Viscosimetria de Líquidos

Novos Fluidos de Referência

Viscometry of Liquids
New Reference Fluids

Fernando Caetano
Lisbon 2006

Project: POCTI/34951/EQU/2000
 Summary
Aim

Motivation

Foundations for Implementation

- Standard Reference Candidate
- Experimental Technique - vibrating-wire

- Design /
constrution
- Validation

Experimental Part
-Viscosity measurements
-Performance Assessment

Concluding Remarks
- Future developments on the experimental technique
- On going work on the reference fluid proposal
- Conclusions

20Feb2006
 Final aim
New viscosity reference liquid for
moderately high viscosity

Construction of a new vibrating-wire sensor -

able to measure viscosities in a large range of
viscosities;
Selection of a liquid with adequate characteristics to
be a viscosity reference candidate;
Perform viscosity measurements with this selected
liquid.
20Feb2006
 Aim

A new vibrating-wire viscometer:

n Measurements over a large range of
viscosities (0.5 to about 100 mPa.s) with
one single sensor;
n Ensuring traceability to the primary viscosity
reference liquid;
n Avoid or reduce error propagation in the
successive calibration procedures;
n Precision of the order of ±0.5 %.

20Feb2006
 Summary

Motivation

20Feb2006
 Motivation
Viscosity is a property of paramount economic
importance:
n Design and separation processes;
n Process control;
n Measurement of flow rate;
n Quality assurance of products.

Liquids have a large viscosity range:

p10-4Pa.s to 1013 Pa.s

Only one primary viscosity reference value, based on the

value reported by Swindels et al.(*) (1.0019 mPa.s, water @
20ºC and normal atmospheric pressure)

(* )
Swindels, J.F., Coe, J.R., Godfrey, T.B., Absolute Viscosity of Water at
20ºC, J. Res. N.B.S., 1952 48(1) 1-31

20Feb2006
 Motivation

High viscosity fluids – are very common in

industrial applications;
Their viscosities are usually several orders of
magnitude higher than that of the primary standard
reference;
Capillary viscometers are the most used
viscometers, therefore there is a need to perform
step-up calibration procedures, leading to:
n High costs;
n High uncertainty.

20Feb2006
 Motivation
Step-up calibration of capillary viscometers

0.5 – 3 0.8 – 5 1.2 – 10 3 – 30 10 – 100 30 – 300

mPa.s mPa.s mPa.s mPa.s mPa.s mPa.s

20Feb2006
 Summary

Foundations for Implementation

- Standard Reference Candidate
- Experimental Technique - vibrating-wire
- Design /
- Validation

20Feb2006
 Standard reference candidate
Diisodecyl phthalate – DIDP O
CH3

O
C28H46O4 CH3

CH3
O

O CH3

Characteristics:
n Liquid state over a wide temperature range
(~ -40ºC to 250 ºC);
n High viscosity (~ 125 mPa.s @ 20 ºC);
n Low vapor pressure (<0.1 Pa @ 20 ºC);
n High purity at low cost;
n Commercial availability.

Ref: Merck Technical Data Sheet

20Feb2006
 Design
Simulation studies
Is it possible to measure high viscosities with a
vibrating-wire sensor?
Which should be the vibrating-wire radius?
Ø Optimize physical parameters of the viscosity sensor

Wire:
n tungsten and stainless steel;
n mechanical tension: (1/3)Y0;
n wire radius range: 50 µm  R  500 µm;

Simulation results:
n Using the theoretical model to generate resonance curves for each
material and several wire radius

20Feb2006
 Simulation studies
Z

R = 50 µ m

R = 250 µ m

400 600 800 1000 1200 1400

f / Hz

Material: tungsten;
Radius: 190 μm to 250 μm
20Feb2006
 Tests

Prototype
n viscosities measured (@ 0.1 MPa)
from:
p 0.5 mPa.s (toluene @ 298K);
p 90 mPa.s (dibuthylphthalate @ 268 K).

(Rnom ≈ 242 μm)

20Feb2006
 Vibrating-wire technique
Theoretical (hydrodynamic) model restrictions
as guidance to the design of the sensor
n Linear behavior

n Compressibility effects

n Outer boundary
corrections <
0.25%

Must be checked to confirm the elongation is not too large

ref.: T. Retsina, S.M. Richardson, W.A. Wakeham, App. Sci. Research, 43, 127 (1986)
20Feb2006
 Vibrating-wire sensor
Mechanical device
to:
- adjust vertical
tension

tungsten rods
= 4 mm

tungsten wire
L ~ 0.06m
Rnom= 190 µm

Supporting
system made of
inconel
20Feb2006
 Assembling

Vessel – parallelepiped
þ Reduce the magnetic field gap
ü increase magnetic induction (up to 0.6 T) at the center of the
gap where the vibrating-wire is placed
þ Reduce volume sample - as a side effect
 Instrumentation
Lock-in amplifier simultaneously used as signal
generator and voltmeter;
The sensor is connected in series to a calibrated
resistor;
Applied current:
n 4 mA – sensor synthetizer
0.1Ω
0.1Ω
immersed in low
viscosity liquids; Lockin
sensor
sensor
n 20 mA – sensor
immersed in high A
viscosity liquids; input
B

20Feb2006
 Obtaining viscosity

Residuals / ohm
5e-05

-5e-05

0.14

0.135
imp / ohm

0.13

0.125

0.12

0.115
880 900 920 940
f / Hz

20Feb2006
Residuals / ohm
Obtaining viscosity
5e-05

-5e-05
Fitting to electromechanical model:
0.14
ØResonance frequency - ωr
ØHalf width - Δω
0.135
imp / ohm

0.13

0.125

0.12

0.115
880 900 920 940
f / Hz

Other data:
ØFluid density -  Theoretical model
ØSensor radius - R

Viscosity

20Feb2006
 New vibrating-wire sensor
Has been:

þ Calibrated using water

þTo calculate the wire radius
þEnsuring traceability to the primary reference point

Validated at both extremes of the viscosity range

þ Low viscosity - 2,2,4-trimethylpentane (99.8% GC) – dried with
molecular sieves;
þ High viscosity – standard reference fluids: 100B from PTB and
S60 from Paragon

Instrument performance

20Feb2006
 Calibration with water
Single parameter needed: wire radius
Experimental run: 293.15 K @ 0.1 MPa

Viscosity of water:
Residuals (%)

0.1

-0.1
1.002 ± 0.001 mPa·s
(reference value)
0.11

0.1

0.09
Z/ohm

0.08

0.07

0.06

0.05
Ø Average wire radius:
0.04 199.68 ± 0.12 μm
0.03
1045 1085 1125 1165 1205 1245
freq./Hz

Water – distilled and de-ionized by a Millipore system (Milli-Q® Plus – electrical resistivity of the
sample: 18.2 MΩ·cm);

20Feb2006
 Validation tests
Viscosity standard specimen 100B from PTB @ 293.15K
n 125 mPa·s
Residuals (%)

0.02

-0.02

0.037

0.036

0.035
Z/ohm

0.034

0.033

0.032

0.031
660 840 1020 1200 1380 1560
freq./Hz

20Feb2006
 Validation tests

20Feb2006
 milestone

Range of the validation measurements of

the vibrating-wire instrument:
0.5 135 mPa
Repeatability: 0.1 %
Estimated overall uncertainty: 0.8 %

F.J.P. Caetano, J.M.N.A. Fareleira, C.M.B.P. Oliveira, W.A. Wakeham, Validation of a

Vibrating-wire Viscometer: Measurements in the Range of 0.5 to 135 mPa.s, J.
Chem. Eng. Data. 50 (2005) 201-205. DOI: 10.1021/je049733f
20Feb2006
 Summary

Experimental Part
-Viscosity measurements
- Performance Assessment

20Feb2006
 DIDP Viscosity measurements
with the new vibrating-wire sensor

300

250

200
η /mPa.s

150

100

50

0
280 285 290 295 300 305 310 315
T/K

20Feb2006
 DIDP Viscosity measurements
with the new vibrating-wire sensor
1.00

0.80

0.60
(η exp-η fitt)/η fitt / %

0.40

0.20

0.00

-0.20

-0.40

-0.60

-0.80

-1.00
280 285 290 295 300 305 310 315

T/K

20Feb2006
 Performance assessment of the new
viscometer
þ Measurements were made beyond the validation
range and design goal

Range (0.5 - 267 mPa·s) higher viscosity

measured;
After calibration with water at 20ºC

Precision: better than ±0.5 %;

Estimated overall uncertainty: ±1 %;

F.J.P. Caetano, J.M.N.A. Fareleira, C.M.B.P. Oliveira, W.A. Wakeham, New

Measurements of the Viscosity of Diisodecyl Phthalate Using a Vibrating Wire
Technique, J. Chem. Eng. Data 50 (2005) 1875-1878. DOI: 10.1021/je050151n

20Feb2006
 Summary

Concluding Remarks
- Future developments on the experimental technique
- On going work on the reference fluid proposal
- Conclusions

20Feb2006
 Future developments of the
experimental technique
Improvements/modifications for the
vibrating-wire sensor:
n viscosity measurements as a function of
pressure;
pIndustrial need.
n make faster measurements – free decay
operating method;
pMeasuring cells for work on-line and in-situ.

20Feb2006
 On going work on reference
viscosity fluid proposal
Project coordinated within IATP (Int. Association for
Transport Properties):
throughout the world…
n F. Caetano, J. Fareleira, C. Oliveira @ IST, Portugal
n W.A. Wakeham @ Univ. Southampton, UK
n A.P. Froba, A. Leipertz @ LTT, Erlangen, Germany
n K.R. Harris @ Univ. New South Wales, Camberra, Australia
n H. Bauer @ PTB, Germany
n M. Trusler @ Imperial College, London, UK

availability of more DIDP viscosity data

n Involving:
p different techniques: capillary, vibrating-wire, falling body and SLS;
p different laboratories;

20Feb2006
 Deviation plot of the most recent
results of 99.8% DIDP
2.50
2.00
1.50
(η exp -η fitt)/η fitt / %

1.00
0.50
0.00
-0.50
-1.00
-1.50
-2.00
-2.50
280 285 290 295 300 305 310 315
T/K

K. Harris Fluka cap. Merck cap. A. Froba H. Bauer

20Feb2006
 On going work on reference
viscosity fluid proposal
Measurements (IST):
n Surface tension in capillary viscometers;
pinfluence on the accuracy of cap. measurements;

n Purity effect on DIDP viscosity;

pWater content on DIDP;
pDIDP characterization (elemental analysis,
refractive index, NMR, GC-MS…)
pChemical stability

20Feb2006
 Conclusions
Two DIDP samples (Merck and Fluka) from different production lines
(Germany and Japan) – same nominal purity 99.8 %
n different isomeric composition
Comparison: capillary viscosity measurements

Final viscosity reference fluid proposal

n IATP meeting @ NIST, Boulder, USA (July 2006)

20Feb2006
 DIDP production

Source: European
Chemicals Bureau – Institute
for Health and Consumer O
Protection, European Union
Risk Assessment Report – O
1,2-Benzenedicarboxylic
acid, di-C9-11-branched alkyl O
esters, C-10 rich and
di-”isodecyl” phthalate; EUR
20785 EN; PL-2, 36;
European Commission, Joint
Research Centre: 2003

20Feb2006
 On going work on reference
viscosity fluid proposal
n Ester hydrolysis

O O

H+
R C O R' + H 2 O R C OH + HOR'
(excess)
OH -

n GC of a “contaminated” DIDP sample (Merck) which was probably hydrolyzed

20Feb2006
 On going work on reference
viscosity fluid proposal
n MS obtained for “contaminated” DIDP sample, indicating alcohols

20Feb2006
 On going work on reference
viscosity fluid proposal
13C-NMR comparison between the two DIDP samples (Merck and Fluka):

DIDP
Merck

DIDP
Fluka

20Feb2006
 Viscosities measured
It should be noted that:
n This is the first vibrating-wire sensor able to measure over
such a wide range of viscosities and calibrated only at the
primary viscosity reference point;

20Feb2006
20Feb2006
 NeFeB
magnetic
magnets
induction at the
gap: ~0.6T

Magnetic
circuit

20Feb2006
 Assembling

magnetic
NeFeB induction at the
magnets gap: ~0.6T

Magnetic
circuit

20Feb2006
 Temperature

Maximum temperature deviation from

mean value in one measurement: ±2.5 mK;

Temperature (ITS 90) reading uncertainty:

± 0.01 K

20Feb2006
 Primary Viscosity Reference Standard*

Water at 20.000 ºC and normal atmospheric

pressure (0.101325 MPa)

η = 1.001 6 mPa.s || ν = 1.003 4

mm2/s
uncertainty: 0.17 %

* ISO/TR 3666:1998(E)

20Feb2006
 Uncertainty estimation
1. Estimated error due to current changing after calibrating with water and when
measuring with at high viscosity (=120 mPas): + 0.4 %.
2. Calibration: 0.2 % (systematic 0.17 %   0 %
v s s t
3. Δ0 error : 0.08 %
4. Wire density: 0.1 %
5. Random error (validation meas. = 0.1 %; DIDP meas. (120 mPa.s) ≈ 0.25 %; DIDP
meas (all range) ≈ 0.35 %)
6. Outer boundary (@ 120 mPas): -0.11 % [(ηfinit- ηinf)/ηinf] (not subtracted)

Uncertainty (random errors)

Estimated global uncertainty (validation): u + 0.4 % (point 1.): 0.34% + 0.4% ≤ 0.8 %

Estimated global uncertainty (all viscosity range): u + 0.4 % (point 1.): 0.42% + 0.4% ≤ 1 %

20Feb2006
 DIDP fluids with the same nominal purity (99.8%) from different
production lines (Germany and Japan):
n Merck pa
n Fluka Chemie GmbH (Selectophore).

Design and develop or implement:

n A new vibrating-wire sensor;
n A new magnetic circuit;
n A new electronic measuring system;
n New support apparatus and ancillary equipment.

More results from

p K. Harris (Australia)
p M. Trusler (UK)
Conclusion of surface tension tests (IST)

20Feb2006
 Complementary measurements regarding the
proposal of a high viscosity reference fluid

Measurements:
n Density (DMA 5000 Anton Paar densimeter);
n Capillary measurements (Ubbelohde viscometer):
p These are needed:
– Capillary method - most used routine technique;
– Lack of high viscosity data for comparison with the vibrating-wire
sensor;
n Surface tension measurements;
n Effect of water content on viscosity;
n DIDP characterization;

20Feb2006
 Need of calibration with a viscosity reference
fluid at the measuring temperature and
pressure.
n All viscosity measurements of fluids used as
standards must be traceable to the viscosity of
water at 20 ºC.

Search for a reference fluid with high viscosity

§ The IATP - International Association for Transport
Properties (former IUPAC Subcommittee on Transport
Properties) participates in this study.

20Feb2006
 Aim

The new vibrating-wire viscometer should:

n Perform measurements over a large range of
viscosities (0.5 to about 100 mPa.s) with one
single sensor;
n Ensure traceability to the primary viscosity
reference liquid;
n Avoid or reduce error propagation in the
successive calibration procedures;
n Enable a measurement precision of the order of
±0.5 %.

20Feb2006