Structural characterization of APPJ treated and

Bismaleimide coatings and heat treated Titania-BMI

S.Shrinidhi1, S. Suman1, A.Shah1, P.Prabhakar1, A. Chaurasia1
A. Kumar1, K. G. Chauhan1, A.S.Bhattacharyya1, 2*
1Centre

for Nanotechnology and 2 Centre of Excellence in Green and Efficient

Energy Technology (CoE-GEET)
Central University of Jharkhand, Ranchi 835 205, India,

*e-mail: 2006asb@gmail.com ; arnab.bhattacharya@cuj.ac.in

Bismaleimide (BMI) are thermosetting polymers mainly used in aerospace

applications having properties of dimensional stability, low shrinkage, chemical
resistance, fire resistance, good mechanical properties and high resistance against
various solvents, acids, and water. BMI is commercially available as Homide 250.
BMI coating has also been used for the corrosion protection. Metallization (AL) of
BMI using vacuum evaporation was done which serves the purpose of prevention
of space charge accumulation in aircraft bodies. Addition of inorganic materials
like metal oxides can influence the properties of the polymer as an inorganicorganic composite. The organic-ionorganic composites have wide applications in
electronics, optics, chemistry and medicine. Titanium dioxide (TiO2, Titania) has a
wide range of applications starting from photocatalysis, dye-sensitized solar cells
to optical coatings and electronics. A BMI-TiO2 composite was prepared by
chemical route. Atmospheric Plasma Jet (APPJ) using Helium gas was also treated
on BMI. XRD and FTIR studies of the composite system prepared at different
temperatures showed its crystalline and structural configuration.

Keywords: Bismaleimide (BMI), inorganic-organic composite, APPJ, TiO2

Introduction

Titanium dioxide (TiO2, Titania) has a wide range of applications

starting from photocatalysis, dye-sensitized solar cells to optical
coatings and electronics. Bismaleimide (BMI) on the other hand are
thermosetting polymers having properties of dimensional stability,
low shrinkage, chemical resistance, fire resistance, good mechanical
properties and high resistance against various solvents, acids, and
water [1, 2]. BMI is commercially available as Homide 250 [3]. BMI
coating has also been used for the corrosion protection [4].
Metallization as well as surface properties of BMI are published
elsewhere [5, 6]. Addition of inorganic materials like metal oxides
can influence the properties of the polymer as an inorganic-organic
composite.

The

organic-ionorganic

composites

have

wide

applications in electronics, optics, chemistry and medicine [7, 8]. The

BMI-TiO2 nanocomposite structurally has a shape somewhat as
shown in fig1.

Fig 1 : A schematic representation of BMI-TiO2 composite system[7, 8]

Experimental
Bismaleimide (BMI) coatings were deposited on aluminium sheets
by sprinkling Homide 250 BMI powders and putting the samples in
2

oven [5]. Plasma surface modification of the polymer coatings were

carried out in Argon

atmosphere using Atmospheric Pressure

Plasma Jet (APPJ). In Plasma surface modification (PSM), gasses

dissociate in plasma and form reactive chemical species which react
with the surface improving wettability, corrosion resistance,
hardness and wear properties. It finds major applications in biomedical, electronics and aerospace fields. The advantage of using
APPJ lies in the fact that it overcomes the disadvantages of vacuum
creation and hence large areas can be treated. The jet temperature is
around 25-200 oC, charged particle density of 1011-1012 cm-3 and gas
velocity of 12 m/s [9].The physicochemical changes of surface of the
polymer before and after plasma modification and after polymer
coating were thoroughly studied.
A TiO2-BMI composite system was made by taking TiO2 powder,
PVA and BMI (10 gm) and using magnetic stirrer. The system was
quite homogenous and had no precipitation. A coating of the
composite was made by uniformly depositing on a glass slide and
allowing it to dry. Proto XRD at Centre of Excellence for Green
Energy and Efficient Technology (CoE-GEET) CUJ was used for the
XRD studies where monochromatic Cu-K radiation having a
wavelength of 1.54 was used. Sample preparation for XRD consists
of filling up the stub upto the surface in case of powder samples. For
the TiO2-BMI composite solution was made like a film on a glass
slide as shown above

and put over the stub which was

subsequently transferred to the XRD chamber.

Results and Discussions

X-ray diffraction studies on BMI coatings on aluminum and
3

different temperatures are shown in fig 2 which showed substrate

effect of Al and mild steel. The samples BMI/Al 3 and BMI/AL 9
were bismaleimide coatings on Al showing peaks at 38o, 44 o, 65

and 78 o which are characteristic of aluminum substrate. The sample

BMI/MS was BMI on mild steel substrate which showed peak
around 44 o corresponding to Fe (110). The trilayer of mild steel, BMI
and AL also showed peak in the same region indicating little effect
of the topmost Al layer. Fig 3 shows the effect of APPJ on the
crystallinity. 1 and 2 stands for samples which have been baked in
the muffle furnace starting from and initial temperature of 21oc and
200oC to 350 oC respectively. The names 1/a and 2/a indicates the
samples prepared in 1 and 2 conditions but APPJ treated.
Interestingly some crystallinity was observed in sample 2/a which
was not coming from the substrate which has been enlarged and
shown separately in Fig 4.

MS/BMI/Al
BMI/MS

Intensity (a. u)

BMI film

BMI/Al 9

BMI/Al 3

10

20

30

40

50

60

70

80

Fig 2: XRD of BMI coatings on different substrates and conditions

Intensity (a.u)

2 / APPJ
2

1 / APPJ

30

60

90

Intensity (a.u)

Fig 3: XRD of BMI coatings on Al substrates and APPJ treated

10

15

20

25

30

Fig 4: XRD showing crystallinity in APPJ treated BMI

The XRD of TiO2-BMI cured at different temperatures is shown in fig 5. Shifts

in the peaks were observed at 400oC indicating stress being generated due to
5

temperature. It was also observed that peak around 19oC arising due to BMI
got diminished as we increased the curing temperature and was totally absent
at 400oC. The crystallinity in polymer is due to packing of molecular chains so
as to produce an ordered atomic array. The sharp diffraction peaks of the indicates
that its a brittle resin [10].

The polymer molecules are only partially crystalline with crystalline regions
dispersed in amorphous regions as per fringed-micelle model [11]. An increase
in temperature results in chain disorder causing twisting and coiling of the
chains preventing the strict ordering of the chain segments resulting in loss in
crystallinity. The XRD pattern of the TiO2-BMI sample treated at 400oC after
seven days showed improved crystallinity which is probably due to the
presence of TiO2 which has prevented the BMI to cross link completely and as
a result aided it to regain it shape on cooling. Crystallinity in polymers
indicates strength and resistance to dissolution and softening by heat [12].

Intensity (a,u)

400 C

150 C

RT
10

20

30

40

50

60

70

80

Fig 5: XRD of TiO2-BMI cured at different temperatures

XRD of the TiO2-BMI sample cured at 400oC was again taken after seven days
to see the effect of time as shown in Fig 6. It was observed that 101 peak of
6

anatase was much more intense compared to other phases showing a

preferential crystallographic orientation of the TiO2 crystallites in the

Intensity (a.u)

composite.

after 7 days

20

40

60

80

Fig 6 : XRD of TiO2-BMI cured at 400oC after 7 days

The FTIR studies are shown in fig 7. The broad peak at 3400 cm-1 corresponds
to N-H stretch. According to the literature published a band at 670 cm-1
corresponds to TiO2 (Ti-O-Ti) which is seen in the spectra of the sample at RT
and which was not visible in spectra of samples at higher temperature. The
peak at 830 cm-1 at 150 oC and 400 oC corresponds to Ti-O-C. The peak at 2900
cm-1 is due to sp3 C-H stretch. The peak at 1904 cm-1 is due to CO which is
absent at 400oC. Carbonyl (C=O) groups were observed at 1710 cm-1 which
showed a shift to 1725 cm-1 at RT indicating strengthening of H bonding due to
temperature[13]. The peak at 1640 cm-1 is due to benzene ring. The peak at
1515 cm-1 at 150oC and 1504 cm-1 at 400oC was due to Benzene ring. The peaks
at 950 cm-1 at higher temperature was again due to R-CH=CH-R bonds in the
middle of the chain. Lu et al has however discussed about end chain bonds R7

CH=CH2 at 920cm-1 which were absent in this case [8]. The details of the
different peaks are given in Table 1, 2 and 3.

75

R-CH=CH-R

70

Maleimide

%T

C-O

C-N-C

CH

65

150 C

sp3 C-H

C=O

N-H stretch
C-O

60

RT
55

Benzene ring
o

400 C
50

45
0

500

1000

1500

2000

2500

3000

3500

4000

4500

Wavenumebr / cm-1
Fig 7: FTIR of TiO2-BMI cured at different temperatures

Table 1: The FTIR peaks for TiO2-BMI at room temperature (RT)

Temp

RT

Peak Positions
(cm-1)

Signature

3426

N-H stretch

2926

C-H stretching

1904

C-O

1720

C=O
symmetrical
stretching

1393

CN
and
stretching

1390

C-O stretching

1511

Benzene ring

CNC

949

maleimide

580

TiO2 bonds / CH

Table 2: The FTIR peaks for TiO2-BMI at 150oC

Temp

Peak
(cm-1)

Positions

Signature

150

3426

N-H stretch

1904

C-O

1710

C=C

1720

C=O

1509

Benzene ring

1390

C-O stretch

1055

C-O stretch

833

maleimide

950

maleimide

1393

CN
and
stretching

CNC

Table 3: The FTIR peaks for TiO2-BMI at 400 oC

Temp

Peak
(cm-1)

Positions

Signature

400

1633

Alkenyl C=C stretch

and amide C=O stretch

2930

alkyl C-H stretch

and carboxylic acid
O-H stretch

3435

N-H stretch

1055

C-O stretching

Raman studies of both pristine and APPJ treated samples showed

no active modes (Fig 8) which indicates no polarizability change.

Intensity (a.u)

250 C

100 C
o

200 C

300 C

500

1000

1500

2000

wavenumber / cm

2500

3000

3500

-1

Fig 10: Raman Spectra of BMI/Al coatings at different conditions

Summary
Bismaleimide (BMI) coatings were deposited on aluminium sheets by a
simple process of powder sprinkling and baking. The coating were well
adhered to the substrate and were treated with APPJ using He gas.
Crystallinity was observed in the APPJ treated BMI coatings by XRD.
The samples were not Raman active. The BMI powders were blended
with TiO2 to form an organic-ionganic composite system. Temperature
was found to have significant effect on the structure and composition
of the composite system. The future scopes of work include using other
gas plasma like Oxygen or Nitrogen and see the morphological as well
as chemical changes taking place. Blending BMI with other materials to
form composites and characterization through XPS can also be done.

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Acknowledgements

The research was funded by DST Young Scientist Fast Track Scheme
(SERB-Start up Research Grant SR/FTP/ETA-35/2011 and Centre of
Excellence in Green and Efficient Energy technology (CoE-GEET) under
FAST Scheme, MHRD India.

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