Progress in Organic Coatings 53 (2005) 183190

Preparation of moisture curable polysilazane coatings

Part I. Elucidation of low temperature curing kinetics by
FT-IR spectroscopy
Frank Bauer a, , Ulrich Decker a , Andreas Dierdorf b , Horst Ernst c ,
Roswitha Heller a , Hubert Liebe b , Reiner Mehnert a
a

Institut fur Oberachenmodizierung, Permoserstr. 15, D-04318 Leipzig, Germany

b Clariant GmbH, Am Unisys-Park 1, D-65843 Sulzbach am Taunus, Germany
Universitat Leipzig, Inst. fur Experimentelle Physik I, Linnestr. 5, D-04103 Leipzig, Germany
Received 15 December 2004; accepted 15 February 2005

Abstract
Moisture-curing of perhydropolysilazane and polyorganosilazanes to pre-ceramics has been studied at temperatures ranging from room
temperature to about 150 C. Results of FT-IR experiments with a diamond ATR adapter clearly showed that rapid curing required the presence
of a moisture-containing atmosphere of about 80% relative humidity and the introduction of a catalytic curing agent such as ammonia or an
amine. With respect to the curing rate, the effect of temperature increase can be compensated by a decrease of humidity, that is why moistening
furnace are recommended for polysilazane transformation. The mechanism of moisture-cure mainly based on the hydrolysis of SiH and
SiN bonds by water vapor to promote subsequent cross-linking of intermediately formed silanols via condensation reactions.
Compared to neat polyorganosilazanes, blends with perhydropolysilazane revealed both higher curing rate and improved surface hardness.
Polysilazane films of about 3 m thickness coated on polycarbonate plates and cured at 50 C in air of about 80% relative humidity for
1 h exhibited microhardness of about 450 N mm2 compared to about 250 N mm2 obtained for acrylate/silica nano-composite coatings.
These findings point to dense polysilazane films what makes them very promising as coatings for technical applications, e.g., reduced gas
permeability and improved corrosion resistance.
2005 Elsevier B.V. All rights reserved.
Keywords: Coatings; Polyorganosilazane; Perhydropolysilazane; Moisture-curing

1. Introduction
Polysilazane derived ceramics have been intensively studied in recent years [1]. Polyorganosilazanes, as well as
perhydropolysilazane (PHPS), can be produced in large quantities via ammonolysis of dichlorosilanes R2 SiCl2 and subsequent base-catalyzed dehydrogenative coupling [2,3]. At
temperatures of about 1000 C, polymeric silazanes can be
transformed to amorphous, hydrogen free silicon carbonitrides, and at temperatures above 1440 C the amorphous
networks finally crystallize to give silicon nitride (Si3 N4 )

Corresponding author. Tel.: +49 341 235 3288; fax: +49 341 235 3400.
E-mail address: fbauer@rz.uni-leipzig.de (F. Bauer).

0300-9440/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2005.02.006

and silicon carbide (SiC). A very crucial step during the high
temperature polymer-to-ceramic transformation is the curing
or cross-linking of the green film to obtain a crackfree coating with high chemical resistance and enhanced mechanical
properties at elevated temperatures. The large shrinkage associated with the polymer-to-ceramic transformation leads
to formation of cracks if the thickness of the PHPS coating
exceeds a critical value, typically in the region of 12 m.
These problems can be overcome by dispersing appropriate
fillers within the polysilazane material [47].
Based on the relatively cheap dichloromethylsilane,
CH3 SiHCl2 , a variety of molecular, oligomeric and polymeric organosilazanes, such as polymethyl(hydro)silazane
(PMS), polymethyl(hydro)/polydimethylsilazane (PMDMS)

184

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

and polymethyl/polymethyvinylsilazane (PMVS), can be

produced. Polyorganosilazanes, as well as molecular
organosilizanes, are commercially available and can be considered, similar to PHPS, as highly efficient ceramic precursors. For example, organosilazanes are decomposed in
chemical reactors to form ceramic coatings in order to reduce the rate of coke formation during industrial pyrolysis
of hydrocarbons [8]. For this purpose, the ceramic precursor
compounds are injected into a steam carrier gas. The temperature of deposition can vary from about 600 to 1000 C.
Typically, polyorganosilazane coatings with up to 20 m are
thicker than PHPS films.
To avoid deficiencies such as voids, pinholes and cracks
caused by shrinkage during the high-temperature polymer-toceramic transformation, low-temperature curing and crosslinking of PHPS at 100300 C has been described to give
glass-like hard solids [9]. Even at about 90 C, PHPS can be
converted to silica without lattice defects and having a density
of 1.3 g/cm3 [10]. Moreover, at temperatures of 80120 C
the curing rate can be increased by treating PHPS films with
pyridine and NH3 [11]. Using methylsubstituted piperidine,
alkylamines or acids as catalysts, PHPS curing at room temperatures is claimed to provide dense coatings impermeable
for oxygen and, thereby, preventing oxidation of metal surfaces [12].
Another field of low-temperature conversion of silazanebased polymers concerns ceramic films on substrates used
in electronic products or as plastic films where conventional
methods for the ceramic-transformation, i.e., calcination at a
high-temperature in the order of 900 C, cannot be applied.
By using ceramic-transformation promoting agents, such as
an amine, an acid compound, and a peroxide PHPS has been
found to be smoothly transformed into a ceramic material
even at a temperature as low as 50 C [13]. Typically, curing of
the PHPS coated film occurred through a moistening furnace
maintained at 95 C and a relative humidity of 80%. Thus,
substantial improvements of oxygen and steam permeability
as well as scratch resistance has been obtained for PET and
PES film substrates having a thickness of 75 m.
Furthermore, post-synthesis modification of organic polymers by soaking with PHPS has proposed to obtain organic/silica nano-composites [10]. Because PHPS is soluble
in many solvents, such as benzene, xylene, cyclohexane, pyridine, etc., it can penetrate into pre-swollen organic polymer
films and will be selectively introduced in polymeric domains
with hydroxyl groups, e.g., poly(2-hydroxyethyl methacrylate). Subsequently, the soaked film was calcinated under
steam at 90 C for 3 h to convert PHPS to silica.
Organosilazane and organosiloxane can be composed to
form room temperature curable organosiloxazane polymers
[14,15]. When the organosiloxazane polymer, preferably, in
the form of a solution is coated on a substrate followed by drying to form a film, the polymer is cross-linked by the reaction
with the atmospheric moisture to form a cured surface film
on the substrate surface. Recently, alkoxy silyl substituted
polysilazanes are proposed for coatings with good thermal

stability and nonwetting properties, including oxidation and

corrosion resistance to metal substrates [16]. Due to the selectively substituted alkoxy silyl groups the polysilazanes and
polysiloxazanes polymers are capable of undergoing rapid
moisture-cure at temperatures ranging from room temperature to about 50 C without requiring the introduction of a
catalytic curing agent.
Besides as pristine coating liquids, PHPS and polyorganosilazanes are also proposed as binders for nano-sized
particles such as metal borides and metal oxides [17]. A curing temperature of 100 C or below is mentioned as a result
of the addition of an oxidizing catalyst. Comparable with
functionalised trialkoxysilanes, organosilazane compounds
are described to act as agents for surface treatment of finely
powdered silica [18].
Low-temperature curing is claimed for polymethyl(hydro)silazane used with up to 5 wt.% as component of a
primer for pretreating glass in readiness for waterproof bonding to other substrates [19]. Likewise, organosilizanes are
employed at room temperatures in the circuit board industry to improve bonding between layers in multilayer circuit
boards [20].
Compared with the overwhelming number of papers related to the polysilazane derived ceramics formed during
high-temperature transformations [1], low-temperature curing of PHPS and polyorganosilazanes has been mainly
described in the patent literature. In this study, the lowtemperature conversion of different commercially available
polysilazanes and mixtures thereof have been investigated in
order to correlate the reaction conditions, such as temperature, humidity, atmosphere and catalyst, with the curing rate
as well as the properties of the coatings. Whereas kinetic experiments were performed using FT-IR spectroscopy with a
heatable ATR adapter, 29 Si CP MAS NMR spectroscopy, secondary electron microscopy (SEM) and microhardness were
applied to characterize the cured polysilazane films.

2. Experimental
2.1. Materials
All of the polysilazanes under study are available
from Clariant. PHPS/xylene solution (20 wt.% PHPS
with 0.15 wt.% 4,4 -trimethylenbis(1-methylpiperidin) as
catalyst), polymethyl(hydro)silazane, polymethyl(hydro)/
polydimethylsilazane, polymethyl/polymethylvinylsilazane
and trialkoxy silyl substituted polymethyl/polydimethylsilazane (subPMDMS) were used as received.
2.2. Equipment
FT-IR spectra were obtained using a Biorad IR Spectrometer FTS6000 with a diamond Golden Gate ATR adapter
(Specac) heatable up to 200 C. After depositing the polysilazane film, the ATR crystal was covered with home-made

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

185

glass dome including a tubular reservoir for water and 5%

aqueous ammonium hydroxide solution. Spectra were taken
each 30 s during a typical study of 900 min and a resolution
of 4 cm1 was chosen.
Solid-state 29 Si MAS NMR measurements were carried
out using a Bruker MSL 500 spectrometer using a spinning
rate of 5 kHz. The contact time in the 29 Si CP MAS NMR
experiments was 15 ms.
The abrasion resistance was measured with the Haze Gard
plus (Byk Gardner) after 100 cycles Taber Abraser 5150
(Taber Industries, CS 10 rolls, 5 N). Haze is given in percentage. The microscratch hardness was determined by Fischerscope H100C.
2.3. Curing of polysilanzane lms
To assess the curing behavior of pristine polyorganosilazanes, films prepared by dip-coating were allowed to
moisture-cure by setting on the lab bench at room temperature and ambient humidity. The coating made of polymethyl(hydro)silazane was dry to the touch in 13 h and fully
cured overnight to clear, colorless, hard coatings. Trialkoxy
silyl substituted polymethyl/polydimethylsilazane are fully
cured by the next day and PMVS need about 36 h to cure.
PMDMS failed to cure when allowed to remain for several
days at ambient room conditions. Therefore, an ammoniacontaining atmosphere and the addition of different amines
to the formulations were used to accelerate polysilazane curing.
After adding a catalytic curing agent and dip-coating
on different substrates, the polysilazane films were dried at
100 C for 15 min to remove any solvents, exposed at 50 C
to an ammonia-containing atmosphere of about 90% relative
humidity for 60 min and finally heat treated in air at 150 C
(depending on the substrate) for 60 min.

Fig. 1. FT-IR spectra of PHPS after different curing times at 50 C and 90%
relative humidity.

Polysilazanes formed by ammonolysis of dichlorosilanes

R2 SiCl2 and subsequent dehydrocoupling reactions involving Si H and N H groups [21] consist of a mixture of linear
and cyclic oligomers. To simplify matters, the composition of
polysilazanes is given by the linear polymeric subunit, e.g.,

The reaction rate of PHPS transformation can be determined by the disappearance of Si H vibrations (N H vibrations) and the emergence of Si O Si oscillations according to an IR spectroscopic analysis (Fig. 1). The absorption
bands at 2140 and 885 cm1 can be assigned to Si H vibrations, whereas bands at 3380 and 1160 cm1 based on N H
groups. According to the IR spectrum atlas, bands between
1020 and 820 cm1 can be designed to Si N Si vibrations.
Note, PHPS is delivered as a 20 wt.% solution in xylene, i.e.,
a short drying period is necessary for solvent vaporization.
At 50 C and a relative humidity of 90% together
with presence of an amine catalyst (0.15 wt.% 4,4 trimethylenbis(1-methylpiperidin)), the disappearance of
Si H vibrations at 2140 cm1 and the formation of Si O Si
structures (bands at 1025 and 760 cm1 ) clearly indicates
the curing of PHPS under these reaction conditions. After
180 min curing time, the Si H band still remains to a considerable extent. However, there is a significant effect of humidity on curing rate (Fig. 2). After 180 min at 50 C in dry
air, the conversion of Si H groups is about 15% compared to

The huge amount of Si H groups explains why PHPS is

highly reactive with hydroxyl groups. After hydrolysis with
water, silanol groups are formed as short living intermediates.
Finally, condensation and cross-linking reactions result in the
formation of silica.

about 55% in the presence of moisture. The essential role of

water (i.e., partial pressure of water vapor) during the hydrolysis/condensation process of polysilazanes is also indicated
by the lower reaction rate obtained at 100 C in dry air

3. Results and discussion

3.1. Curing of PHPS

186

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

Fig. 2. PHPS curing at 50 C under different moisture conditions. Effect of

curing time on Si H vibrations (peak area at 2170 cm1 ).
Fig. 4.

(Fig. 3). On the other hand, significant enhancement of the

curing rate can be obtained by basic catalysts in the presence of water vapor. For example, after adding about 5 wt.%
diethylaminoethanol as catalyst a Si H conversion of about
90% has been observed during 60 min curing at 50 C and
90% humidity (Fig. 3). Note, during polysilazanes curing
ammonia is released which can autocatalytically increase the
rate of PHPS hydrolysis and condensation if not flushed away.
Finally, a silica glass film has been produced. Consequently, the 29 Si MAS NMR spectrum of cured PHPS (Fig. 4)
reveals no signal in the region 10 to 10 ppm, where chemical shifts of silazanes are typically observed [22]. But, low
temperature curing cannot be expected to form dense coatings
of pure silica. The desired SiO2 is characterized by siloxane
Si(OSi)4 groups (Q4 ) by the signal at 108.8 ppm, whereas
the signal at 100.1 ppm has to be assigned to Si(OSi)3 OH
groups (Q3 ). Low amounts of geminal silanols (Q2 ) are indicated by a shoulder at about 90 ppm. The very broad
signal at about 33.4 ppm can be assigned to partially hydrolyzed silicon atoms. More detailed information can be
obtained by 29 Si cross-polarization (CP) MAS NMR tech-

Fig. 3. PHPS curing under different reaction conditions. Effect of curing

time on Si H vibrations (peak area at 2170 cm1 ).

29 Si

MAS NMR spectra of PHPS cured at 50 C.

nique, which enhances the sensibility of silicon atoms in

the neighborhood of H atoms (Fig. 5). The signals with 29 Si
chemical shifts between 35 and 85 ppm are assumed to
point to R Si(OSi)3 x OHx siloxane structures similar to the
29 Si NMR pattern of condensed or surface grafted products
of functionalized trialkoxysilanes [23,24]. Signals of grafted
organosilanes are typically observed in the 45 to 50 ppm,
55 to 60 ppm, and 65 to 70 ppm regions and are assigned to mono(T1 )-, di(T2 )- and tri(T3 )-fold Si O-linked
silicons, respectively. Thus, the assignment of the signal
at 37.2 ppm to T1 structures, i.e., H Si(OSi)OH2 and/or
HN Si(OSi)OH2 groups, is tentative and requires confirmation by 29 Si15 N coupling constants.
3.2. Curing of polyorganosilazanes
Based on ammonolysis of dichloromethylsilanes
RCH3 SiCl2 (R H, CH3 , CH CH2 ) the IR spectra of all
polyorganosilazanes have as a common feature a band at

Fig. 5.

29 Si

CP MAS NMR spectra of PHPS cured at 50 C.

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

187

Fig. 6. FT-IR spectra of polymethyl(hydro)silazane (1 wt.% 4,4 trimethylenbis(1-methylpiperidin) as catalyst) after different curing times
at 50 C and 90% relative humidity.

Fig. 7. FT-IR spectra of polymethyl/polymethylvinylsilazane (1 wt.% 4,4 trimethylenbis(1-methylpiperidin) as catalyst) after different curing times at
50 C and 90% relative humidity.

about 1260 cm1 based on the non-hydrolysable Si CH3

group, which can be taken for comparing spectra. Due to
the incorporation of methyl, vinyl and trialkoxyalkylsilyl
functionalities polyorganosilazane are less reactive with
OH groups than PHPS. The transformation to dense SiOC
coatings occurs comparable to PHPS via hydrolysis with
moisture, condensation and cross-linking. The IR spectra
observed during curing of polymethyl(hydro)silazane at
50 C over 900 min reveal that the absorptions at 3380 and
1160 cm1 based on N H vibrations and at wavenumbers
of about 2120 cm1 based on Si H groups still remained
to a considerable extent (Fig. 6). Correspondingly, the
appearance of Si O Si bands at 1040 cm1 is retarded.
Even using a catalyst and high humidity, the curing time of
all the polyorganosilazane at 50 C in the range of more than
15 h is insufficient.
With respect to the hydrolysis/condensation process two
points are of special interest: (i) are the hydrolysis rates of
Si H and Si N bonds quite different and (ii) are the hydrolysis rates of Si H and Si N bonds different from the
condensation rates (formation of Si O Si bonds). Based
on the IR spectra of PMVS during curing (Fig. 7), the decrease of IR band intensities of Si H groups (2120 cm1 ) and
N H groups (3380 cm1 ; as representative for Si N bonds)
as well as the increase of Si O Si vibrations (1025 cm1 )
are shown in Fig. 8. The concentration versus curing time
plot reveals that the kinetics of Si H and N H transformation is hardly different and the intensity of the Si O Si
vibrations increases proportionally with the decrease of the
Si H/N H bands. Therefore, polysilazanes are assumed to
possess a similar reactivity of Si H and Si N bonds with OH
groups. Moreover, silanol groups intermediately formed will
quickly condense to siloxane structures, otherwise an initial
time lag of Si O Si formation should have been observed
(Fig. 8).

In addition to condensation reactions forming Si O Si

bonds, cross-linking based on alkenyl groups is assumed
to improve the tearing strength of the cured polysilazane film. Therefore, a small quantity of a free radical generator is recommended for the thermal curing
of PMVS. The proportion of vinyl groups in polymethyl(hydro)/polymethylvinylsilazane can roughly estimated by comparison of the bands at about 1400 cm1 (C C
vibrations) and 1260 cm1 (CH3 vibrations). Their reactivity has been elucidated by UV-induced polymerization with
the aid of 5 wt.% photoinitiator (Lucirin TPOL, available
from BASF) and a conventional medium pressure Hg lamp
(250 mW cm2 ). To reduce the detrimental effect of radical
capture by oxygen, the UV curing experiments were done

Fig. 8. Curing of polymethyl/polymethylvinylsilazane (1 wt.% 4,4 trimethylenbis(1-methylpiperidin) as catalyst) at 50 C and 90% relative humidity. Effect of curing time on Si H vibrations (peak area at 2170 cm1 ),
N H vibrations (peak area at 3380 cm1 ) and Si O Si vibrations (peak
area at 1025 cm1 ).

188

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

Fig. 9. FT-IR spectra of polymethyl/polymethylvinylsilazane (5 wt.% Lucirin TPOL as photoinitiator) at 30 C under nitrogen flushing and UV radiation (250 mW cm2 ). Inset: effect of UV curing time on C C vibrations
(peak area at 1400 cm1 ).

under nitrogen flushing. UV radiation with a duration of 600 s

resulted in a 10% decrease of the characteristic C C vibrations at 1400 cm1 (Fig. 9). For comparison, acrylate formulations reveal within 2 s a typical C C conversion of about
80% under identical conditions. Therefore, cross-linking via
vinyl groups will only take a small contribution to polymethylvinylsilazane curing.
3.3. Curing of PHPS/polyorganosilazane lms
Excellent corrosion resistance can be obtained by coating
the surface of metals with PHPS and heating to 100600 C
in air, thereby converting PHPS into a silica glass film. However, the thickness of the wet coating film is limited to about
12 m at most, otherwise defects such as crack and deformation are likely to occur during the heat treatment. On the other
hand, the thickness of the coating film has to be increased to
cover surface defects on metals such as sharp scratches, pinholes and deep irregularities. To solve the problem, mixtures
of PHPS and polyorganosilazane are claimed to obtain coatings thicker than 2 m, which are both dense and flexible
[25].
The addition of PHPS to polyorganosilazanes increased
considerably the curing rate (Fig. 10). For example, the
transformation of Si H groups with pure PMVS was about
35% after 180 min at 50 C and 90% humidity (see Fig. 8).
Under the same conditions, a 1:1 mixture of PMVS and
PHPS achieved 80% conversion (Fig. 11). This strong
effect cannot be explained by the simple addition of a
catalyst (PHPS contains 0.15 wt.% 4,4 -trimethylenbis(1methylpiperidin)). Therefore, PHPS is assumed to transport water molecules via its own hydrolysis/condensation
throughout the polyorganosilazane film quicker than regular
diffusion.

Fig. 10. FT-IR spectra of 1:1 mixture of PHPS/PMDMS after different curing times at 50 C and 90% relative humidity of an ammonia-containing
atmosphere.

3.4. Surface properties and hardness of

PHPS/polyorganosilazane coatings
After dip coating on a substrate (PC plate or 80 m PET
film) and drying at 100 C for 10 min, the polysilazane films
were maintained at 50 C and a relative humidity of 90%
for 120 min and finally heat treated at 150 C for 60 min.
The thickness of coatings were determined by SEM after
cryobraking. For example, a 1:1 mixture of PHPS and PMVS
resulted in a typical thickness of about 3 m (Fig. 12). The
SEM picture revealed that formation of microdomains in the
extent of 100 nm occurred during polysilazane curing. As
a result, diffusion at the microdomain interfaces can have
an impact on the desired gas barrier effect as well as the
surface of polysilazane coatings will exhibit some roughness
(Fig. 13).

Fig. 11. Curing of 1:1 mixtures of PHPS and polyorganosilazanes at 50 C

and 90% relative humidity of an ammonia-containing atmosphere. Effect of
curing time on Si H vibrations (peak area at 2170 cm1 ).

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

189

Table 1
Abrasion resistance of polysilazane coatings on polycarbonate (film thickness: 3 m; 100 cycles Taber Abraser 5150; Taber Industries, CS 10 rolls,
5 N)
Coating

Haze (%)

PMVS PHPS (3 m)
SubPMDMS /PHPS (3 m)
SiO2 /acrylate (40 m)
Polycarbonate

3.6
5.1
2.16.4
58.7

Fig. 12. SEM image of a slice through a PHPS/PMVS coating on a 80 m

PET film substrate.

For transparent coatings, micro-abrasion by small, shallow scratches affecting the visual properties can be assessed
with a haze-meter. In the Taber Haze test, the abrasion damage by fine aluminum oxide particles is recommended to
measure after 500 cycles Taber Abraser with CS 10 rolls.
This cycle number, however, would disguise the abrasion
resistance of the 3 m thick films coated on polycarbonate
plates due to rubbing off the whole film. Therefore, Haze
has been determined after 100 cycles Taber Abraser with
CS 10F rolls. The comparison with UV-cured acrylate/SiO2
nano-composite coatings of about 40 m thickness yielded a
satisfactory surface hardness for the 1:1 blends of PHPS and
polyorganosilazanes with only 3 m thickness (Table 1).
For thin coatings, the hardness value may be affected by
substrate material. A reliable estimation of surface hardness
does not allow scratch depth to be more than 1/10 of coat
thickness. Indentation (microhardness) is a method to identify the mechanical properties of materials near their surfaces,
i.e., normal hardness and yield stress as a function of strain.

Fig. 14. Microhardness of 1:1 mixtures of PHPS and polyorganosilazanes

on glass plates (cured at 50 C and 90% relative humidity of an ammoniacontaining atmosphere).

This test can even be performed on thin coatings with a thickness below 3 m. The microhardness of cured polyorganosilazane films is comparable with that of polycarbonate
(180 N mm2 ) or worse, e.g., polymethyl(hydro)silazane at
about 160 N mm2 and polymethyl/polymethylvinylsilazane
at about 80 N mm2 . Coatings based on 1:1 mixtures of
PHPS and polyorganosilazanes exhibited significantly improved surface hardness (Fig. 14). These polysilazanes surfaces are even harder than UV-cured polyacrylate coatings
reinforced by silica nanoparticle [26]. In addition, varying
the ratio of the contents of PHPS and polyorganosilazane
provide an opportunity to adjust the hardness and flexibility of the polysilazane coatings according to intended use or
customer request.
Obviously, the PHPS/polyorganosilazane coatings cannot achieve the scratch resistance of a SiO2 layer prepared
from PHPS (2100 N mm2 [27]) or even that for silica
(30003700 N mm2 ). Nevertheless, short curing times, improved surface hardness and maintaining flexibility makes
blends of PHPS and polyorganosilazanes very promising as
coatings for technical applications.

4. Conclusions

Fig. 13. SEM image of the surface of a PHPS/PMVS coating on a 80 m

PET film substrate.

Coatings prepared on the base of commercially available

perhydropolysilazane and polyorganosilazanes are curable
by reactions with moisture at temperatures ranging from

190

F. Bauer et al. / Progress in Organic Coatings 53 (2005) 183190

room temperature to about 150 C. Rapid curing required

the presence of a moisture-containing atmosphere of about
80% relative humidity and the introduction of a catalytic curing agent such as ammonia or an amine. The mechanism
of moisture-cure relies mainly on the activation of Si H and
Si N bonds by OH group containing substances such as water
to promote subsequent cross-linking of intermediate silanols
via condensation reactions.
Compared to pure polyorganosilazanes, blends with
perhydropolysilazane revealed both higher curing rate and
improved surface hardness. Blends of PHPS and polyorganosilazanes of about 3 m thickness coated on polycarbonate plates exhibited microhardness of about 450 N mm2
compared to 250 N mm2 of a silica nanoparticle reinforced
polyacrylate clear coat of 40 m thickness, i.e., thin polysilazane films are an alternative solution for scratch and abrasion resistant coatings. Due to the ratio of the contents of
PHPS and polyorganosilazane the hardness and flexibility of
polysilazane coatings can be adjusted for various technical
applications.

References
[1] E. Kroke, Y.L. Li, C. Konetschny, E. Lecomte, C. Fasel, R. Riedel,
Mater. Sci. Eng. 26 (2000) 97.
[2] D. Seyferth, G.H. Wiseman, Am. Chem. Soc. Polym. Div., Polym.
Prep. 25 (1984) 10.
[3] D. Seyferth, G.H. Wiseman, J. Am. Ceram. Soc. 67 (1984) 132.
[4] C. Konetschny, D. Galusek, S. Reschke, C. Fasel, R. Riedel, J. Eur.
Ceram. Soc. 19 (1999) 2789.
[5] M. Labrousse, M. Nanot, P. Boch, E. Chassgneux, Ceram. Int. 19
(1993) 259.
[6] G.S. Lum, C.J. Langlois, US Patent 5,258,229 (1993).

[7] D. Heimann, J. Bill, F. Aldinger, P. Schanz, F. Gern, W. Krenkel,

R. Kochendoerfer, Z. Flugwissenschaften Weltraumforschung 19-3
(1995) 180.
[8] T. Clark, R. Cruse, S. Rohman, R. Mininni, US Patent 5,424,095
(1995).
[9] T. Morozumi, K. Sato, A. Tezuka, H. Kaya, T. Isoda, Proceeding of
the Topical Symposium on Advanced Structural Fibre Composites
of the 8th CIMTECWorld Ceramic Congress and Forum on New
Material, Florence, 1994.
[10] Y. Mori, R. Saito, Polymer 45 (2004) 95.
[11] O. Funayama, Y. Tashiro, A. Kamo, M. Okumura, T. Isoda, J. Mater.
Sci. 29 (1994) 4883.
[12] H. Ahrens, DE Patent 10320180 (2003).
[13] Y. Shimizu, H. Matsuo, K. Yamada, US Patent 5,922,411 (1999).
[14] K. Itoh, S. Kozakai, Y. Hida, H. Okinoshima, F. Okada, T.
Oba, H. Shimizu, Y. Hinoto, H. Yoshioka, US Patent 4,678,688,
(1987).
[15] G.J. Knasiak, I.A. Lukacs, R. Mouk, A.E. Abel, US Patent 6,534,184
(2003).
[16] I.A. Lukacs, G.J. Knasiak, US Patent 6,652,978 (2003).
[17] H. Kuno, H. Takeda, K. Adachi, US Patent 6,277,187 (2001).
[18] H. Fujiki, K. Tanaka, US Patent 5,767,193 (1998).
[19] R. Oezelli, H.-J. Hoffman, H.-P. Kohlstadt, US Patent 4,735,830
(1988).
[20] J.R. Montano, J.P. Cahalen, US Patent 6,743,303 (2004).
[21] N.S. Choong Kwet Yive, R.J.P. Corriu, D. Leclerq, P.H. Mutin, A.
Vioux, Chem. Mater. 4 (1992) 141.
[22] Y. Takeuchi, T. Takayama, in: Z. Rappoport, Y. Apeloig (Eds.), The
Chemistry of Organic Silicon Compounds, vol. 2, Wiley & Sons
Ltd., 1998, p. 267.
[23] K. Albert, E. Bayer, B. Pfleiderer, J. Chromatogr. 506 (1990) 343.
[24] F. Bauer, H. Ernst, U. Decker, M. Findeisen, H.-J. Glasel, H.
Langguth, E. Hartmann, R. Mehnert, C. Peuker, Macromol. Chem.
Phys. 201 (2000) 2654.
[25] T. Shindo, US Patent 6,627,559 (2003).
[26] H.-J. Glasel, F. Bauer, H. Ernst, M. Findeisen, E. Hartmann, H.
Langguth, R. Mehnert, R. Schubert, Macromol. Chem. Phys. 201
(2000) 2765.
[27] S. Stojanovic, personal communication (2003).