Fresenius J Anal Chem (2000) 368 : 820–831
O R I G I N A L PA P E R
T. Mundry · P. Surmann · T. Schurreit
Surface characterization of polydimethylsiloxane
treated pharmaceutical glass containers
by X-ray-excited photo- and Auger electron spectroscopy
Received: 5 July 2000 / Revised: 25 August 2000 / Accepted: 31 August 2000
Abstract The siliconization of pharmaceutical glass con-
tainers is an industrially frequently applied procedure. It
is done by spreading an aqueous silicone oil emulsion
film on the inner surface and successive heat curing treat-
ment at temperatures above 300 °C for 10–30 min. It was
often proposed that a covalent bonding of PDMS to the
glass or branching of the linear PDMS occurs during heat
treatment. The present study was performed for a detailed
investigation of the glass and silicone (polydimethylsilox-
ane = PDMS) chemical state before and after heat-curing
treatment and analysis of the bond nature. Combined
X–ray excited photoelectron (XPS) and Auger electron
spectroscopy as well as angle resolved XPS-measure-
ments were used for analysis of the glass samples. The sil-
icon surface atoms of the borosilicate container glass were
transformed to a quartz-like compound whereas the for-
mer linear PDMS had a branched, two-dimensional struc-
ture after the heat curing treatment. It was concluded that
the branching indicates the formation of new siloxane
bonds to the glass surface via hydroxyl groups. Further
evidence for the presence of bonded PDMS at the glass
surface can be found in the valence band spectra of the sil-
iconized and untreated samples. However, this bond could
not be detected directly due to its very similar nature to
the siloxane bonds of the glass matrix and the organosili-
con backbone of PDMS. Due to the high variation of data
from the siliconized samples it was concluded, that the
silicone film is not homogeneous. Previously raised theo-
ries of reactions during heat-curing glass siliconization
are supported by the XPS data of this investigation. Yet,
the postulation of fixing or baking the silicone on the
glass surface is only partially true since the bonded layer
T. Mundry () · T. Schurreit
Schering AG, Pharmaceutical Development,
Department: Pharma Labor, Müllerstr. 174–178, 13342 Berlin
e-mail: tobias.mundry@schering.de
P. Surmann
Humboldt University Berlin, Institut of Pharmacy,
Goethestr. 54, 13086 Berlin
© Springer-Verlag 2000
is very thin and most of the silicone originally on the sur-
face after heat curing can be removed by suitable sol-
vents. This fraction can therefore still interact with drug
products being in contact to the siliconized container wall.
1 Introduction
The siliconization of pharmaceutical glass containers is
carried out to create lubricating films on the inner walls of
prefilled syringes or for a hydrophobic deactivation of the
glass wall for clear draining solutions, e.g. in injection
vials (assuring the deliverable volume of a container). This
siliconization is performed in a so called heat-curing pro-
cess in which medical grade silicone oils are applied in
form of aqueous emulsions and heat treated thereafter at
temperatures above 300 °C for about 10–30 min. These
medical grade silicone oils are chemically characterized as
trimethylsiloxy-endblocked polydimethylsiloxane (PDMS).
Aside from sterilization and depyrogenation the heat
treatment results in changes of the PDMS-original com-
position and a suggested bonding to the glass surface. The
curing process has often been designated in the literature
[1–6] as heat fixing, heat curing or baking in the assump-
tion that silicone oil is immobilized by the treatment.
However, it was never proved experimentally. This gave
the reason for a surface analytical X-ray photoelectron
spectroscopy (XPS) study to enlighten the bonding behav-
ior of PDMS under the conditions of a typical pharmaceu-
tical siliconization process to understand better the prop-
erties of the silicone after the treatment. It should be de-
termined to what extent the silicone is fixed by heat asso-
ciated reactions on the glass container surface. Conclu-
sions about the mobility or migration behavior in contact
with drug products should be drawn. There are early state-
ments in the literature about possible reactions between
glass and PDMS during heat curing siliconization [2, 7,
8]. However, in these studies surface analysis was per-
formed by contact angle measurements, and thus no de-
tailed information of the components molecular structure
could be derived.

Silica surfaces exhibit a complex reactivity due to
several surface functional groups. Mainly three different
silicon structures can be found. These are the geminal
and single silanol as well as the siloxane structure
which can be assigned as (–O)2Si(OH)2, (–O)3SiOH and
(O)3Si–O–Si(O)3, respectively. The geminal and single
silanol functions are considered to be the most reactive
centers, however controversy discussed as reported by
Miller et al. [23]. Single silanol groups are often stabilized
in form of vicinal OH-groups with intermolecular hydro-
gen bonds which appears to be an even more reactive con-
formation. Numerous studies have been published about
silica surface groups mostly using infrared spectroscopy
(IR) [9–17] and 29Si CP-MAS nuclear magnetic resonance
(NMR) spectroscopy [18–23] for analysis. More literature
references can be found in Miller et al. [23] (solid state
NMR) and Bush et al. [24] (IR). A key issue of silica sur-
face chemistry is the hydration and dehydration behavior
by physically and chemically adsorbed water and the tem-
perature dependence of these effects. The reactivity and
distribution of different silanol species on the surface is
affected by hydrothermal conditions and was often stud-
ied by chemical modification of the silanol groups
[11–17, 20–23]. Without chemical modification, silica
surfaces can be thermally modified as studied by NMR
[19] and XPS [25]. Rising the temperature up to 700 °C,
physically adsorbed water is removed and geminal or vic-
inal silanols are condensed and siloxane bonds newly
formed. These effects are reversible in contact with water
or during storage in ambient atmosphere.
Many authors used XPS and other surface sensitive
techniques for the analysis of silicones or silane coatings
on glass and silica materials [26–30] as well as PDMS
block and graft polymers [31–36]. Petersen et al. [37]
gives a current overview of the use of XPS for analyzing
silicon compounds. Further XPS studies have been per-
formed for analysis of PDMS-based mould separating
agents [38], textile PDMS fiber coatings [39], elastomeric
PDMS surfaces [40–43] and pure organosilicon com-
pounds [44, 45]. Organosilicon layers on inorganic silicon
substrates and siloxane polymers have also been investi-
gated by means of Auger electron spectroscopy (AES) us-
ing electron excitement [46–48]. Using X-ray excited
photo- and auger electron spectroscopy, Wagner devel-
oped the “chemical state” concept [49] to further charac-
terize very similar compounds by XPS. He worked out
large data sets for various elements [50, 51], e.g. for many
inorganic and organic silicon-oxygen compounds [52].
Bertoti, Toth et al. [53] applied the concept of the “chem-
ical state” to various Si–O and Al–O compounds.
2 Methods and materials
2.1 Sample preparation
Samples were prepared from two different types of glass contain-
ers: injection vials made of Schott tubing glass (FiolaxTM) with a
volume of 20 mL, both siliconized and non-siliconized, and glass
cartridge cylinders also made of Schott tubing glass (FiolaxTM)
821
with a volume of 100 ml, siliconized and non-siliconized. All sam-
ples were drawn from authentic production batches. Two commer-
cially available silicone oil emulsions were used for siliconization,
both containing 36% of trimethylsiloxy-endcapped PDMS and
2–4% of nonionic emulsifiers.
Baysilone oil emulsion-HTM was sprayed into the injection bot-
tles which were heat treated subsequently for 15 min at 320 °C in a
hot-air tunnel. The cartridge barrels were siliconized with Dow
Corning 365TM medical grade emulsion and subsequently treated
for 20 min at 320 °C in the hot-air tunnel. The emulsions were di-
luted to 2.5% (Baysilone) or 1.8% (Dow Corning) with water for
injections (WFI) before application. The basic silicone oils from
the emulsions (polydimethylsiloxane [–(CH3)2SiO]n, trimethyl-
siloxy endcapped) and a silicone resin (polymethylsilsesquioxane
[PMSSO = CH3SiO1/2]n) were taken for comparison, respectively.
The silicone oils (Baysilone MPHTM,100 cSt.; DC 360TM, 350 cSt.)
and the PMSSO were purchased from the Bayer-AG, Dow Corn-
ing and from ABCR-Gelest, respectively. The siliconized and un-
treated glass samples were cut to the appropriate size (1 × 1 cm)
needed for the XPS analysis and then heated for 3 h with refluxing
toluene. After filtering and rinsing several times with toluene, the
samples were subsequently dried at room temperature. A third se-
ries of samples was prepared by heating previously siliconized and
solvent extracted containers for 3 h at 600 °C in a muffle furnace.
50 µL of a solution of the silicone oil and resin (1 mg/mL in
hexane p.a.) were spread on a silicon wafer sputtered ahead of time
with gold. After evaporating the solvent, the remaining film was
analyzed. Another sample specimen was prepared similarly. Here,
a piece of a non siliconized glass vial bottom of a surface of 4 cm2
was doped with 10 µL of a solution of silicone oil (0.1 mg/mL in
hexane p.a.) and the solvent evaporated at room temperature
(monolayer preparation).
BorofloatTM flat glasses (produced by Schott-glass, same com-
position as DuranTM laboratory glassware) for angle resolved XPS
measurements were prepared in the following way: Samples of the
size of 1 × 1 cm were cut and siliconized by immersing them for
5 min in 2.5% Baysilone oil emulsion–H. After dripping off ex-
cessive emulsion they were cured at 330 °C for 20 min in a muffle
furnace. From these objects, unfixed silicone was removed by
treating them in refluxing toluene in the same way as the container
glass samples.
2.2 Instrumental parameters
Both spectrometers were calibrated including testing the linear-
ity of the energy scales according to standard draft 2 of
ISO/TC201/SC 7 N23 [54]. With respect to the small spot XPS
(SS-XPS) device the spectral resolution was FWHM = 0.9 eV for
Au 4f7/2 or FWHM = 0.84 eV for Ag 3d5/2. For the non-monochro-
matic XPS spectrometer resolution was FWHM = 1.0/1.1 eV
(Mg/Al) for Au 4f7/2 or FWHM = 1.1 (Al) eV for Ag 3d5/2. The an-
alyzer of the latter device was operated with a pass energy of
10 eV in the FAT mode (= fixed analyzer transmission) used for
line scans and a FRR (fixed retarding ratio) of 10 for survey spec-
tra and quantitative analysis.
The high resolution spectra were recorded in five (three) bind-
ing energy (BE) regions (data from SS-XPS in parentheses):
Region 1: BE: 85–120 (94–108) eV (Si 2p), region 2: BE: 145–
175 eV (Si 2s), region 3: BE: 280–310 (276–290) eV (C 1s), re-
gion 4: BE: 555–525 (522–556) eV (O 1s), and region 5: kinetic
energy (KE): 1585–1620 eV (Si KLL).
Static sample charging of the high-resolution and valence
band spectra was corrected for all samples with reference to the
C 1s signal for carbohydrates [55] at 284.6 eV. The element quan-
tification was done according to the model of homogeneous distri-
bution within the analyzed volume (analyzed area x analysis depth
≈ 10 nm). Quantitative calculations were based upon the element
specific photoionization cross-sections and mean free paths from
the literature [56]. All other instrumental parameters are listed in
Table 1.
822
Table 1 XPS analysis parameters
Parameter Small spot XPS Conventional XPS
Spectrometer SSX-100 ESCALAB 200-X
Manufacturer Surface Science Instruments, VG scientific,
East Grindsted, UK
Analyzer 180° hemispherical 180° hemispherical
(chaney type)
Dimension of ellipsoid: circle:
analyzed area 0.25 × 1.0 mm 3.0 mm
Sample fixing copper mask double-sided tape
Charge low energy none
compensation flood gun (1 eV)
Residual 5 × 10–8 mbar 10–8–10–9 mbar
pressure during
analysis
Pre-vacuum turbomolecular turbomolecular
pump
Main vacuum cryo ion getter
pump
Data interval 1.08 eV 0.50 eV
(survey) (0–1100 eV) (0–1200 eV)
Data interval 0.11 eV 0.10 eV
(high resolution)
Software X-probe, V. 8.62D, Scienta ESCA 300,
release for HP V. 1.66
Excitation monochromatic: non-monochromatic
Al-Kα (1486.6 eV) Al-Kα (1486.6 eV)
Mg-Kα (1253.6 eV)
X-ray operation 200 W 300 W
power
Acceleration 10 kV 15 kV
voltage
Curve fitting 80% Gauss Voigt + variable
model 20% Lorentz Gauss/Lorentz

Fig. 1 XPS/AES survey spectra of glass and polysiloxane samples

a) non-siliconized glass; b) siliconized glass; c) siliconized glass,
3 Results and discussion 600 °C treated; d) PDMS; e) PMSSO; *recorded with non-mono-
chromatic X-ray excitement
Generally, data from the monochromatic SS-XPS and
non-monochromatic XPS are displayed in the same fig- Table 2 Quantitative elemental composition of glass samples and
ures and tables. Non-monochromatic data are marked in polysiloxanes [atom %]
figures and captions.
Sample O Si C Na B N Al Ca
Untreated glass 43.1 16.0 30.0 2.1 2.8 2.2 3.0 0.9
3.1 Elemental composition Siliconized glass 28.4 20.3 48.0 0.4 n.d n.d 2.8 n.d
Siliconized glass, 43.4 19.6 30.1 1.3 2.5 1.4 1.4 0.4
Figure 1 shows representative survey spectra of each sam- 600 °C
ple type (spectrum from cold siliconized glass not PDMS 27.4 21.3 51.3 – – – – –
shown). This cold silicone layer on glass was prepared in aPMSSO 48.0 23.3 28.8 – – – – –
bGlass experim.
order to get a sample for comparison with the heat cured 63.1 26.9 – 3.5 4.2 3.1 0.6 –
cBulk glass
type. Here, the survey spectra were only used to verify 52.0 35.0 – 5.2 3.2 – 2.6 1.0
that the silicone film is thin enough for analysis in that a data from non-monochromatic XPS; b without C and N; c nominal
both typical signals from glass and silicone were de- bulk composition of glass type FiolaxTM, (n.d.: not detected)
tectable. Note that the samples a) and b) were measured
with Mg–Kα excitation, c), d) and e), however, with
Al–Kα radiation. This leads to the Auger transitions Al were found, typical for the borosilicate glass used. The
(CKL1, OKL1) appearing in the spectrum with apparently peaks of the trace elements Ba and K were also identified
different binding energies. in individual cases (not shown). In the spectrum of the sil-
The elemental composition of the four investigated iconized sample (Fig. 1 b) we also found a very slight con-
samples is shown in Table 2. In the spectrum of the un- tribution from typical glass elements, in particular alu-
treated glass (Fig. 1 a), the elements Si, O, Na, B, Ca and minium, sodium and boron (B not shown). Noticeable
 823

was a significantly higher carbon content of the sili- Table 3 Relative atomic numbers of Si, O, and C and interatomic
conized sample increasing the C/O ratio. The siliconized ratios (RSD in % in parentheses)
sample which was extracted and afterwards treated at Sample composition (Si/C/O)
600 °C had a composition close to the untreated one
(Fig. 1 c). Apart from the elements typical for the borosil- Atomic number Ratio
icate glass, we detected large amounts of carbon and
Sample type Si C O C/Si Si/O C/O
1–2% nitrogen in the surface layer of the non-siliconized
and the secondary heated sample. These are probably or- Untreated glass 0.63 1.29 1.65 2.06 0.38 0.79
ganic impurities from the sample preparation (solvent ex- (12.2) (16.5) (9.2)
traction and heat treatment in air) and the layer of adven- Siliconized glass 0.94 1.70 1.23 1.80 0.76 1.37
(10.2) (9.5) (6.0)
titious C. It is possible to remove the carbon peak by sput-
Siliconized glass, 0.80 0.98 1.88 1.21 0.43 0.52
tering, however there might occur uncontrolled changes 600 °C treated (4.9) (42.3) (12.4)
in the surface chemical bonds on the surface as Rothaar et PDMS 1.06 1.90 0.96 1.87 1.10 2.06
al. [57] showed on borosilicate glass surfaces and Barr (silicone oil) (0.4) (0.6) (1.8)
[58] on SiO2/Al2O3 materials. Therefore, we did not un- aPMSSO 0.93 1.15 1.92 1.24 0.48 0.60
dertake any sputter attempts to remove the carbon layer. (silicone resin) (0.2) (0.0) (0.2)
bBulk glass
The percentage elemental composition of PDMS (Fig. 1 d) – – – – 0.67 –
agreed to values specified in the literature [59]. a data from non-monochromatic XPS, b nominal value from
It is obvious that the spectrum of the siliconized sam- FiolaxTM glass
ple is something like a mixed spectrum of glass and sili-
cone oil. The reoccurrence of the trace element peaks
from the glass after heating the siliconized sample at
600 °C proves that an uncoated glass surface similar to the this treatment were not reproducible with respect to the
initial state is restored by pyrolysis of the organic layer. C fraction. However, this sample better represents the
In Table 2, additional data are given for the theoretical conditions of a pure glass surface that theoretically does
bulk composition of the glass and the experimental com- not contain carbon at all and is somewhat “cleaner” than
position calculated from the analysis data without carbon the starting materials.
and nitrogen values. It can be seen that the glass surface The oxygen fraction decreases through the surface
has a significantly higher oxygen and lower silicon frac- modification by PDMS and increases again after the sec-
tion compared to the theoretical values. The other ele- ond heating at 600 °C. An explanation for the latter obser-
ments were detected with lower contents. The higher oxy- vation can be the fact that the fraction of oxidized com-
gen fraction can be related to a higher number of free hy- pounds in the adhering carbon layer is increased by the
droxyl functions at the surface compared to the bulk ma- heat treatment (Fig. 2 c). Another rationale may be the for-
terial. However, it has to be considered that within this mation of more free silanol groups on the glass surface af-
value the oxygen from oxidized carbon compounds is also ter annealing in air and rehydration in ambient atmo-
contained which cannot be subtracted for this calculation. sphere. Generally, the siliconized sample exhibited an in-
termediate state between the untreated glass and pure
PDMS.
3.1.1 Elemental ratios of Si, O and C

We calculated the relative atomic numbers and inter-
atomic ratios of silicon, oxygen and carbon (Table 3)
to observe the change of the glass surface composition af-
ter various treatments. For PDMS (Fig. 1 d) and PMSSO
(Fig. 1 e) the O : Si : C ratios are 0.96 : 1.06 : 1.90 (1 : 1 : 2)
and 1.7 : 0.82 : 0.98 (1.5 : 1 : 1), respectively (theoretical
values [59] in parentheses). In comparison with the exper-
imental data of the Si/O ratio of 0.38 (Table 3) the ratio of
the theoretical composition calculates to 0.67. Silicon as
well as the other elements has therefore a decreased frac-
tion at the surface.
The relative proportion of Si increases by approxi-
mately 50% through the heat curing treatment. After heat-
ing, it drops to a level that is still higher than the initial
value. There is also a rise of the carbon fraction after the
siliconization, but a drop to lower values than in the initial
state after the second heat treatment. This is due to the py-
rolysis of organic substance at 600 °C. The high relative
standard deviation (RSD) shows that the reactions during
3.2 High-resolution spectra of Si 2p, Si KLL, O 1s,
O KLL and C 1s
3.2.1 Peak shape and maxima
First, the relative positions of the Si, C and O lines were
determined by calculating the binding energy (BE) differ-
ence (Table 4). These differences underlie changes of up
to 1 eV, characteristic for each sample specimen as a re-
sult of chemical shift. However, for an accurate compari-
son and fit analysis all of the spectra had to be referenced
to one fixed peak which was done with respect to the C 1s
hydrocarbon signal. The value established in the literature
most frequently for the adventitious C 1s signal is 284.6
eV although the method of BE referencing continues to be
discussed controversially. Swift presents the advantages
and disadvantages of the C 1s reference method in his
critical review [60]. After charge referencing, the maxi-
mum of each peak was determined (Table 5). The aver-
824
Table 4 Binding energy – difference between Si, O and C photo- resolution spectra. Generally, we observed only a slight
lines chemical shift of the peak maxima within 0.5 and 1.0 eV.
BE difference The values for the polymer samples PDMS and PMSSO
agree with the values given by Wagner [52] for the com-
Sample type O 1s–Si 2p C 1s–Si 2p O 1s–C 1s pounds he assigned as polydimethylsilicone and methyl-
Untreated glass 429.39 182.13 247.26 silicone resin, respectively. When at least two components
Siliconized glass 430.06 182.32 247.74 overlapped, the bands were asymmetrical [Si 2p: b)+d); Si
Siliconized glass, 429.35 181.77 247.59 KLL: b); O 1s: c); C 1s: a-d)+f) or broadened (O 1s: a)].
600 °C treated
Glass + cold silicone layer 430.10 182.53 247.58
PDMS (silicone oil) 430.39 182.77 247.62 3.2.2 Multiple-component curve fitting
aPMSSO (silicone resin) 429.67 181.82 247.85
a data from non-monochromatic XPS The fitted spectra of all photoelectron and Auger lines are
displayed by Fig. 2. Table 6 and Table 7 show the binding
Table 5 Peak maxima of Si, O, C photo- and Auger lines (aver- and kinetic energy data and the modified Auger parameter
age, n = 2) for Si, calculated according to the relationship: α′ = BE
(photoelectron) + KE (Auger electron).
BE (photolines) and KE (Auger lines) in [eV]

Sample type Si 2p O 1s C 1s *Si KLL *O KLL 3.2.2.1 Si 2p/SiKL23 L23 spectra. The Si 2p line is subject
Untreated glass 102.47 531.86 284.60 1609.20 508.15
to a spin orbital split (Si 2p3/2 and Si 2p1/2). We decided
Siliconized glass 102.28 532.34 284.60 1608.55 507.25
not to display the splitting for a clearer illustration. The
Siliconized glass, 102.83 532.18 284.60 – – analysis of the symmetrical Si 2p peak of the untreated
600 °C treated glass surfaces (Fig. 2 a) yields one component with BE =
Glass + cold 101.87 532.17 284.60 – – 102.5 eV (FWHM: 1.8; chi-square: 1.39–2.35). Hence,
silicone layer there were only silicon atoms in a similar chemical state.
PDMS 101.83 532.22 284.60 1609.68 507.75 It was possible to fit two components in the asymmetrical
aPMSSO 102.78 532.45 284.60 1608.75 507.50 Si 2p and Si KLL signal from the siliconized glass surface
a data from non-monochromatic XPS
(Fig. 2 b). Since the curve fit information from these two
silicon lines is generally the same, the discussion here is
based only on the Si 2p signal. We found a major compo-
ages from 4 determinations are given for all of the glass nent at 102.2 eV and a minor component at 103.3 eV (chi-
samples, respectively (PDMS/PMSSO: n = 2, mixed sam- square: 1.53–2.27). These components have an approxi-
ple: n = 3). Figure 2 shows all of the corresponding high- mate ratio of 1 : 3. The major component at 102.2 eV

Table 6 Results of the curve fitting calculations: binding energy in eV; standard deviation in (eV); fraction in [%]
Photoline Si 2p O 1s C 1s

Sample type Si 2p2 Si 2p1 O 1s2 O 1s1 C 1s4 C 1s3 C 1s2 C 1s1
Untreated glass 102.47 – 532.20 531.15 288.39 287.12 285.92 284.60
(0.04) (0.09) (0.14) (0.27) (0.26) (0.18) (0.00)
[100.0] [60.0] [40.0] [6.4] [7.2] [16.8] [69.6]
Siliconized glass 103.32 102.19 532.31 – 288.22 287.11 285.61 284.60
(0.05) (0.04) (0.06) (0.22) (0.10) (0.28) (0.00)
[26.3] [73.7] [100.0] [5.7] [6.9] [6.6] [80.8]
Siliconized glass, 102.74 – 532.18 531.16 288.39 287.36 285.88 284.60
600 °C tempered (0.17) (0.08) (0.33) (0.08) (0.07) (0.06) (0.00)
[100.0] [20.5] [79.5] [9.5] [12.1] [16.3] [62.1]
Glass + cold 102.78 101.97 532.15 – 288.65 287.58 285.83 284.60
PDMS layer (0.11) (0.01) (0.08) (0.42) (0.10) ] (0.33) (0.00)
[71.7] [28.3] [100.0] [2.0] [0.7 [3.6] [93.7]
PDMS – 101.81 532.17 – – – – 284.60
(0.04) (0.04) (0.00)
[100.0] [100.0] [100.0]
aPMSSO 102.58 – 532.47 – – – 285.87 284.60
(0.06) (0.00) (0.05) (0.00)
[100.0] [100.0] [9.7] [90.2]
a data from non-monochromatic XPS
 825
Table 7 Fit results for silicon and oxygen Auger species in eV: cone oil. We received a BE difference of 1.1 eV that could
(average, n = 2); fraction in [%] be extraordinarily well reproduced (SD = 0.04–0.05 eV).
BE/KE O KLL O1s + Si KLL Si 2p3/2 + KLL In contrast, 0.7 eV between silicone oil and glass or
KLL 0.8 eV were measured with the cold silicone sample. This
Component 1 α′ 1 2 α′ 1 α′ 2 reflects a change related to their initial state. The increase
Untreated 508.34 1040.4 1609.2 – 1711.6 – in the BE of the organic component by approximately
glass [100.0] [100.0] 0.4 eV in comparison to pure PDMS could indicate that a
Siliconized 507.71 1040.3 1609.2 1608.3 1711.5 1711.6 bond was formed to the silanol (Si–OH) functions of the
glass [100.0] [65.1] [34.3] glass surface as was previously postulated [7]. The forma-
PDMS 507.86 1040.2 1609.1 – 1711.8 – tion of tri-functional (T-) siloxane units in the PDMS
[100.0] [100.0] chains (=R–Si–O3) would explain a chemical shift to-
PMSSO 507.69 1040.2 1608.8 – 1711.4 – wards higher BE values. Since this reaction is considered
[100.0] [100.0]
to occur only with a low fraction of the dimethylsiloxane
α′ = modified Auger parameter (D-) units (=R2–Si–O2) and the chemical shift between
D- and T-siloxane groups is small, a new T-siloxane com-
pound could not be discriminated in a three-component fit
shows a lower oxygen coordination (=Si(O)1–2) whereas analysis.
the component at 103.3 eV shows a higher one (=Si(O)3–4).
Thus, the two components may be assigned to a more
glassy, organic and a more inorganic, silica-like state. Fig. 2 High resolution curve fitted photo- and Auger electron lines
a) non-siliconized glass; b) siliconized glass; c) siliconized glass,
The location of the BE peaks of the fitted curves in the 600 °C treated; d) cold silicone on glass; e) silicone oil (PDMS); f)
spectrum of the siliconized sample was significantly dif- silicone resin (PMSSO); *recorded with non-monochromatic X-ray
ferent from that of the pure components of glass and sili- excitement
826
The ‘inorganic’ peak component from the glass has
also been shifted to higher values (+0.8 eV). It now has
the character of a silicon dioxide [50]. Apparently, the sil-
icon surface atoms of the glass were chemically trans-
formed to a significant extent by siliconization. Since a
further oxidation is not possible due to the state of silicon
in glasses of this type we assume a change from the glassy
to a more crystalline or silica-like chemical state. Accord-
ing to Miller and Linton [25], the Si BE would have to
shift to lower values as a result of silanol reaction or con-
densation. However, it is questionable whether it is gener-
ally possible to observe this effect by XPS because of the
difficult discrimination of silanol/siloxane bonds using
the Si 2p line.
After the second heating of the siliconized glass sur-
faces at 600 °C (Fig. 2 c), the organic component disap-
peared. The analysis exhibited one component at BE =
102.7 eV with a FWHM of 1.9 (chi-square: 1.55–2.52).
The fit analysis of the silicon line of PDMS and PMSSO
yielded one component, too (FWHM: 1.35/1.75; chi-
square 1.26–1.41).
The asymmetrical Si peak of the cold PDMS layer on
glass can be divided into two components whose ratio
varies as a result of the preparation (Fig. 2 e). These sig-
nals at BE = 101.97 eV and BE = 102.78 eV correspond to
the pure silicone oil and the glass (FWHM: 1.28/1.40; chi-
square: 2.1) revealing that in contrast a reaction between
both components was not affected during cold siliconiza-
tion of the glass surface.
3.2.2.2 O 1s/O KLL spectra. The fit analysis of the asym-
metrical signal of the untreated glass surface (Fig. 2 a)
showed the presence of two oxygen components. One
major compound at BE = 532.2 eV and one with a
smaller proportion at BE = 531.2 eV. These components
have an approximate ratio of 3:2. It is difficult to inter-
pret this finding. The assumption that they are the signals
of the siloxane (Si–O–Si) and silanol (Si–OH) oxygen is
questioned by the contrary discussion in the literature.
Although their discrimination is considered to be diffi-
cult in most cases (e.g. Gross et al. [61]), some authors
[25] do multiple-component analysis, e.g. with silica ma-
terials [62]. The silanol component is usually determined
at approximately 533.2 eV [25, 63]. Therefore, this the-
ory offers no plausible explanation. Relating the minor-
ity component to the oxidized carbon compounds is also
restricted because of their similarity to the siloxanes. To
us it seemed most reasonable to assign the second O 1s
component with low BE to the bonds of the metal oxides
from the glass, such as Al2O3+NaO or heterosiloxane
bonds like Si–O–Al. This was supported by various data
from the literature, e.g. Sprenger and Anderson [64]
(Si/Al ceramics: Al–O–Al at 531.6 eV), Barr [58] (SiO2
catalysts; shoulder at 531 eV related to metal oxides),
Merlen et al. [63] (Si/Al oxides (zeolites); Si–O–Al at
531.2 eV) and Wagner [52]. No Auger parameter was
calculated for this component because it is only of low
interest for the silicone coating and therefore negligible
in this study.
The O1s curve fitting of the siliconized glass sample
(Fig. 2 b) yielded a singlet at 532.3 eV (FWHM = 1.55; chi-
square: 2.11–2.93). The O 1s photoline is probably domi-
nated by the siloxane component (Si–O–Si) of the ad-
sorbed PDMS with this sample. Although we may assume
that there was additional information from the glass ma-
trix in this line, it was not possible to distinguish the or-
ganic and inorganic component by XPS since the binding
state, also Si–O–Si in glass, is almost identical. This com-
plies with Wagner’s data [52], too. He gave almost the
same values for soda glass and “polydimethylsilicone”
(difference: 0.05 eV).
The BE is also very close to the value given by other
authors for PDMS [59]. It is no longer possible to resolve
the metal oxide component from the spectrum dominated
by the organic layer since its contribution is too low.
The siliconized and secondary heated sample (Fig. 2 c)
yielded the same two-component result (chi-square 2.13–
2.25) as the untreated. Their ratio has changed in favor
of the major component to approximately 4:1. The fit
analysis of the O 1 s line with pure PDMS and PMSSO
(Fig. 2 e + f) supplied a symmetrical component as ex-
pected (FWHM: 1.35/1.73; chi-square: 1.26–1.41). The
corresponding BE peaks of 532.2 eV agreed with the val-
ues stated by Wagner [52]. In the high-resolution spec-
trum of the PDMS/glass mixed sample (Fig. 2 e), only one
symmetrical line was found (BE = 532.15; FWHM =
1.33; chi-square = 1.95). We suggest that the heat curing
glass siliconization does not have an effect on the binding
state of oxygen in both materials, since no chemical shift
was detected. The line difference of approximately 0.1 eV
was within the usual measuring uncertainty.
The O KLL line is rather complex consisting of four
overlapping transitions. No curve fitting was performed
here and the modified Auger parameter was calculated us-
ing the strongest component at about 508 eV. The shape of
the O KLL line (Fig. 2) is almost identical with the poly-
mer samples and the siliconized glass. The pronounced
shoulder at the lower KE side represents a typical O KLL
feature observed at uncharged siloxane bonds according
to [52]. A slight difference can be recognized at the un-
treated glass sample. Here, the missing shoulder shows a
more polar character of the oxygen bond, e.g. in silicates
or aluminium oxides.
3.2.2.3 C 1s spectra. With all of the samples, a decompo-
sition of the C1s line into four components was tried (Fig.
2). The following data were calculated for chi-square: un-
treated glasses (1.67–2.12), siliconized glasses (1.35–
1.96), siliconized, secondary heated glass surface (1.67–
2.17), PDMS (2.24–2.56), PMSSO (1.95–2.18) and cold
PDMS layer on glass 1.72–2.43.
Among the glass spectra, there were peaks at approxi-
mately 285.6, 287.1 and 288.2 eV (± 0.2 eV respectively)
beside the main component at 284.6 eV. These com-
pounds represent single or multiple oxidation states of
carbon and may be assigned to the general structures
R3C–OH, R2C=O, and R1COOR2 [65]. They probably
originate from the sample preparation (solvents/stoppers).

Concerning the non-siliconized glasses (Fig. 2 a), the aver-
age contribution of these components is 30% of the entire
carbohydrate fraction. Singly oxidized compounds pre-
dominate. The proportion of the oxidized compounds was
considerably decreased after siliconization (Fig. 2 b) to ap-
proximately 12% affected by the silicone surface layer
whose methyl groups make a crucial contribution to the
signal.
The oxidized carbon fraction has increased signifi-
cantly again to approximately 40% after the 2nd heat
treatment at 600 °C (Fig. 2 c). The silicone layer adsorbed
on the glass was burned off as a result of annealing in an
oxygen containing atmosphere. A carbon containing
residue, free of Si (SiO2 was not detected) was left.
As expected, it was possible to fit one component into
the PDMS spectrum (Fig. 2 e) (FWHM: 1.3; chi-square:
2.24–2.56). A higher oxidized component was identified
in the C 1s line of the silicone resin (Fig. 2 f), although the
resin only contains CHx atoms. This may possibly be an
impurity in the sample substance. Apart from the domi-
nant CHx signal, we also found oxidized C-species in the
spectrum of the cold silicone sample. They can be traced
back to carbon contamination of the glass surface below
the silicone oil similar to the untreated sample (Fig. 2 d).
Since the carbon fraction is not considered to contribute to
the reaction between glass and silicone oil, we did not de-
termine an Auger parameter using the C KLL line. A sin-
glet is detected in the C 1s line of the PDMS sample.
3.3 Valence band spectra
The valence band spectra of all types of samples (except
PMSSO) are displayed in Fig. 3. Especially noticeable are
the two relatively symmetrical bands at approximately 26
and 17 eV in the spectrum of PDMS. Ferenczy et al. [44]
assigned them to the O 2s and the C 2s orbital. In the
spectrum of PDMS (Fig. 3 b) two weaker and broader
bands at approximately 13–14 eV and 8–9 eV are de-
tected. According to Ferenczy [44], these bands originate
from Si–O bonds and oxygen lone pairs. Generally, the
Fig. 3 Valence band spectra of glass samples and PDMS a) cold
silicone layer on glass; b) PDMS; c) siliconized glass; d) sili-
conized glass, 600 °C treated; e) untreated glass
827
valence band structure of the two silicone oils investi-
gated here was in accordance with spectra from other au-
thors [44, 59].
The untreated glass sample (Fig. 3 e) differs from that
significantly. The O 2s line is just as pronounced as in the
spectrum of PDMS. The C 2s structure at BE = 17 eV is
missing. The clear band at approximately 13 eV is not vis-
ible here. Instead, there is a very broad, poorly resolved
band between 10 and 16 eV. The spectrum of the sili-
conized sample (Fig. 3 c) is very similar to the spectrum of
PDMS. The bands are clearly distinguished at 17 eV
(C 2s) and at 13–14 eV (Si-O). The intensity of the C 2s
structure is weaker compared to the pure PDMS. The
structure in the range between 10 and 12 eV is deformed
in relation to PDMS and resembles more the correspond-
ing range in the glass spectra (Fig. 3 d + e). There is also a
high similarity with the spectrum of PMSSO which was
available in the literature [44]. The structures typical for
PDMS could not be recognized anymore after the second
thermal treatment (Fig. 3 d). The sample with the cold sil-
icone layer (Fig. 3 a) showed all typical structures of the
PDMS spectrum. From the high structural similarity of
the siliconized glass and PDMS spectra (especially the ap-
pearance of the C 2s band and its disappearance after high-
temperature treatment) we may conclude that the ab-
sorbed layer is in an intermediate state between PDMS
and PMSSO. Since it is not possible to see differences be-
tween the cold or heat curing siliconized sample, the va-
lence band spectra yield no indication of new bonds being
formed between the glass surface and PDMS. This might,
however, be due to the similar nature of the suggested
newly formed Si–O bonds compared to the siloxane
bonds of the glass and PDMS itself.
3.4 Chemical state analysis
Figure 4 illustrates the combined binding and kinetic en-
ergies of the silicon photo- and Auger signals graphically
Fig. 4 Silicon chemical state plot (error bars = SDV, N = 2);
empty square: siliconized glass, organic compound; filled square:
siliconized glass, inorganic compound; triangle: PMSSO; filled
circle: PDMS; rhombus: untreated glass
828
(all data from non-monochromatic XPS). All of the modi-
fied Auger parameters were found in a narrow band of
(diagonal) between 1711.0 and 1712.0 eV. Three regions
of data were received. In the upper right area the less oxi-
dized PDMS is recognized. In the lower left region of the
plot with BE 103.3 eV, the filled square shows the state of
the uppermost glass layer after heat curing glass sili-
conization. In this area of the plot, SiO2 or quartz glass
compounds are usually located. Between these two ex-
posed states, there is a region with three data points near
to each other. One of these is the branched silicone with
an oxygen co-ordination of SiO3/2. There are two further
species, one of which shows the initial silicon state of the
glass surface (rhombus). This borosilicate material con-
sists predominantly of amorphous glass with silicate in-
clusions. The data point on the right of it (unfilled square)
represents the state of the former silicone oil after
heat curing glass siliconization. Data points in this range
are typical for the SiOx compounds and also silicates
(=MexSiO3). Both components have significantly shifted
from their original state. The advance of the organic
PDMS component value into the SiOx region makes it
fairly probable that there is a direct bond formation to the
glass surface. Therefore, the polymer molecule has
changed into a state that resembles the silicone resin and
is also very similar to the glassy silicon state of the un-
treated surface. Since we did not detect silicon atoms in
the initial state, we may assume that a great percentage of
the Si atoms of PDMS have been converted. In general,
the surface of the siliconized samples may be described as
a carbon contaminated SiOx layer.
The proximity to the state of the former glass matrix
shows that there is something like a transition state be-
tween silicone and a structure similar to a silicate. Since
the two potential layers (SiOx /carbon and silicone resin)
are similar with reference to their carbon, oxygen and sil-
icon content as well as to their BE data, XPS cannot dis-
criminate unambiguously between them. In comparison
to Wagner’s data [52], the quartz glass and the silicon
T-resin state were determined almost identically. The
Fig. 5 Oxygen chemical state plot for Si-O compounds (error bars
= SDV, N = 2); square: siliconized glass, both compounds; circle:
PDMS; triangle: PMSSO; rhombus: untreated glass
borosilicate glass used here differs from the soda glass in
Wagner’s Si–O plot with respect to α’. The low propor-
tion of sodium apparently leads to an electronically differ-
ent Si environment. As discussed before it also leads to a
differently shaped oxygen KLL peak. The data for the un-
treated PDMS differ from those of Wagner [52] as well as
Bertoti’s [53] data. They found values of {102.4/1609.1}
eV and {102.2/1609.58} eV for PDMS and a compound
named dimethylsilicone polymer, respectively. This poly-
mer was not further characterized. With Bertoti, it corre-
sponded to the formula –[OSi(CH3)2]n–, i.e., a cyclic
PDMS. One has to be aware of the fact that the term poly-
dimethylsiloxane in the literature is used both for silicone
oil and for crosslinked, (e.g. vinyl-) siloxane elastomers
although they are chemically different and therefore give
probably also different values by XPS analysis.
In the illustration of the oxygen chemical state
plot (Fig. 5), the differences are not strongly pronounced.
Only a weak effect can be observed between the SiO2
bonds (BE 532.6 eV) and the SiOx bonds (between 532.0
and 532.5 eV). All were found within a narrow Auger pa-
rameter band between 1040.0 and 1039.0 eV. However, a
great number of compounds of this type can be found
here. The decomposition of the O 1s or O KLL line of sil-
iconized glass into two components as with the Si lines
was not possible with oxygen. Thus, in the oxygen chem-
ical state plot, both partners of the new compound could
not be discriminated. Since oxygen is localized in silox-
ane bonds on both sides of the new network, this is not
surprising. Nevertheless, we can see a slight shift of the
oxygen BE from the untreated to the siliconized glass
sample although the Auger parameter almost remains the
same. The binding state of the glass-silicone interface is
apparently strongly dominated by the quartz glass compo-
nent.
3.5 Angle resolved XPS-analysis
PDMS copolymers [34, 36] and oxide layers on metal and
PDMS solids [66, 41] have been previously investigated
using angle resolved XPS (AR-XPS) detecting photoelec-
trons under different take off angles (TOA). The objective
of our model AR-XPS analysis was to gain depth infor-
mation from the coated glass samples which was not pos-
Table 8 Angle dependent atomic ratios of Si, O and C from sili-
conized BorofloatTM glass; RSD in (%); all data from non-mono-
chromatic XPS
Sample ΣC/ΣSi ΣO/ΣSi SiO2/ΣSi
Survey spectrum (20 °C) 0.81 (2.64) 2.64 (0.54) 0.42 (3.37)
Region Si 2s, O 1s 0.77 (0.00) 2.61 (2.44) 0.43 (4.99)
and C1s (20 °)
Region Si 2s, O 1s 0.97 (0.73) 2.50 (3.39) 0.43 (8.32)
and C1s (40 °)
Region Si 2s, O 1s 1.47 (9.62) 2.24 (3.47) 0.40 (100.0)
and C1s (60 °)
 829

alyzed in this case, too. Therefore, the calculated O/Si-ra-

tio is determined too high while the actual oxygen co-or-
dination is probably lower. However, from the location of
the values in the silicon chemical state plot (Fig. 4), an
oxygen co-ordination of 1.2–1.4. can be estimated that
corresponds to an intermediate state between silicone oil
(Si : O = 2/2) and silicone resin (Si : O = 3/2).
Two selected photolines of silicon (Si 2 s) and oxygen
(O 1 s) were curve fitted after recording their spectra (Fig. 6)
at different take off angles (results: Table 9). None of the
percentage fractions showed a tendency that could be cor-
related to the TOA of the sample. From these data the ratio
of the oxidized Si component to the total amount of Si was
calculated after curve fitting (SiO2/ΣSi in Table 8). It
hardly showed a measurable angular dependency, the indi-
vidual samples, however, yielded very different results. The
Si spectrum of a selected sample (Fig. 6, left), however,
Fig. 6 Angle-resolved, curve fitted Si 2 s and O 1 s region of a sil-
showed an angular correlation. Here, the intensity of the
icone coated flat glass oxidized Si glass component decreases with an increasing
TOA. A reason for the poor reproducibility could be the
Table 9 Fit results of Si and O components on siliconized flat heterogeneous nature of the silicone coating. A further rea-
glasses at different take off angle. (Binding energy (BE) in eV; son might be the thickness of the layer of the silicone film
fraction in [%] being unevenly distributed. There was generally no angular
Element O 1s Si 2s
effect visible in the O 1s spectra with respect to the metal
oxide component of the glass, although the fraction is not
Component O 1s/1 O1s/2 Si 2s/2 Si 2s/1 equal in the different spectra. Here as well, the reason is
presumably the heterogeneous nature of the silicone layer.
Survey (20°) 532.6 530.8 154.6 153.8
[95.6] [4.4] [43.2] [56.8]
Line scan (20°) 532.5 530.7 154.5 153.7
[96.0] [4.0] [41.3] [58.7] 4 Conclusion
Line scan (40°) 532.5 530.7 154.5 153.7
[96.4] [3.6] [42.4] [52.6] Purpose of the presented study was to provide a more de-
Line scan (60°) 532.4 530.6 154.3 153.5 tailed description of pharmaceutical glass container sur-
[93.9] [6.1] [39.6] [60.4] faces after a heat curing siliconization treatment.
Mean 532.5 530.7 154.5 153.7 According to the chemical state analysis, an oxidized
SDV 0.07 0.07 0.12 0.12 compound (intermediate state between SiO2 and PDMS)
has developed from the silicone oil that shows similarities
to a PMSSO polymer as well as to the glass surface in its
sible with the strongly bent glasses from the original sili- initial state. A change of the glass surface layer from its
conized containers. Since the sample material Schott- typical state (SiOx) to a substance comparable to silica gel
FiolaxTM was not available in flat specimen, we prepared or SiO2 is indicated by the data, too. These two results re-
samples from another borosilicate glass (BorofloatTM, cor- flect a covalent bond formation of some Si atoms of the
responding to Schott-DuranTM). glass surface with the silicone, thereby both changing
Survey spectra at 20° TOA and high-resolution spectra their chemical state. Additionally, the valence band analy-
of the Si 2p, Si 2s and O 1s regions at 20°, 40° and 60° TOA sis supported the conclusion of an adsorbed silicone layer
line were recorded. Atomic ratios were calculated from the with mixed properties of PDMS and PMSSO. The bond-
XPS data and listed in Table 8. The main elements are not ing is considered to be realized by crosslinking of the
homogeneously distributed within the analyzed surface PDMS to the silanol groups of the glass surface. Regret-
depth. The C/Si ratio increases with rising TOA. The O/Si tably, silanol condensation could not be determined by
ratio decreases correspondingly because the silicone coat- XPS since it is difficult to resolve Si-OH states in Si 2p
ing has a lower oxygen content in relation to the SiO2-like and O 1s spectra. Because PDMS is a highly thermostable
glass surface. We also used the O/Si ratios of the silicone and inert polymer the bond formation is surprising. There-
polymers PDMS (1.29) and PMSSO (2.07) for compari- fore, we assume specific reasons for the activation of the
son (reciprocal values of Si/O data in Table 3). It was im- coupling reaction. During heat curing, a hydrothermal en-
possible to estimate the oxygen co-ordination of the iso- vironment is created by the silicone oil emulsion (contain-
lated organic layer from this data, because one cannot ing more than 95% water) heated on the glass surface. By
state whether the analysis data were only derived from the rehydration, this leads to an increased silanol activity. We
coating even during the 60° experiment. We should rather also suggested that the stability of the silicone is de-
assume the higher oxidized glass layer below has been an- creased by present traces of excipients like emulsifiers
830
and preservatives. As a result the PDMS can be easier hy-
drolyzed, and thus be activated for the bond formation.
Aside from the pyrolysis of PDMS at 600 °C, a thermal
modification of the glass without silicone might be also
possible particularly concerning the silanol groups. Ex-
cept a small decrease of the metal oxide fraction no sig-
nificant change of the original glass composition was ob-
served after the high temperature treatment. We relate this
to the surface restructuring during storage in ambient at-
mosphere since all samples were stored for several days
before analysis. The 600 °C treatment was performed
above the glass transition temperatures (Tg °C) of Fio-
laxTM at about 560 °C. However, the glass viscosity is still
very high at this temperature and a physical deformation
thus impossible.
The analytical results from AR-XPS lead to the con-
clusion of a very thin film of silicone, which is non-closed
and of varying thickness or uneven distribution over the
surface.
The analyses were carried out on glass containers sili-
conized with two different techniques (different viscosi-
ties of the basic oils). In the spectra of these two types,
there were no indications for differences. The viscosity or
average molecular weight of the products used for sili-
conization apparently had no effect on the bonding behav-
ior on the glass surface.
Since all of the analyses were carried out after solvent
extraction, the characterization of the siliconized glass sur-
faces presented here refers only to the bonded silicone
layer. In the pharmaceutical production, the remaining
oily, extractable overlayer is usually not removed with
solvents but used as a lubricant, e.g. in glass syringes.
Thus, a general fixing or baking of silicone oil to the sur-
face, as was previously postulated, did not happen. The
unfixed silicone oil overlayer can therefore still be subject
to interactions with the drug product by migration effects.
In conclusion, the final state of the heat curing siliconiza-
tion has therefore to be considered even more complex
and may be described by other techniques of analysis.
Acknowledgements The authors would like to thank Dr. A Lip-
pitz, Dr. Th. Gross and Dr. W. Unger from the Federal Institute of
Materials Research and Testing (BAM) in Berlin for carefully per-
forming our surface analysis as well as for the enlightening discus-
sions about the capabilities and limits of ESCA.
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