Silicon
DOI 10.1007/s12633-014-9182-6
ORIGINAL PAPER
Quantification of Si in Silicone Oils by ICP-OES
Qian Wang · Zhenyu Yang
Received: 19 August 2013 / Accepted: 22 January 2014
© Springer Science+Business Media Dordrecht 2014
Abstract A new simple and low cost method of quantifica-
tion of trace amounts of silicon (Si) in silicone oils has been
developed by combining the silicone emulsion and induc-
tively coupled plasma optical emission spectroscopy (ICP-
OES) analysis. Silicone oils that contained phenyl groups in
the viscosity range from 20 to 1000 mPa.s formed stable oil
in water emulsions in the presence of Tween 80 surfactant
and methylisobutylketone (MIBK). The Si in the emulsions
was further quantified by ICP-OES. The calibration was
performed using spiked inorganic silicon standard in the
emulsions and the method was verified by the standard ref-
erence material SRM1066a. The precision and accuracy of
the emulsion method applied to three phenyl containing
silicone oils and polydimethylsiloxane (PDMS) with low
viscosity (10 cSt) were good and acceptable (RSD<10 %
and the error range <10 %) with the limits of detection
(LOD) in the emulsion as 0.5 ppm Si. Compared to the Si
determination by the direct organic solvent ICP-OES, this
method is much more convenient, where a regular ICP-OES
instrument can be directly used for the quantification of Si in
the silicone oils obtained via extraction by organic solvents
from plastics and other samples.
Keywords Silicone oil · Emulsion · ICP-OES · Methyl
isobutylketone (MIBK) · Si measurement
Q. Wang ()
Section of Chemical Engineering, Department of Biotechnology,
Chemistry and Environmental Engineering, Aalborg University,
Niels Bohrs Vej 8, 6700 Esbjerg, Denmark
e-mail: qwang@bio.aau.dk
Z. Yang
Department of Energy Technology, Aalborg University,
Niels Bohrs Vej 8, 6700 Esbjerg, Denmark
1 Introduction
Silicone oils are synthetic organic silicon polymers. They
have (SiR2 -O)n backbones with different polymerization
degrees (n) and chain lengths. The side group R is com-
monly methyl and phenyl groups. Other functional groups,
such as hydrogen, alkoxy, amine and higher number alkyl
groups can also be introduced both to the side and to the
end group of silicone oils. Silicone oils have low surface
tension, high hydrophobicity and can wet most surfaces. In
addition to these properties, silicone oils have also excellent
lubricating and insulating functions, as well as high ther-
mal, weather and chemical resistance. Due to these unique
properties, silicone oils have been widely used in indus-
trial and consumer products. For example, silicones are used
as active ingredients in foods, cosmetic and personal care
goods, as heat transfer fluids, as lubricants and sealing mate-
rial, as well as additives in plastics and other final use
products [1–3]. In many cases, even low levels of silicone
oils can have a significant effect on a systems performance.
For example; small amounts of silicone oils present as addi-
tives in shampoo formulations and deposited on hair after-
wards lead to significant improvements in detangling and
wet comb performance of human hair [4]. Trace amounts
of silicone oil present in the feedstocks of coking processes
are capable of deactivating the hydrogenation catalysts [5].
The adsorption of silicone oil on the cleaned metal parts will
result in the bad wetting and adhesion of lacquers on them.
Therefore, it is desirable to quantify the exact amount of sil-
icone oil in the sample, especially when the organic silicon
amount is at trace level.
Methods for quantitative determination of Si in organic
silicon compounds have long been established and reported
[6, 7]. The analytical methods that can specify and quantify
organic silicon compounds include FTIR, Raman and NMR.

FTIR and Raman techniques, however, have higher limits of
detection (LOD), while NMR needs special techniques to
quantify trace amounts of silicon. Some hyphenated meth-
ods, which combine the separation function of gas chro-
matography (GC), HPLC, supercritical fluid chromatogra-
phy (SFC) or gel permeation chromatography (GPC) with
the highly sensitive elemental quantification techniques,
such as ICP-OES, atomic absorbance spectroscopy (AAS),
atomic emission detector (AED), NMR and ICP-MS, have
been investigated and used for the trace amounts analysis of
silicones and their degradation products [8–10]. Electrother-
mal atomic absorption spectroscopy (ETAAS) is highly
sensitive and has been explored to quantify trace amount
of silicon in biological samples. In the case of organic sil-
icones, due to their low decomposition temperatures, loss
of analyte during the ashing step limits the application of
ETAAS in the direct analysis of silicone in the sample [11].
The above mentioned techniques for trace silicone anal-
ysis frequently involve sample preparation steps because
they are present in the sample matrix at low levels. To pre-
pare the sample for analysis, the silicones need to be either
extracted from the sample by organic solvent or by solvent
mixtures, or the whole sample needs to be decomposed to
get all the silicon dissolved in clear aqueous solution before
analysis. In general, depending on the sample matrices, acid
mixtures (for example, H2 SO4 /HNO3 , HNO3 , HNO3 /HF,
HNO3 /H2 O2 ) can be used to convert the whole sample
to soluble Si. The addition of boric acid to complex the
extra amount of HF and the addition of water soluble ter-
tiary amines are used to improve the precision and LOD
[12]. Some silicones may be volatile under the heat during
digestion, which will result in loss of sample affecting the
accuracy of the quantification of silicon. Furthermore, these
digestion methods are time consuming. Fusion with alka-
lines (LiBO2 or Li2 B4 O7 ) or peroxide (sodium peroxide
in case of volatile silicones) followed with acid dissolution
is also a common method to get soluble Si for analysis.
Silicon dissolved in aqueous digestion mixture can then
be quantified. However, Parr-type bomb shall be used to
combust the sample. Recently, the digestion of silicones
in non-oxidative alkaline media in a microwave oven has
been reported to avoid the sample loss. The digested sam-
ple was afterwards analysed by ICP-OES. The LOD of the
developed method was 2 kg.cm−3 , which is about one order
higher than the inorganic soluble silicon quantification by
the same instrument [13].
Besides using digestion to convert the sample into solu-
ble silicon form for analysis, methods to analyse silicones
just after their extraction into an organic solvent are also
available. The relatively fast determination of silicone poly-
mers by organic solvent FAAS (Flame Atomic Absorption
Spectroscopy) has been developed as a standard method
[14]. Similar trace metal analysis using ICP-OES in crude
Silicon
oils dissolved in organic solvents and in organic solvents
after extraction or by HPLC separation have been exten-
sively investigated [15, 16]. The ICP-OES analysis based on
organic solvents, however, needs an increase of the radiofre-
quency power and the plasma argon flow rate during the
measurement. In addition, extra accessories such as a con-
denser installed after the spray chamber and the introduction
of reactive gas (such as O2 ) have to be mounted on the reg-
ular apparatus. Special tubings for sample uptake are also
needed. These installations of extra accessories increase the
economic investment as well. Furthermore, the use of pure
organic solvent (methylisobutylketone, tetrachloromethane,
toluene, etc.) can pose high health risks for the analysers.
An alternative to avoid too many modifications on a regular
ICP-OES instrument for the silicone analysis is to decrease
the sample uptake rate to obtain stable plasma for analy-
sis. However, this solution will lead to a long analysis time
which will again increase the analysis expense [17].
Emulsion techniques have been frequently used to dis-
perse oils in water or vice versa. Silicone oils by themselves
have been prepared in emulsions for various applications.
For the analysis of trace metals in crude oils or plant oils,
emulsion methods have been successfully applied in the
ICP-MS (mass spectroscopy) and ICP-OES analysis. It has
been found that the combination of these sensitive detection
methods and the emulsion sample preparation can make the
analysis fast, easy, as well as accurate, at low analyte levels
[18–20]. For example, Lord [21] made crude oil emulsions
for Ni, V and Co analysis using ICP-MS. The total organic
amount (including crude oil, organic solvent and surfactant)
in the emulsion was only 4 wt%. The oil emulsions were
stable for 3 months in the presence of the surfactant that
was used. Chirinos et al. [22] reported the analysis of S,
Ni and V in the emulsified heavy crude oils by ICP-OES
method. Other authors, Borszeki et al. [23] and Benzo et al.
[24] also reported the preparation of oily or plant oil emul-
sions, which were then analysed by ICP-OES to determine
the amounts of trace metals in the sample. The advantages
of the emulsion method lie in the fact that no modifica-
tions of the regular instrument are needed, and since only
small amounts of organic solvent will be used, exposure to
organic solvents during sample preparation and analysis will
be reduced [25].
To our knowledge, the use of emulsion techniques for
silicone determination has not been investigated yet. This
work investigated the application of the emulsion technique
for the quantification of silicon in some silicone oils by
ICP-OES technique. The preparation of the silicone emul-
sions, the calibration with spiked inorganic silicon standard
in the emulsions, the verification with organic silicon stan-
dard reference materials, as well as the application of
the method in the quantification of four silicone oils are
described.
Silicon
2 Experimental
2.1 Materials
2.1.1 Si Standards
Inorganic Si standard stock solution of 1000 ppm Si was
obtained from SCP Science, Canada. Standard reference
material SRM 1066a (octylphenylcyclotetrasiloxane) was
purchased from NIST.
2.1.2 Solvents
MIBK (methylisobutylketone) was of analytical grade from
Merck (Germany). Distilled deionized water (apparatus
Köttermann 1034, Struers) was used for all the sample
preparations.
2.1.3 Surfactants
Triton X-100 (C8 H17 C6 H4 (OCH2 CH2 )n OH, n = 9–10,
d20/4 1.064–1.067, Merck), Tween 20 (C58H114 O26 , d20/4
1.100–1.110, hydroxyl value 96-108, saponification value
40–50, Merck) and Tween 80 (bp 100o C, d 1.064, Sigma,
USA) were all of analytical grade. The chemical structures
of the three surfactants are shown in Scheme 1.
Tween 20
Tween 80
Triton X-100, n=9-10
Scheme 1 The chemical structures of Tween 20, Tween 80 and Triton
X-100
2.1.4 Silicone Oils
Analytical grade silicone oil AR20, AS100 and AP1000
containing both methyl and phenyl side groups were
from Sigma-aldrich and had viscosities of 20, 100 and
1000 mPa.s, respectively. Silicone oils based on poly-
dimethylsiloxane (PDMS) with different viscosities were
also from Sigma Aldrich. The names, densities and vis-
cosities of all the silicone samples used are listed in
Table 1.
2.2 Emulsion Preparation
The silicone oil stock solution in MIBK was weighed in a
50 ml borate-glass volume flask followed by the addition of
the surfactant. The flask was then hand shaken to mix the
components well. Distilled deionized water was then added
in five portions, where each portion weighed about 0.5 g.
After the addition of each portion of water, a vigorous hand
shaking of the flask was done to ensure thorough mixing.
After about 2.5 g water had been added, the total weight
of the emulsion was made up to 50 g by adding distilled
deionized water at one time.
2.3 ICP-OES Parameters
Silicone oil emulsions and the aqueous Si standard solutions
were analysed on Perkin Elmer Optima 3000DV with soft-
ware Winlab32 for the instrument control, data acquisition
and processing. The instrumental parameters are shown in
Table 2. Si line at 251.66 nm was used for Si quantification.
2.4 FTIR Analysis
Silicone oils were dropped onto KBr tablet to get transmis-
sion FTIR spectra. Avatar 370 FTIR spectrometer (Thermo
Nicolet, USA Madison WI) equipped with the OMNIC soft-
ware was used to collect the spectra. The spectra were
obtained on the average of 4 scans with resolution of
4 cm−1 .
2.5 Acid Wet-Digestion of Silicone Oils
The acid wet digestions of silicone oils were carried out by
following the procedure described in literature [26].
3 Results and Discussion
3.1 Emulsion Preparation
In order to make stable silicone oil emulsions as well as to
keep stable plasma during the ICP-OES analysis, the type of
 Silicon

Table 1 The information of silicone oils analysed in this study

Name Viscosity Density (g/ml) Producer

AR20 20 mPa.s 1.01 (20◦ C) Germany

AS100 100 mPa.s 1.06 (20◦ C) Germany
AP1000 1,000 mPa.s 1.09 (20◦ C) Germany
D4 (98 %) 0.956 (25◦ C) USA
PDMS 10 10 cSt 0.93 (25◦ C) Dow Corning
PDMS 100 100 cSt 0.96 (25◦ C) Dow Corning
PDMS 1,000 1,000 cSt 0.97 (25◦ C) Dow Corning
PDMS 10,000 10,000 cSt 0.97 (25◦ C) Dow Corning
PDMS 100,000 100,000 cSt 0.97 (25◦ C) Dow Corning
PDMS hydroxy terminated 18,000–22,000 cSt 0.97 (25◦ C) Dow Corning

surfactants, the amounts of silicone oil and organic solvent
were studied.
The HLB (hydrophile-lipophile balance) of a surfactant
has been widely used as a measure for the surfactant or
surfactant pair selection in order to achieve the desired
solubility of the different ingredients in the cosmetic and
detergency industry. The HLB value of a non-ionic sur-
factant can be calculated as HLB=20Mh/M, where Mh is
the molecular mass of the hydrophilic portion in the non-
ionic surfactant, and M is the molecular mass of the whole
molecule [27]. From Becher [28], it is summarized that the
HLB of a non-ionic surfactant that can stabilize an oil-in-
water emulsion should be in the range of 8–18. Surfactants
in this range, such as Triton X-100, Tween 20, Tween 80 and
phenylester, have been used to make crude oil or plant oil
emulsions [17, 21–24]. In this work, Triton X-100, Tween
20 and Tween 80 were tested as emulsifiers in combination
with an organic solvent. Triton X-100 and Tween 20 could
not give a stable homogeneous silicone oil emulsion, as a
separate upper oily layer formed after storing the mixture
for 12 h. This could be due to the short chains in these two
surfactants. Tween 80, however, which has long hydrophilic
polyether chain and a relatively bulk hydrophobic moiety
with higher molecular weight than the other two surfactants,
could stabilize the silicone oils used in this study. Therefore,
Table 2 The instrumental parameters of ICP-OES for Si analysis in
emulsion
Item Value Unit
Instrument Optima 3000
Plasma outer flow 15 ml/min
Nebulizer flow 0.3 ml/min
Auxillary flow 0.6 ml/min
Rf power 1500 W The concentration range of the surfactant was between 1.61
Sample uptake rate 1.0 ml/min
only Tween 80 was used as the surfactant in the following
emulsion preparations.
Emulsions with silicone oil, surfactant and distilled
deionized water were made with various surfactant to sil-
icone oil weight ratios. After vigorous hand shaking, the
mixtures were put to stand alone for 12 h. All the mixtures
then formed two phases, where the upper phase was a milky
white dispersion and the bottom phase was a white precip-
itate. The more silicone oil added, the thicker the bottom
precipitate phase was. The highest surfactant to oil ratio was
4:1 in this study. This result indicates that Tween 80 will not
efficiently emulsify the silicone oil by simple hand shak-
ing at such a high oil amount. Further attempt to reduce the
amount of silicone oil was not done due to the fact that it is
difficult to weigh a sample size of lower than mg accurately.
Since the aim of this work was to quantify Si at ppm
level, the concentration of silicone oil did not need to be
higher. Organic solvents, such as tetraline and xylene, have
been used to disperse crude oil in the emulsion. In addition,
another advantage of using organic solvent in this study is
that the organic solvent is frequently used to extract the sil-
icone oil additives in the plastics, as well as to extract any
soluble organic silicone compounds in the environmental
samples. Therefore, in most cases, the real-life sample to
be analysed will be organic silicone compounds dissolved
in organic solvents. The common solvents for silicone poly-
mers are MIBK, toluene, chloroform, etc.. MIBK was used
in this study due to its relative low toxicity.
The influence of the amount of surfactant Tween 80 on
the background signals was studied at first. It was found
(data not shown) that the ICP-OES background Si counts
didn’t vary significantly in the surfactant range from 0.25 to
4.5 wt%.
Secondly, the ICP-OES background signals of the emul-
sions with various MIBK to surfactant ratios were studied.
to 4.00 wt%, and the MIBK was from 0.1 to 0.5 wt%.
Silicon

The results (data not shown) showed that the background Si 250000
counts increased slightly due to the addition of MIBK in the
mixture. Furthermore, the plasma was either non-stable or A B C
gave slightly higher background Si counts when the MIBK 200000 D E
concentration approached or was higher than 0.5 wt%.
Based on the above results, emulsions with either
0.4 wt% or 0.5 wt% of MIBK, and with Tween 80 to MIBK 150000

Si counts
weight ratios from 3:1 to 8:1 were made (see Table 3). The
emulsions were then spiked with the inorganic Si standard
solution to make the final Si concentrations to vary from 100000
0.5 to 15 ppm. The measured Si counts in these emulsions
are shown in Fig. 1, where all the samples fall onto a linear
line no matter their variations on the MIBK concentrations 50000
and the surfactant to MIBK ratios. These results indicate
that small variations in the surfactant and the MIBK con-
centration during the emulsion preparation will not have 0
significant influence on the quantification of Si. 0 5 10 15 20
In general, emulsion with 0.4 wt% MIBK and with Si concentration (ppm)
Tween 80 to MIBK weight ratio of 5:1 was selected as a Fig. 1 Si signal counts by ICP-OES of the spiked Si emulsions with
standard formulation for the further method development. different MIBK, Tween 80 and Si amounts. Red square, sample series
The emulsions were optically clear and transparent. (a) green triangle, sample series (b) brown circle, sample series (c)
blue parallelogram, sample series (d) and grey cross, sample series (e).
For the detailed data, see Table 3
3.2 Calibration and Verification

Calibrations were carried out both in the distilled water
solutions and in the emulsions which were all spiked with
inorganic Si standard stock solution. Figure 2 shows the cal-
ibration curves of the two standard series. It can be seen that
the Si element in water solutions produce relatively higher
signals. Similar results for the crude oil emulsions have
been reported by Chirinos et al. [22]. The reason could be
due to the lowering of plasma temperature in the presence
of MIBK, which could also decrease the silicon emission
counts. Therefore, silicon standards in the emulsions were
used to make the calibration curve in this work.
The certified reference material SRM 1066a was used
to verify the Si quantification in the emulsions. A series of
emulsions with known amounts of SRM 1066a were made

160000
Table 3 The ICP-OES Si signals with different amounts of spiked Si,
MIBK and Tween 80 140000

Sample Spiked Si (ppm) MIBK (wt%) Tween 80 (wt%) Si counts 120000

A 0 0.40 1.61 1012.3

0.5069 6966.6 100000
1.0810 14117.2
Si count

5.0899 64717 80000

B 0 0.40 2.00 1037.4
0.5073 7222.5
60000 Si in water
1.0918 14197.9
5.3370 66323.1 Si in emulsion
10.3195 130747.8 40000
15.3575 194147 SRM in emulsion
C 0 0.50 2.02 1058.1 20000
0.5048 7738.5
D 0 0.50 2.49 1222.2
0.5127 7665.2 0
0 5 10 15 20
1.0121 14968.5
Si concentration (ppm)
5.1533 65586.4
10.3121 131208.5 Fig. 2 Calibration curves of the Si standards by ICP-OES. Blue
15.1839 198861.8 parallelogram, inorganic Si standards in distilled water; red square,
E 1.0301 0.50 4.00 14300.8 inorganic Si standards in emulsion; and green triangle, SRM 1066a
4.7774 68529.8 standards in emulsion

and measured under the same ICP-OES parameters. The
results are shown in Fig. 3 and Table 4, where the listed Si
concentration in each sample is the average of three mea-
surements with RSD<5 %. Both from Table 4 and Fig. 3, it
is clear that the emulsion method can give accurate and pre-
cise Si measurements in the Si concentration range from 0.5
to 15 ppm. It is interesting to notice that when dimethyltetra-
cyclosiloxane (D4) was used to verify the emulsion method,
systematically very high Si signals were obtained. Although
good emulsions can be obtained for the D4 samples, the
emulsion method is not suitable to analyse silicon in the
D4. Todolı́ et al. [29] have also reported higher Si signals
obtained from ICP-OES analysis in some siloxanes with low
boiling points and high volatility.
3.3 Limits of Detection (LOD)
The limits of detection were calculated according to the
method described by Miller and Miller [30]. It is defined
as the concentration of the analyte that gives a signal equal
to the blank signal plus three times of the standard devia-
tion of the blank. The results are summarized in Table 5. It
can be seen that the LOD of the emulsion method is in the
same range of that from the water solution under the same
ICP-OES operating condition. This indicates that the LOD
does not decrease by the components used in the emulsion.
It is noticeable that the tabled background emission concen-
tration (BEC) value at line 215.611 nm in water solution
under the optimum ICP-OES condition for the instrument is
0.40 ppm.
140000
120000
100000
AR20
80000
Si count
AS100
60000
AP1000
40000
SRM 1066a
20000 PDMS10
0 The FTIR results agree well with the founding from the
0 20 40 60 80 100
silicone oil concentration (ppm)
Fig. 3 Plot of silicone oil concentrations in emulsion against silicon
counts from ICP-OES analysis. Light blue asterisk, PDMS10 with vis-
cosity 10 cSt; blue parallelogram, AR20; red square, AS100; green
triangle, AP1000; purple cross, SRM1066a
Silicon
3.4 Application of the Emulsion Method in Si
Determination in Silicone Oils that Contain Phenyl
Groups
The emulsion method was used to quantify the Si amount
in three silicone oils. Silicone oils with viscosity range from
20 to 1000 mPa.s were selected in order to find out whether
stable emulsions can be made in samples with different vis-
cosities. For each type of silicone oil, a series of emulsions
were prepared with known oil concentrations. The Si con-
centrations were calculated based on the calibration curve
made from the standard emulsions that spiked with inor-
ganic Si standard solution. Results shown in Table 4 indicate
that the precisions of the emulsion ICP-OES method for
the three silicone oils in the concentration range between
1 to 40 ppm are good or acceptable (RSD<10 %). It can
also be seen that the silicon concentrations in the three oil
samples are different. Thus, the classical acid wet-digestion
method to determine the silicon amount in the silicone poly-
mers was also carried out, which was used as a measure for
the accuracy evaluation of the emulsion ICP-OES method.
From Table 4, it can be seen that the results obtained from
the wet-digestion agree well with those obtained from the
emulsion ICP-OES method for sample AR10 and AP1000.
Sample AS100 had higher amounts of Si found by the
acid digestion method, and the obtained SiO2 ash could not
be totally dissolved in acid as the other two samples did.
In addition, since the silicon amounts found in the three
silicone oils are different, the FTIR analysis was then con-
ducted on the silicones. Figure 4 shows the FTIR spectra of
all the silicones. In the FTIR spectra, the peak at 698 cm−1
and the multi-peaks between 3004 and 3100 cm−1 were
found, which originate from the phenyl group absorption.
According to Lady et al. [31] the ratio of the peak height
A1430 :A1261 can be used to correlate the phenyl (C6 H5 -Si)
to methyl group (CH3 -Si) ratio in the silicone sample. Cal-
culations were then performed and the results for the three
samples are listed in Table 4. The calculated results show
that the amounts of phenyl groups in the three samples are in
the order of AP1000 > AS100 > AR20. By assuming that
only phenyl and methyl groups are the side groups in the
backbone of the three silicone oils, the lower the amounts of
the phenyl group, the higher percentage of Si will be mea-
sured in the oil. The increase in the density of the three
silicone oils (see Table 1) with the increase of sample vis-
cosity also indicates that the amounts of phenyl groups in
the samples follow the order of AP1000 > AS100 > AR20.
120
ICP-OES analysis. Therefore, the developed method can be
applied in quantification of Si in the studied silicone oils.
Besides that, from Fig. 3, it can be seen that all three sili-
cone oils have linear Si response curves in relation to their
concentration ranges from 1 to 40 ppm. This indicates that
Silicon

Table 4 Comparison of Si determination of silicone oils by emulsion ICP-OES and acid digestiona

Sample Aphenyl /Amethyl Concentration Si ICP-OES Si acid RSD (ICP-OES) RSD (acid digestion) Error (%)
(ppm) (wt%) digestion (wt%) (%) (%)

RSM 1066a 8:0 3.3529 14.747

6.8442 14.733
28.254 15.073 3.67 / 2.47
68.019 14.192
106.84 13.728
14.49 ± 0.53 14.14 ± 0.07 b
AR20 0.26:1 1.2814 29.252 32.32
2.4677 31.018 32.45
12.880 33.823 7.20 0.28 0.65
25.154 34.568
39.632 34.337
32.60 ± 2.35 32.39 ± 0.09
AS100 0.41:1 1.1600 28.168 35.66
2.4272 32.650 35.61
11.887 32.998 35.30 6.90 0.85 13.8c
25.076 29.194 35.16
39.621 29.672
30.50 ± 2.10 35.40 ± 0.30
AP1000 0.79:1 0.9634 25.287 25.00
1.8228 23.688 25.40
12.455 26.182 3.68 1.12 0.16
24.395 25.485
37.063 25.544
25.24 ± 0.93 25.20 ± 0.28
PDMS10 2.3088 34.954 34.58
13.339 33.726 34.86 1.71 0.58 0.40
26.154 34.994
39.534 34.664
34.58 ± 0.59 34.72 ± 0.20

a The italic data are the average mean values plus the standard deviations
b The value is given by NIST along with the received standard
c The ash obtained from acid digestion contains insoluble elements other than Si

if one has pure silicone oil, then the oil can be used to make 3.5 Stability of the Emulsions
the calibration curve, which can be further used to quantify
the amount of the same type of silicone oil in an unknown The stability of the Si spiked water standard solutions,
sample. Si spiked emulsion standard solutions, the series solutions
made from SRM 1066a, and the series solutions made from
the three phenyl groups containing silicone oils were studied
in this work. The samples had been stored at room tem-
Table 5 The limits of detection (LOD) of Si in water and emulsion
perature for 70 days and then analysed on ICP-OES again.
from ICP-OES analysis
Although no visible changes are observed in the solutions,
Standard solution LOD (ppm) it is found that both the Si spiked water and emulsion stan-
dard samples have increased Si signals after 70 days storage
Inorganic Si spiked in water solution 0.40
(see Fig. 5). The increased Si signals from both the water
Inorganic Si spiked in emulsion 0.17–0.52
and emulsion standard Si solutions are most probably due to
 Silicon

amount of phenyl groups gave increased Si signals after

PDMS10
70 days storage at room temperature. Furthermore, the other
two silicone oils AS100 and AP1000, as well as the SRM
1066a, had increased Si signals in the concentration range
between 1 and 7 ppm of silicone oils. The freshly made Si
AR2 spiked emulsion standards were used to make the calibration
curve and similar Si counts were obtained for the Si emul-
sion standards measured before storage (see Fig. 5). This
transmittance

AS100
excludes that the increased Si signals are due to the differ-
ent instrumental performance at different analyzing times.
The reason for the increased Si signals in the low viscosity
AP1000 AR10 and other silicone oils at low concentrations between
1 to 7 ppm is unknown at this moment.
Unlike the low concentration silicone samples, no sig-
nificant changes in the Si concentrations were found in the
samples made from SRM 1066a, AS100 and AP1000 in the
3900 3400 2900 2400 1900 1400 900 400 concentration range from 10 to 100 ppm after 70 days stor-
wavenumber (cm -1) age. This result shows that organic silicones that contain
higher amounts of phenyl groups have higher stability in
Fig. 4 FTIR spectra of PDMS10, AR20, AS100 and AP1000
the emulsion than those with more dimethyl groups and low
molecular weights.
the HF that was introduced from the inorganic Si stock solu-
tion, which etched the glass wall of the volume flask and
released some soluble Si compounds from the flask during
the storage. 160000
In addition, as seen in Fig. 6 and Table 6, all samples
made from AR20 with the lowest viscosity and the least
140000

250000
Si in water 0 day 120000
Si in water 70 days

Si in emulsion 0 day -1 100000

200000
Si in emulsion 70 days -1
Si counts

Si in emulsion 0 day -2
80000
SRM1066a 70 days
150000
AS100 70 days
Si counts

60000
AR10 70 days

AP1000 70 days
100000 40000
SRM1066a 0 day

AP1000 0 day
20000
AS100 0 day
50000
AR10 0 day
0
0 50 100 150
Silicone oil concentration (ppm)
0
0 5 10 15 20 Fig. 6 The changes of measured Si counts in the silicones after
Si concentration (ppm) 70 days storage at room temperature. Green triangle and green long
line: AR10 series; red square and red short line: AS100 series;
Fig. 5 The changes of measured Si counts of the Si standards in water blue plus and purple cross: AP1000 series; orange circle and blue
and emulsion after 70 days storage at room temperature parallelogram: SRM 1066a series
Silicon

Table 6 Comparison of measured Si after 70 days storage of emulsion system for the high molecular weight PDMS silicone oils
by ICP-OES dissolved in organic solvent.
Sample Concentration (ppm) Si (wt%)

0 day 70 days 4 Conclusions

RSM 1066a 3.3529 15.761 20.214
The emulsion ICP-OES method was developed for the quan-
6.8442 14.733 17.011
tification of Si in organic silicone oils that contain phenyl
28.254 15.073 14.407
groups. The emulsion contained silicone oil, MIBK, surfac-
68.019 14.192 13.903
tant Tween 80 and distilled water. A linear relationship of
106.84 13.728 13.514
Si signals response were found in the surfactant range from
AR20 1.2814 29.252 61.975
1.60 to 4 wt%, the MIBK concentration range between 0.4
2.4677 31.018 51.446
and 0.5 wt%, and the Si concentration range between 0.5
12.880 33.823 45.626 and 15 ppm. The MIBK (0.4 wt%) and the surfactant to
25.154 34.568 43.751 (MIBK + silicone oil) ratio of 5:1 were then used for all
39.632 34.337 42.163 sample preparations in this study. The total organic amount
AS100 1.1600 28.168 66.566 in the emulsion was 2.4 wt%.
2.4272 32.650 45.862 This method shows good precision and accuracy for the
11.887 32.998 35.393 SRM 1066a and three silicone oils with viscosities ranging
25.076 29.194 32.521 from 20 to 1000 mPa.s. The emulsion ICP-OES method has
39.621 29.672 28.703 low limits of detection down to 0.5 ppm Si in the emulsion,
AP1000 0.9634 25.287 74.764 which equals to about 200 ppm Si in the silicone MIBK
1.8228 23.688 48.350 solution.
12.455 26.182 26.999 The developed method can also be used for Si determi-
24.395 25.485 24.005 nation in PDMS oil with low viscosity (10 cSt). In addition,
37.063 25.544 25.080 the organic solvent can also be varied. This method could
be applied to quantify soluble organic silicone compounds
extracted from plastics, lubricants, composites, and envi-
ronmental samples as well as some biological samples,
3.6 Application of the Emulsion Method in Si that is, wherever a stable emulsion solution can be formed.
Determination in PDMS The organic extracts can be concentrated if the Si level
is out of the detection range of the developed method,
Since many silicone oils are polydimethylsiloxanes which makes the whole process more flexible and will
(PDMS), it is valuable to test the same emulsion approach not solely depend on the Si concentration in the original
for silicon determination in PDMS. Silicone oils made sample.
of PDMS with different viscosities were selected for the
emulsion preparation. The names and viscosities of the
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