to the organizer for the opportunity to be here!
http://people.alfred.edu/~giesche/Publications.htm