Turbidimetry for the Stability Evaluation of Emulsions Used in

Machining Industry
Benjamin Glasse,1* Cristhiane Assenhaimer,2 Roberto Guardani2 and Udo Fritsching3
1. Particles and Process Engineering, University Bremen, Badgasteiner Strae 3 28359, Bremen, Germany
2. Chemical Engineering Department, University So Paulo, So Paulo, Brazil
3. Particles and Process Engineering, University Bremen, Bremen, Germany

Emulsied uids are used in many industrial and consumer areas, for instance as products in the food or health industry as well as technical uids in the
machining industry. Metalworking uids (MWF) are used as coolants and lubricants in metalworking processes. During their usage MWF emulsions
may change their physical and chemical properties, which inuences their performance and decrease the physical stability and therefore their lifetime.
This article discusses results of turbidimetric spectra measurement of MWF emulsions to be used for process control, MWF quality monitoring and
formulation purposes. Therefore, laboratory experiments have been carried out investigating the physical stability. Metal working emulsions have
been treated and destabilised by different concentrations of salts. The destabilisation process was monitored by undiluted turbidity measurements
and evaluated by the temporal change of the wavelength exponent. Thus, it was possible to determine specic conditions, for example a specic
critical salt concentration for maintaining, stability of the MWF formulations.
Keywords: metal working fluid, emulsion stability, turbidity analysis

INTRODUCTION
Metal Working Fluids
etal working uids (MWF) are used in metal processing
operations such as rolling, grinding and turning, as well as
for enhanced manufacturing process stability, work piece
quality and increased tool life.[1] Most MWF are formulated as oilin
water (O/W) emulsions.[24] The use of MWF decreases the thermal,
chemical and mechanical stresses caused by shearing and friction in
the contact zone of the tool and the work piece of the machining
processes as well as ushes away the created nes and chips from
the nascent metal surface, thus preventing rewelding and providing
protection for the newly formed surface by wetting it.[3]
Depending on the machining processing operation and the work
piece material, the disperse phase concentration in a MWF is in the
order of 210% v/v with a mean droplet size of 0.12.0 mm.[5,6]
MWF emulsions contain mixtures of different oils (mainly mineral
oils) and chemical additives, for example emulsiers, corrosion
inhibitors, biocides and defoamers, which increase the performance of the MWF. More than 300 different components may be
used in MWF formulations, where a single mixture may contain up
to 60 different components.[5,7] Socalled green or biodegradable
oils recently are gaining more interest for the formulation of MWF.
The participation of biodegradable oils or additives in metal
working processes has increased in recent years due to an
increased regulation of industry contamination and pollution
and an increased awareness of the public, leading to an increased
environmental friendly production.[8,9]
MWF are mainly stabilised by adsorption of amphiphilic surface
active molecules (emulsiers at the liquidliquid phase boundary
due to electrostatic (ionic emulsiers) and steric (nonionic
emulsiers) barrier), preventing destabilisation processes like
creaming, sedimentation, occulation/aggregation and coalescence, that can lead to the complete phase separation of the water
and oil phase.[10] Due to biological, thermal and chemical

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processes in metal working machining operations, the MWF

composition and morphology may change during usage, resulting
in an increased and broader droplet size distribution (DSD), which
directly affects the MWF performance.[5,11] For analysing the
behaviour and stability of MWFemulsions under laboratory
conditions, the emulsions may be articially aged. Two main
mechanisms may be used to destabilise a MWF emulsion in a
controlled way: chemical methods like the addition of salt or
acids,[12] and physical methods, like an increased temperature or
an electric eld.[3] According to the DLVO theory, admixed cations
reduce the surface potential of the oil droplets since they adsorb
partly at the oil surface and lower the repulsive and electrostatic
barriers at the surface of the droplets. An increased temperature
can accelerate the destabilisation by decreasing the viscosity
causing an increase in Brownian motion and coalescence rate, and
changing the cloud point, where some dissolved solids are no
longer completely dissolved.[3,10]
Turbidity Spectroscopy
Turbidity spectroscopy (also referred to as turbidimetry or UVVis
spectroscopy) is an easily applied light scattering measurement
technique,[1315] providing information about the chemical composition, droplet size, internal structure and concentration of the
dispersed phase of an emulsion.[16,17] The measured turbidity t(l0)
is given by the path length L, the emitted light intensity I0 and the
attenuated light intensity I for wavelength l0 in vacuum as:

*Author to whom correspondence may be addressed.

Email address: glasse@iwt.uni-bremen.de
Can. J. Chem. Eng. 92:324329, 2014
2013 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21930
Published online 31 October 2013 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 92, FEBRUARY 2014

tl0

 
1
I0
ln
L
I

where the term ln(I0/I) is the absorbance or optical density. The

wavelength l0 is calculated by:
lm

l0
nm

where lm is the wavelength in the medium and nm the refractive

index of the continuous medium at wavelength lm. The turbidity
spectrum consists of the absorption of the materials and the
scattering of the dispersed droplets over a wavelength range.[18]
Therefore, turbidimetric techniques may be used to follow the
destabilisation process of MWF, since the turbidity is related to
concentration as well as to the particle size of the dispersed
medium.[12,1921]
Wavelength Exponent
An analytical method for the evaluation of turbidity spectra is the
wavelength exponent z, dened by:
z

d lntl0
d ln1=lm

calculated from a linear regression applied to the whole measured

turbidity spectrum. The derivation of the wavelength exponent
from the turbidity spectra (Figure 1a) of two monomodal log
normal droplet size distributions (DSD) is illustrated in Figure 1b,
where the wavelength exponent amounts 2.84 for a mean droplet
size of 200 nm and 2.25 for a mean droplet size of 500 nm.
According to Deluhery and Rajagopalan[19] the turbidity of two
widely separated wavelengths leads to the wavelength exponent z
for spherical monodisperse particles, which are independent from
the concentration of the dispersed phase, if multiple scattering is
avoided. A temporal change of the wavelength exponent indicates
a change of the droplet size.[14,19]
Figure 2 illustrates the dependency of the wavelength exponent
versus the mean droplet size DG of a simulated monomodal log
normal droplet size distribution in the size range of 5040 000 nm
with differing standard deviations s (0.1  s  0.5), where the
inner gure illustrates the principle inuence of the broadness s on
the size distribution. The simulations have been carried out with a
numerical code, where the calculation of the Mie theory[22] is done
with MATLAB codes based on Bohren and Huffmann.[18]
The wavelength exponent decreases to a global minimum for
droplet sizes of 2 0003 000 nm, and oscillates around value of zero
for increasing droplet sizes where the amplitude of this oscillation
decreases for increasing droplet sizes. A decrease of the wavelength
exponent indicates an increase of the droplet size for submicron
MWF emulsions, due to the nonobjectivity since no wavelength
exponent could be assigned to one specic droplet size for micron
emulsions. The oscillation of the wavelength exponent around a
value of zero vanishes for droplet sizes >10 mm due to scattering
attributes of the droplets, a broader droplet size distribution
increases this cushioning due to an overlapping of the local
maxima and minima of the droplets.

Figure 1. (a) Simulated turbidity spectra for two lognormal monomodal

droplet size distributions with a mean droplet size of 200 and 500 nm.
(b) Determination of the wavelength exponent with a linear regression t
from the turbidity spectra.

MATERIALS AND METHODS

Materials
Different salts were used to destabilise the MWF under laboratory
conditions. Technical pure aluminium chloride, magnesium

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Figure 2. Dependence of the wavelength exponent from the mean droplet

size of a monomodal lognormal size distribution with differing
broadnesses of the distribution.

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325

chloride and calcium chloride have been applied without further

purication. Two different MWFformulations from different
suppliers have been tested (MWF1 and MWF2) that are commercial available green MWF emulsions, since their formulation is
based on renewable materials.
Methods
Stable oilinwater emulsions have been prepared by adding MWF
samples to deionised water in the range of 0.422.9 mass%. The
different salts were dissolved in deionised water in order to
produce ionic solutions at a concentration of 10 mass%. The MWF
samples and the salt solution were separately shaken on a vibrating
table for several minutes, creating a stable oilinwater emulsion
and ionic solution. Afterwards the ionic solution was gradually
added to the MWF emulsion until the desired concentration was
reached and the system was homogenised.
The turbidity of different samples was measured in the visible to
near infrared light range of 4001100 nm with a HR2000
spectrometer which was connected via a dip probe (300 mm bre
and 2 mm path length) with a DH2000BAL light source (all Ocean
Optics). The dark noise and reference spectra (deionised water)
were recorded prior to the measurements. The spectra were
obtained with an integration time of 10 ms and averaged over 10
different measurements. The wavelength exponent was calculated
by Equation 3 for all recorded measurements in the range of 600
700 nm with a spectral resolution of Dl 0.47 nm and tted to a
linear regression.
RESULTS AND DISCUSION
Concentration
Figure 3a illustrates the measured wavelength exponent of MWF1
for different MWF concentrations, whereas Figure 3b illustrates
the corresponding turbidity spectra. The wavelength exponent
concentration curve may be divided into four regions. The rst
concentration region of about 02 mass% is characterised by a at
shape of the absorbance spectra and thus high wavelength
exponents, which surpass even the calculated maximal wavelength
exponent of four for synthetic data shown in Figure 2; this
concentration marks the lower boundary for this MWF emulsion,
due to the dependency of the wavelength exponent from
the concentration. The second region of 215 mass% shows
continuously decreasing absorbance for increasing wavelengths of
the light in the absorbance spectra and an independency of the
wavelength exponent from the concentration; therefore, this is the
range of application for this measurement technique which also
marks the conventional range of concentrations of MWF emulsions.
A saturation in the absorbance readings at low wavelengths
(l 400450 nm) is observed when the MWF concentration is
further increased. This saturation extends over the whole wavelength
range for further increasing of the concentration (l 400550 nm),
which is characterised by the third region for a concentration of
approximately 1517 mass%. Hence, the third region marks the
upper boundary of application of the technique due to the
dependency of the wavelength exponent from the concentration, a
further increased concentration of >17 mass% leads to a wavelength
exponent of about zero due to the noisy at shape of the absorbance
spectra, because of the high turbidity of the dispersion in this region.
The dependency of the wavelength exponent from the absorbance at a single wavelength of 650 nm can be divided into three
regions as shown in Figure 4. The rst and the third region show a
dependency of the wavelength exponent form the absorbance. The
wavelength exponent is independent from the absorbance in

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Figure 3. (a) Dependence of the wavelength exponent for different

concentrations of MWF1. (b) Turbidity spectra for different concentrations
of MWF1.

the second region, where an absorbance >0.3 indicates multiple

scattering.[23,24] Thus, the wavelength exponent may be applied
for concentrations with occurring multiple scattering. The
corresponding monomodal narrow droplet size distribution of

Figure 4. Dependence of the wavelength exponent from a single

absorbance at a wavelength of 650 nm.

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the fresh MWF emulsion with a mean droplet size of approximately

d4,3  150 nm (measured via laser diffraction) is not affected by the
concentration for short time periods, but may lead to a decreased
longterm physical stability due to the increased coagulation
probability of the droplets.

Figure 5. (a) Determination of the physical stability of MWF1 for CaCl2.

(b) Determination of the physical stability of MWF1 for Al2Cl3.
(c) Determination of the physical stability of MWF1 for MgCl2.

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Destabilisation
A change in the wavelength exponent may indicate a change in the
emulsion droplet size. In this study ionic solutions were used to
decrease the physical stability of MWF emulsions. However, since
commercial products have been used, admixed hard water agents
to the MWF may provide some tolerance with respect to the salts.
Turbidity spectra of sample MWF1 with different salt concentrations are shown in Figure 5 for a) CaCl2, b) Al2Cl3 and c) MgCl2.
A change of the wavelength exponent may be used as an indicator
of the physical stability of a MWF formulation. For a stable disperse
system, the wavelength exponent does not change over time. For
the conditions adopted in the present study, the plots in Figure 5
show that the wavelength exponent tend to decrease over time for
salt concentrations above 7 mass% for CaCl2, 3 mass% for Al2Cl3,
and 6 mass% for MgCl2 (related to the amount of MWF
concentrate). The change of the wavelength exponent for MWF1
with 3.5 mass% of Al2Cl3 takes place at about 6000 seconds,
whereas 3.7 mass% salt addition leads to a practically instantaneous drop. Therefore, the observation time is an important factor
in this method and the proposed time of 10 min by Deluhery and
Rajagopalan[19] may be too short in cases such as those shown
here, where changes of the wavelength exponent were observed
after 10 min (for wavelength exponents >0), for example MWF1
with MgCl2 or MWF2 with Al2Cl3. An increase of admixed ion
concentration leads to an instant decrease of the wavelength
exponent due to the rapid increase in turbidity. This effect has also
been observed by Deluhery and Rajagopalan[19].
Figure 6 shows images illustrating the phase separation of
MWF1 with admixed Al2Cl3 ions, where the amount of added salt
increases from left to the right sample. The rst picture on the left
shows the freshly created MWF emulsion and the last sample
(right) shows the broken emulsion after 12 h. The phase boundary
rises with increasing ion amount due to the density difference
between the aqueous and the oily phase, leading to coagulation and
creaming, and nally to the complete phase separation.
Figure 7 plots the results for an increased destabilisation of
MWF2 for a) CaCl2, b) Al2Cl3 and c) MgCl2, which was observed for
salt concentrations above the following values: CaCl2 5 mass%,
Al2Cl3 3 mass% and MgCl2 6 mass%.
The turbidity spectra of a MWF2 sample with 8.0 mass% CaCl2
as well as the corresponding calculated wavelength exponents are
shown in Figure 8. The turbidity spectra increase over the whole
wavelength range due to an increase of the droplet size as shown
before. Anyway, an increased noise was observed in the nearUV

Figure 6. Bottle test of MWF1 for increasing amount (from left to right
increasing) of admixed CaCl2 solution after 12 h, left: fresh emulsion and
right: highest CaCl2 concentration.

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Figure 8. (a) Absorbance spectra of MWF2 for 8.0 m% CaCl2 for different
measurement times after the addition. (b) Calculated wavelength exponent
of MWF2 for 8.0 m% CaCl2 for different measurement times after the
addition.

in the corresponding values of the wavelength exponents, which

drop towards nearly 40. Thus, a noisy turbidity signal leads to
problems in the calculation of the wavelength exponent.
SUMMARY AND CONCLUSIONS

Figure 7. (a) Determination of the physical stability of MWF2 for CaCl2.

(b) Determination of the physical stability of MWF2 for Al2Cl3.
(c) Determination of the physical stability of MWF2 for MgCl2.

light range which leads to a vanishing of the signal for wavelengths

smaller than 550 nm after 15 min, which spreads towards higher
wavelengths. This behaviour was also observed for the nearIR
light range after 30 min, which spreads towards lower wavelengths. The measurement disturbances have been also observed

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The use of turbidimetry for the characterisation of the stability of

commercially available biobased green metal working uid
(MWF) emulsions has been demonstrated. In laboratory experiments MWF have been destabilised by salts (Al2Cl3, CaCl2 and
MgCl2). This aging effect can also occur during machining
processes, caused by accumulation of ionic solutes. The proposed
setup may be used for the rapid evaluation of different metal
working uid formulations by the identication of a critical salt
concentration or for the online evaluation of the physical stability
of the emulsion, due to the dependency of the wavelength exponent
in relation to the droplet size of the dispersed oleos phase. The
limits of the usability of this method have been identied by Mie
simulations of the wavelength exponent for different droplet sizes
as well as in concentration experiments.
ACKNOWLEDGEMENTS
The authors thank the Deutsche Forschungsgemeinschaft (DFG)
and the Brazilian partners Coordenao de Aperfeioamento de

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Pessoal de Nvel Superior (CAPES), Conselho Nacional de

Desenvolvimento Cientco e Tecnolgico (CNPq), Fundao de
Amparo Pesquisa do Estado de So Paulo (FAPESP) and
Financiadora de Estudos e Projetos (FINEP) who support this
project Emulsion Process Monitor (EPM) in metal working
processes within the Brazilian German Collaborative Research
Initiative in Manufacturing Technology (BRAGECRIM) at the
University of Bremen and University of So Paulo.

[24] A. A. Kokhanovsky, Optics of Light Scattering Media:

Problems And Solutions, 2nd edition, Springer, Berlin,
Germany 2001.
Manuscript received December 28, 2012; revised manuscript
received May 21, 2013; accepted for publication June 09, 2013.

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