Defence Science Journal, Vol 46, No 3. J\lly 1996.

pp 171-174
(C)1996, DESIDOC I
I

FTIR Spectral Evaluation of Polyurethanel Adhesive Bonds in Perspex

.Canopies of Aircraftl

S.P. Panda* and D.S. ~adafule

Institute of Armament Technology,Pune-411025

ABSTRACT
, I.
Failure of capron glue (polyurethane) OOhesivejoint re tween nylon ships and perspex canopy of ain;rnft
has bden studied by Fourie~ trnnsfoml infrnred spectrnl analysis. It is concluded that the bri ttle failure of the joint
is due to time-dependent Cfsslinking of residual isocyanate group with residual hydroxyl or the amino groups
produced as a result of reIW:tionof absorbed moisture with the isocyanate moiety. A service life of eifht years
I has b~n estimated for the glue joint.
I
I. INTRODUCTION aircraft is a polyurethane condensate of sebacic
\ I I
Fourier transform infrared (FTIR) spectral analysis acid-ethyleneglycol diol (Mn = 12000) and toluene
of the ageing characteristic of the polyurethane capron diisocyanate. As the cured materiall did not dissolve in
glue joi~t between nyloh strips and perspex canopies of any solvent and the KBr pellet pf the crosslinked
aircraft h,s proved to be a useful tool for prediction of adhesive did not give any sharply resolved peak in the
I
failure. The gradual pisappearance of the isocyanate IR speytrum, it was decided to go for the FTIR spectral
absorption at 2350 I,cmol -2360 cm-1 indicated analysis of the KBr pellets of the material. Interestingly,
progressive curing ofl the residual isocyanqte groups
this resulted in finding of a method to predict the failure
over several years of use lfading to b'rittle failure of the
of the adhesive bond, with useful accuracy.
adhesive. In t.he recent pas~, failure of the bond between
I
nylon strips l{olding the perspex canop~es in positioh in
2. EXPERIMENTAL METHOD
a few aircraft leading to accidents In air hat! been
suspected. I I A total of 222 samples of small strips of perspex
cut from the canopies of the aircraft joined with nylon
Therefore, an investigation of t*e failure of the
strips with adhesive of varying period of ageing starting
capron glue joint by some suitable ~pectral method, from 7 to 13 years, were procured. A fresh sample which
which could provide continu'ous recording of data on had hot aged was also procured. Almost all the samples
the joint material that ha~ failed, was considered were tested for the ultimate mechanical strength. The
\
worthwhile. It was found that the adhesive used for joint material was then scrapped out of the nylon strips
joining the nylon strips wit~ perspex canopies of the carefully without aff~cting the nylon beneaf\1. The
I

..
, .0II ..0 0 0
0:(=Ni-(6HI.-NH-(- ~0-((H2)2-0-(-((H2)8-(-II II J 0-((H2)2-0-( II

I n I
: O=~=N -(6H~ -NH
Structure I: Polyurethane (capron glue) adhesive molecule.

Received22 March 1995,revised08 December1995

.To whom corresponde~celisto be made

171
 DEF SCll, VOL 46, NO 3, lUL y 1996

powdered material thus obtained was used to make KBr

pellets for FTIR analysis. The FTIR spectrophotometer
used was a Perkin Elmer Model 1605, computerised
equipment.

3. RESULTS & DISCUSSION

From the large number of samples, a random
choice of three samples was made from each lot
belonging to a particular year of ageing of the joint
material for FfIR spectral analysis. Samples with 7 to
8 years of ageing had a strong absorption peak of
2350.cm-l -2360 cm-l, assigned to the assymetric
stretching of the isocyanate group ( -N=C=O). To get rid
of the problem created in the peak heights due to
varying amount of test material in the KBr pellets, the
carbonyl (>C=O) peak at 162p cm-l -1660 cm-l was
chosen to be the standard peak to produce a ratio of the
peak heights at 2350 cm-l -2360 cm-l and 1620 cm-l -
1660 cm-1 in each sample for comparison. Table I
provides the comparison of isocyanate peak absorption
divided by t~e carbonyl (>C=O) peak absorption 68
averaged over three samples in each case for different
66
years of ageing.
64
Table I. FTIR analysIs data for aged capron glue adhesIve of
1 , 62
the alrcran canopIes
z
Q 60
S.No. Years Samples Peak Peak hl/h2 Mean (/) v.v
of height 5!?
height fhllh2 ~ 58
ageing hi (crn) h2 (cm) (/)
at 2350 at 1620
~
to 2360 to 1660 oc
cm-1 crn .1 ~ 59
~ 54
1 14.6 2.15 6.34 6.67
2 16.00 2.15 7
1 128 2.6 4.92 50 : ~--
2 44004000 3000 2000 ,11500 1000 450
5.75 1.2 4.6 4.76
l' 7.7 2.5 3.08 WAVE NUMBER (cm"1) I

4 3.6 1.2 3.00 3.13 Figure 2. FTIR spectrum or a sample or cured pol~urethane
~ 6.3 1.9 3.315 capron glue aged ror IOtYears which raIled.
10 1 , 5.2 2 2.6
Figure 1 gi ves FrIR ~pectfa1 of a sample -of
5.00 2.2 2.2127 2.89
polyurethane capron glue aged for seven years, which
7.8 1.9 3.85 ,
did not fail-, This was compared with the spectrum of a
II Ij 1.2 1.1, 1.~9
similar sa~ple with reduced isocy~nate absorption that
21 1.5 1.00 1.5 1.295
failed after 10 ye~rs ageing as given in Fig. 2.
6. 12 0.6 3.1 0.1909 0.1995 I
When the results reported in Table 1 were put into
7. 13 nil nil nil nil ,
a graph, as shown ~n Fig. 3, after nine years of ageing a
hl = Peak height for isocyanate group absorption
h2 = Peak height for carbonyl roup absorption smoothly decreasing cprve showed irregular
.Received two samples only devi,tions. This chn be attributed tb the briltle fracture
I I

172
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PANDA & SADAFULE: AIRCRAFr ADHESIVE, POL YURErnANES: FrIR CHARACfERISA TION

samples te-sted possessed strong absorption for -OH

gro~ps in between 3500 cm-1 to 3000 cm-l, in addition
~ "' to absorption for residual ( -N=C=O). The -OH groups
<
w ~
Q. .t:; may belong to the hydroxy-terminated polyester that
z
0
0 has not or only partially reacted with (-N=C=O) group
i= ~ of toluene diisocyanate. The -OH group may also come
Q. 11:
a:
0
1- from absorbed moisture over long years of outdoor
(I)
J:
!I) ~ "n- ---(),I exposure. It is well-known that the reaction of moisture
< w
J: 1 with isocyanate group produces GO2 and -NH2 group
'\1,.
with evolution of'heat. Both -OH and -NH2 groups, thus
p+-- , . , , , + ,
J 6 7 8 9 .10 11 12 13 available, are known to enter into crosslinking reaction
with the isocyanate group of toluene diisocyanate I. This
I YEiARS O~ AGEING I
leads to an increase in crosslinkiQg density with a fall
Figure 3. Ratios ofpeak heights, h,/h2 versus years of ageing for
in hl/h2 (peak height for islocyanate groups
cured polyurethdne capron glue.
I absorption/peak height for carbon¥l group absorption)
in the ad~esive joints, as most of the joints failed after
till a thershold value is obtained when the joint turns
9 years of continuous ageing. Based on these results, it
sufficiently brittle. The horizontal ~ortion of the curve
is recommended that t~e adhesive joints be replaced by in Fig. 3 may refer to this threshold limit of hl/h2. After
fresh joints after 8 ye~rs of continuous seryice, when failure of the joint, the residual ( -N=C=O) groups of the
the ratio of absorption pt:ak height of the isocyanate fresh surface react with atmospheric moisture resulting
group and t~at of the ca/bpnyl group. is around 4.76. in a sharp fall of hl/h2. The magnitude of h2 is not
InterestinglyJ this recommendation ffls in line with affected as much as that of hl as the carbonyl groups
those of th~ manufacturers of aircraft for the occur in the ester moiety in addition to being a part of
replacement of t~e aged joints between nylon strips land the isocyanate group.
perpex canopies. These results also help to know the j
number of years of use of an aircraft~y FTIR spectral ACKNOWLEDGEMENTS
testing of t~e polyurethane adhesive used for bonding The authors are thankful to Dr J.P. Aggarwal,
the aircraft canopies and the nylon strip holders. Sci "F: and Dr D.B. Sarwade, Scil 'C' of High Energy
I I Materials Research Laboratory, Pune, for recording the
As the sal1jlples of the Rolyurethane glue with I to
6 years of ageing were not :available from the aircraft
spectra.. The authors-also thank Maj Gen A.P. P~lta,
Director & Dean, IATr Pune, for permitting the authors
that,reniained in active service, the present work leaves
to publish the results. I
scope for further investigation. However, witH the
available FTIR data, ~ chemical explanation .fo~ the REFERENCE
brittle failure of the glue joint between nylon strips and
BilImeyer, F.W. (Jr.). Textbo:ok of polymer science,
perpex canopy can be aitempted. FTIR spectra of all the Ed. 3. Wiley-Jnterscience, New York, 1984. p. 447.
I

Con tribu tors

Dr SP Panda obtained his MSc in Organic Chemistry from Utkal University in 1963 and PhD in
I?olymer themistry from University of Poona, in 1975. He joined DRDO in 1967 and at present is
the Chairman, Faculty of Explosives and Applied Chemistry at the Institute of Armament
I
Technology (IAT), Pune. He has published about 69 research papers in national and international
I journals iin the fields of hypergolic rocket propellants, ram rocket propellants, photocurable
polymers, ballistic composites and fast neutron activation analysis of explosives and polymers. He
J is an invited member of the New York Academy of Sciences, USA.

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DEF SCI I. VOL 46. NO 3, JUL y 1996

Mr DS Sadarule, Technical Officer (A) at IAT, obtained his BSc (hons) from University of Poona,
in 1969 and joined IAT in the same year. 1 ,

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