1202 B. Glasse et al.

Benjamin Glasse1 Research Article

Cristhiane Assenhaimer2
Roberto Guardani2 Analysis of the Stability of Metal Working
Udo Fritsching1
Fluid Emulsions by Turbidity Spectra
1
University Bremen,
Mechanical Process
The physical stability of emulsions can be related to changes in the droplet size
Engineering Department,
distribution over time. Stability control of emulsions used as metal working fluids
Bremen, Germany.
is an important factor for the machining industry due to the decreased perfor-
2
University São Paulo, mance of aged and broken emulsions. Results of turbidimetric spectra measure-
Chemical Engineering ments of metal working fluids for process control purposes and emulsion stability
Department, monitoring are discussed. Metal working emulsions were artificially destabilized
São Paulo, Brazil. by admixing salts which resulted in droplet coagulation. The destabilization pro-
cess was investigated by measuring the droplet size distribution and the turbidity
spectra over time. The results were evaluated based on quantitative criteria pro-
posed in the literature. The applicability of these criteria to evaluate metal work-
ing fluids during machining operations is discussed.

Keywords: Coalescence, Emulsion stability, Metal working fluids, Spectroscopy

Received: October 29, 2012; revised: April 10, 2013; accepted: April 12, 2013
DOI: 10.1002/ceat.201200590

1 Introduction MWF emulsions contain mixtures of different oils and

chemical additives, e.g., emulsifiers, corrosion inhibitors, bio-
Metal working fluids (MWF) are widely used in metal process- cides, and defoamers, which increase the performance of the
ing operations such as rolling, grinding, and turning, because MWF and, therefore, of the process and product. Depending
of enhanced process stability, work piece quality, and tool on the machining processing operation and the work piece
life [1]. The consumption of metal working emulsions in material, the dispersed-phase concentration amounts to
Germany amounts to about 600 000 tons of metal working 2–10 vol % with a mean droplet size of 0.1–2.0 lm [8–10].
emulsions per year [2–4], while it is estimated that 2 × 109 L of While more than 300 different components can take part in
MWF emulsion is consumed worldwide, and the resulting the formulation of MWF emulsions, a single mixture may
waste fluid generation rate may be ten times higher [5, 6]. contain up to 60 different components [9, 11].
MWF are used to decrease the thermal, chemical, and MWF emulsions are mainly stabilized by adsorption of ad-
mechanical stress in the contact zone of machining processes mixed emulsifiers at the liquid-liquid phase boundary due to
which are caused by shearing and friction. Therefore, MWF electrostatic and steric barrier, preventing destabilization pro-
reduce the friction between the tool or abrasive particles cesses like creaming, sedimentation, flocculation/aggregation,
(chips, fines, swarfs, and residues) and the work piece. More- and coalescence as well as the complete breakage of the disper-
over, MWF decrease the accrued heat and dissipate the pro- sion [12]. In laboratory investigations of MWF stability, two
duced heat caused by friction, leading to more uniform tem- main mechanisms are applied to artificially destabilize MWF
perature distribution in the machining process and an emulsions, namely chemical methods like the addition of salts
independence of the ambient room temperature which may be or acids, and physical methods like temperature increase or
important for machining of chemically reactive alloys [7]. In application of an electric field [13, 14]. The admixed cations
addition, MWF flush away the created fines and chips out of reduce the surface potential of the oil droplets in accordance
the contact zone from the nascent metal surface to prevent a to the DLVO theory since they adsorb partly at the oil surface
rewelding and protect the newly formed surface by wetting it, and lower the repulsive and electrostatic barriers at the surface
which is important for, e.g., drilling. of the droplets. Furthermore, the salt increases the density of
the water which promotes the separation process [15, 16].
Thus, the stability of the emulsion decreases due to the in-
creased possibility of coalescence of the droplets and the higher
– coagulation rate. This eventually leads to the complete
Correspondence: B. Glasse (glasse@[Link]), University breakage of the emulsion. An increased temperature acceler-
Bremen, Mechanical Process Engineering Department, Badgasteiner ates most of the chemical reactions (like the hydrolysis of
Straße 3, 28359 Bremen, Germany. certain emulsifiers), reduces the viscosity (by increased Brow-

[Link] © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208
 Spectroscopy 1203

nian motion and coalescence rate), and changes the cloud in which the pre-exponential term K0 incorporates the proper-
point which corresponds to the formation of suspended solid ties contained in the expression for the scattering coefficient
particles [12, 13]. In order to adapt MWF to hard water usage under the Rayleigh scattering regime. Under this regime, the
(with increased salt content), special buffer additives are ad- exponent z is equal to 4 [21] and decreases as the particle size
mixed. increases. Eqs. (2) and (3) can be combined and, for a given
Nevertheless, due to biological, thermal, and chemical pro- particle diameter, e.g., the volumetric mean diameter, d4,3, the
cesses in metal working machining operations, the MWF com- wavelength exponent can be expressed as the slope of ln(s) ver-
position and morphology change during usage, resulting in sus ln(1/k0), as indicated in Eq. (4).
increased and broader droplet size distribution (DSD) which
directly affects the MWF performance and toxicity [9, 17]. d ln…s†
zˆ (4)
Turbidity spectroscopy provides a fast technique for gather- d ln…1=k0 †
ing information on the chemical composition, droplet size, in-
ternal structure, and concentration of the dispersed phase of where k0, wavelength in vacuum, is calculated as:
an emulsion. Analysis of turbidity spectra may be used as a
component of optical sensors for the online and inline size k0 = kmnm (5)
measurement of sub-lm and lm droplets due to the simple
geometrical requirements and simple light scattering method km is the wavelength and nm is the refractive index of the
in a relatively narrow wavelength range (usually from ultravio- continuous medium. Thus, under the mentioned assumptions,
let until near-infrared range) [18–20]. The turbidity of an the wavelength exponent for a given emulsion can be deter-
emulsion is affected by the dispersed phase (particles, droplets, mined from turbidity measurements at different values of km
and bubbles) and is related to the incident and transmitted by fitting Eq. (4) to the data.
light for a path length using a spectrometer. The turbidity The simplified relationship in Eq. (4) has been the basis for
spectrum consists of the absorption by the species present and a number of studies reported in the literature [23, 24] aimed at
the scattering by the dispersed droplets, depending on the using the wavelength exponent as an indicator of the stability
wavelength [21]. Therefore, turbidimetric techniques may be of emulsions. Specifically in the paper by Deluhery and Raja-
used to monitor the stability of MWF, since the turbidity is re- gopalan [23], the decrease in the wavelength exponent over
lated to concentration as well as DSD of the dispersed phase time has been related to the destabilization of emulsions by
[14, 22, 23]. associating this process with the increase in droplet size by
Eq. (1) relates the measured turbidity s(k0) via spectrometry coalescence.
with the optical path length L, the emitted light intensity, In the present study, this application has been further inves-
I0, and the received light intensity I, for light with wavelength tigated by monitoring both the turbidity spectra and the DSD
k0, while the term ln(I0/I) is referred to absorbance or extinc- of emulsions over time, for MWF samples destabilized by add-
tion. ing calcium chloride. For these MWF samples, the time evolu-
tion of the wavelength exponent as well as the fitting quality of
1 I Eq. (4) to the experimental data have been measured and com-
s…k0 † ˆ ln… 0 † (1)
L I pared with DSD measurements.
The absorbance of emulsions is the result of light absorption
by the continuous and dispersed phases plus scattering. For
a nonabsorbing system, the turbidity can be directly related 2 Materials and Methods
to scattering by the suspended droplets in the form of
Eq. (2) [21]: 2.1 Materials

Z∞ A commercial MWF emulsion based on mineral oil was used

p 2
s…k0 † ˆ N D K …a; m†f …D†dD (2) without any further treatment at a concentration of 5 vol %. This
4 MWF type is recommended for general usage in machining
0
processes with hard water. Calcium chloride (CaCl2 × 2H2O,
The scattering coefficient, K(a, m), depends on the droplet purity of 99.5 %) was employed in the artificial MWF destabi-
size parameter a (a = pD/km) and the refractive index lization experiments.
ratio m, evaluated at k0. For dilute dispersions consisting of
monodisperse spherical nonabsorbing particles significantly
smaller than the wavelength of the incident light, scattering 2.2 Laboratory Experiments
is described by the Rayleigh scattering regime [21]. Under this
regime, and if it is assumed that the refractive index Stability experiments were carried out first with different cal-
ratio does not depend significantly on the wavelength, the cium chloride concentrations to visually observe the appear-
scattering coefficient, K, can be expressed in a simplified form ance of haze as well as to measure changes in the DSD. A con-
as Eq. (3): centration of 0.3 wt % CaCl2 led to measurable turbidity and
stabilized DSD in an acceptable time and was used in all ex-
K ≈ K0az (3) periments reported in this study.

Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
1204 B. Glasse et al.

2.3 Workshop Experiments

MWF emulsion samples were taken weekly from the nozzle of

a vertical turning machine. The fluid was recirculated for
5 min prior to sampling for homogenization purposes. The
concentration was approximately 5–7 vol %.

2.4 Emulsion Destabilization Experiments

The MWF was diluted with deionized water at room tempera-

ture to a concentration of 5 vol % and afterwards gently sha-
ken, creating a homogenized emulsion. The CaCl2 was mixed
with deionized water and shaken for 0.5 h on a vibrating table
until all CaCl2 was completely dissolved. Then, the salt
solution was admixed to the metal working emulsion to reach
the desired concentration of 0.3 wt % and stirred to homoge-
Figure 1. Absorbance spectra of an MWF sample at different
nize the dispersion. A series of 13 samples were prepared under
times after addition of 0.3 wt % CaCl2.
the same conditions and used in the destabilization experi-
ments.
previous study by the authors [25], it was observed that no
constituent of this MWF absorbs light in the range from 400
2.5 Turbidity Spectra Measurement to 900 nm. Thus, the observed changes in the spectra in this
range over time are mainly due to changes in the droplet
Absorbance measurements were performed with a UV-Vis- population. In this study, the results are based on the absor-
NIR spectrometer, model HR2000+ES from OceanOptics, with bance measured in the range from 500 to 605 nm, in order to
a light source DH 2000-BAL (200–1100 nm) and a dip probe avoid any oscillation in the spectra that could be related to
with 6.35 mm diameter, 127 mm length, and 2 mm optical light absorption effects.
path length which enables inline monitoring of the MWF Fig. 2 presents results obtained with an MWF sample at two
emulsion. The noise and reference signals were recorded prior different times after addition of CaCl2 solution. The observed
to the measurements and subtracted from the measurement changes in the absorbance spectra (plot (a)) correspond to a
signal with an integration time of 10 ms and averaged for ten significant decrease in the slope of the straight lines (plot (b)),
measurements in the ultraviolet to near-infrared light range i.e., the wavelength exponent z obtained by linear regression of
(215–1050 nm). The light source was initially warmed up for the data based on Eq. 4. Plot (c) indicates that this destabilized
45 min in order to reach its full intensity and the sample was MWF contains two droplet populations.
gently shaken prior to the measurements, in order to homoge- As illustrated in Fig. 2, the addition of CaCl2 resulted in sub-
nize it. stantial changes in the DSD of the MWF, with the formation
of a second droplet population with larger diameters. The
droplet size distribution was monitored over time for the arti-
2.6 Droplet Size Measurement ficially destabilized MWF samples and for the MWF used in
the turning machine. The results are displayed in Fig. 3. The
The volumetric DSDs of the MWF emulsions were measured DSD changes gradually from monomodal to bimodal. The
by laser diffraction with a Malvern Mastersizer 2000 diffrac- larger mode corresponds to the new population formed. This
tometer, applying an independent model and refractive index larger mode gradually shifts towards larger droplet sizes and
of the MWF equal to 1.45. It was necessary to dilute the sam- the DSD curve becomes progressively broader. Fig. 3 b shows a
ples by adding water in order to prevent multiple scattering. similar behavior of the DSD of the MWF used in the turning
No destabilization was observed after water addition, since the machine over time.
DSD of the diluted samples did not change after 1 h. Figs. 4–6 present results for the artificially destabilized MWF
samples after CaCl2 addition. The volumetric mean droplet
diameter, d4,3, increased over time from approx. 150 nm to
3 Results and Discussion 700–1700 nm. This behavior was expected, since the addition
of salts to an emulsion changes the electrostatic balance of the
After addition of the CaCl2 solution, the MWF samples be- system, decreasing the repulsive forces between the droplets
came immediately cloudy. As illustrated in Fig. 1, the absor- and facilitating the coalescence process. However, the DSD ap-
bance measured by the spectrometer increased over the whole parently tends to stabilize after ca. 1000 min. The dispersion of
spectra. Changes in shape and an increase in the oscillations of the DSD curves also increases with time as a consequence of
the turbidity curves are also demonstrated in Fig. 1, indicating the formation of the bimodal distribution and tends to stabi-
that the turbidity spectra are very sensitive to the destabiliza- lize for longer times. The corresponding values of the wave-
tion caused by adding the CaCl2 solution to the MWF. In a length exponent, z, are indicated in Fig. 6. These values were

[Link] © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208
 Spectroscopy 1205

Figure 3. (a) DSD of the MWF samples at different times after

addition of CaCl2; (b) weekly change of the DSD of a used MWF
before refilling of the machine.

Figure 2. Experimental results with an MWF sample at two dif-

ferent times after addition of 0.3 wt % CaCl2. (a) Absorbance
spectra; (b) ln(s) versus ln(1/km) (Eq. (4)); (c) DSD.

estimated by linear regression from turbidity wavelength data

based on Eq. (4). Figure 4. Time evolution of the volumetric mean (d4,3) of the
The decrease of the z-values is in accordance with the results DSD for the MWF samples after addition of 0.3 wt % CaCl2.
reported by Deluhery and Rajagopalan [23] and also with the
predicted tendency from scattering equations [21]. However,
the formation of a bimodal DSD results in a significant de- the increase in d4,3, but there is a significant reduction in the
crease in the quality of the fitting of Eq. (4) to the data. This is quality of the fitting as expressed by the coefficient of determi-
illustrated in Fig. 7 for the artificially destabilized samples. As nation, R2, when the volumetric mean diameter, d4,3, reaches
expected, the wavelength exponent decreases gradually with ca. 10 lm.

Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
1206 B. Glasse et al.

Figure 5. Time evolution of the standard deviation of the DSD

for the MWF samples after addition of 0.3 wt % CaCl2.

Figure 7. Wavelength exponent z and coefficient of determina-

tion R2 for the fitting of Eq. (4) to data of the artificially destabi-
lized MWF samples as a function of d4,3.

Figure 6. Time evolution of the wavelength exponent z (Eq. (4)) the emulsion contains essentially one population of droplets.
for the MWF samples after addition of 0.3 wt % CaCl2.
As a result, the fitting of Eq. (4) is good (R2 equal to 0.997).
For 30 weeks of operation, the DSD is multimodal, and the
The use of the wavelength exponent has been proposed un- fitting of Eq. (4) is significantly worse (R2 equal to 0.481).
der the assumption of a monomodal and monodisperse distri-
bution [23], and the decrease in its value with time has been
associated to the growth in droplet size by coalescence. Thus, 4 Conclusions
according to [23], the stability of an emulsion can be evaluated
by measuring the turbidity at different wavelengths over a cer- The destabilization process of a commercial MWF emulsion
tain time period and monitoring the time evolution of the with MWF concentration of 5 vol % artificially aged with
wavelength exponent obtained by fitting Eq. (4) to the data. CaCl2 was characterized by UV-Vis-NIR spectroscopy. Shortly
However, based on the results in Fig. 7, the fitting quality of after addition of this salt to the MWF, the DSD of the emul-
Eq. (4), e.g., the coefficient of determination, and the resulting sion became bimodal. A new population with larger droplets
wavelength exponent are measured at specific instants of time, increased in volume and in mean droplet size over time, even-
and then the condition of the MWF emulsion can be evaluated tually reaching a stable condition, characterized by the pres-
in real time. ence of two droplet populations.
This method was applied to the monitoring of an MWF Monitoring of the MWF destabilization process by the spec-
under real operation conditions, i.e., in a turning machine. trometric turbidity sensor and the use of the turbidity spectra
The results are illustrated in Fig. 8 for an operating time of to calculate the wavelength exponent pointed to a clear corre-
33 weeks without replacement of the MWF. The wavelength lation with the volumetric mean droplet size.
exponent decreases over time and, after ca. 28 weeks, a sharp The results confirmed the conclusions previously presented
drop in the coefficient of determination is observed. by other authors [23] that the wavelength exponent can serve
In Fig. 9, the condition of the MWF is indicated at different as a quantitative criterion in the monitoring of the emulsion
operating times of the machine. In the first week of operation, destabilization process by observing the change in its value

[Link] © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208
 Spectroscopy 1207

Figure 8. Time change of the wavelength exponent z and the

coefficient of determination R2 for the fitting of Eq. (4) to MWF
samples taken from a turning machine in operation. Figure 9. (a) Illustration of the DSD and (b) fitting of Eq. (4) to
MWF samples taken from a turning machine operation at differ-
ent operating times.
over a given time period. Furthermore, in the present study,
the time evolution of the emulsion structure was further inves-
tigated and the detected decrease in the wavelength exponent gico (CNPq), Fundação de Amparo à Pesquisa do Estado de
was associated with the formation of a second droplet popula- São Paulo (FAPESP), and Financiadora de Estudos e Projetos
tion with larger mode. As the volume fraction of this second (FINEP) who funded this project within the Brazilian German
population with larger mode increases, the quality of the fit- Collaborative Research Initiative in Manufacturing Technology
ting of Eq. (4), expressed by its coefficient of determination, (BRAGECRIM). The authors would like to thank the Manu-
decreases. Thus, the emulsion stability can be evaluated by per- facturing Department of the Foundation Institute of Materials
forming one instantaneous measurement of turbidity at differ- Science Bremen for supporting this project.
ent wavelengths, with computation of the coefficient of deter-
mination of the wavelength exponent fitting. The authors have declared no conflict of interest.
In view of the simple measuring and computation method,
this concept of applying the wavelength exponent was tested
in the operation of a turning machine during approx. Symbols used
30 weeks. The results indicate that the method can be applied
to the in situ characterization of MWF quality in machining d [lm] droplet size
processes. f(D) [lm–1] droplet size distribution density
function
I [cd] received light intensity
Acknowledgment I0 [cd] emitted light intensity
K [–] scattering coefficient in Eq. (1)
The authors would like to thank the Deutsche Forschungs- K0 [–] pre-exponential term in Eq. (3)
gemeinschaft (DFG) and the Brazilian partners Coordenação L [cm] optical path length
de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), N [cm–3] number of particles per unit
Conselho Nacional de Desenvolvimento Científico e Tecnoló- emulsion volume

Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link]
1208 B. Glasse et al.

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[Link] © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2013, 36, No. 7, 1202–1208