ELSEVIER Vibrational Spectroscopy 9 (1995) 139-146

SPELTROSCOPY
Determination of free melamine content in
melamine-formaldehyde resins by Raman spectroscopy
Ma r t i ne L. Sc h e e p e r s b, Robe r t J. Me i e r a , La r s Ma r k wo r t a, J. M. Ge l a n b,
D. J. Va n d e r z a n d e b, Ber t J. Ki p a,*
a DSM Research, P.O. Box 18, 6160 MD Geleen, Netherlands
b Limburg University Department SBG, Universitaire Campus, B3590 Diepenbeek, Belgium
Received 22 September 1994
Abstract
We have shown that Raman spectroscopy can be used to determine the free melamine content in melamine-formalde-
hyde (MF) resins. In contrast to the conventional liquid chromatography method, the Raman spectroscopic method can be
directly applied to cured resins without sample preparation. The necessary assignments of bands were supported by
theoretical analysis of Raman frequencies. In addition, Raman imaging was used to determine the homogeneity of the free
melamine content in cured MF resins.
Keywords: Melamine; Melamine-formaldehyde; Raman spectrometry; Resins
1. Introducti on
In order to characterize mel ami ne- f or mal dehyde
(MF) resins, knowl edge about the free mel ami ne
content is of importance. In particular, for MF resins
with low f or mal dehyde/ mel ami ne ( F / M) ratios, the
concentration of free mel ami ne can be significant.
This mi ght have consequences for the net work struc-
ture, the shelf-life of resins and the mechanical
properties of the cured resin.
Conventionally, the content of free mel ami ne in
MF resins is determined by liquid chromat ography
* Corresponding author.
Elsevier Science B.V.
SSDI 0 9 2 4 - 2 0 3 1 ( 9 4 ) 0 0 0 9 1 - 3
(LC) after extraction with water. This method, how-
ever, can only be applied to the determination of free
mel ami ne in soluble resins, a serious limitation. In
the present paper we describe a Raman spectroscopic
met hod which allows for the determination of free
mel ami ne content, not only in a soluble resin but
also in a cured resin. The accuracy of the Raman
met hod is compared to results obtained using the
more conventional LC analysis.
Typical endproducts of MF resins are pressed
plates. The Raman met hod is applied to these kinds
of plates maki ng use of the ability to obtain local
information about the free mel ami ne content. It will
be shown that mappi ng at the /xm level of the free
mel ami ne content can be done using Raman spec-
troscopy.
140 M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146
2. Experimental
2.1. Ma~rm~
Six partly cured MF resins, still soluble in water,
were used for calibration purposes (calibration
resins). The free melamine content varied between
ca. 10 and 40%. In all cases low F / M ratios were
used.
For testing the method, three resins were cured to
a high extent (test resins). The first was an F / M =
1.7 resin, the second an F / M = 1.0 resin. Both were
cured at elevated pressure and temperature (145C,
85 bar, 45 min). For comparison the F / M = 1.7
cured resin was mixed physically with pure melamine
to obtain an overall F / M ratio of 1.0.
2.2. Methods
LC
A Model 1050 liquid chromatograph (Hewlett
Packard) equipped with a UV spectrophotometric
detector set at 235 nm was used for the determina-
tion of free melamine in still soluble MF resins. A
stainless-steel reversed-phase LC column (125 mm
X 4 mm i.d.) packed with Nucleosil 120-5 C18
(Machery and Nagel) was used. The eluent was a
wat er-acet oni t ri l e mixture at a combined flow-rate
of 1 ml mi n-1. The solvent program was set initially
to 100% water and 0% acetonitrile and then progres-
sively changed to 90% water and 10% acetonitrile
during the analysis period of 25 min.
Raman spectroscopy
Most of the Raman spectra were recorded on a
Bruker Model FRA 106 FT Raman module, attached
to a Bruker IFS 66 spectrometer and using a Nd:YAG
excitation at 1064 nm. No sample preparation was
used. Each spectrum represents a collection of 100
scans at a resolution of 4 cm- 1. All collected spectra
were transferred to a PC for further analysis using
Spectra Calc software (Galactic Industries) for curve
fitting.
Raman imaging was performed on a Dilor XY800
Raman spectrometer equipped with an imaging en-
trance chamber. By using a scanner, the incoming
laser beam is focused along a line at the sample
surface. Spectra of individual points are collected
using a CCD detector. Excitation was done with an
Ar + laser operating at 514.5 nm, the spectral resolu-
tion was 2 cm- 1, the total acquisition time for the
image was ca. 10 min using a laser power of about
25 mW at the sample. All spectra were collected in a
confocal way, ensuring high spatial resolution, both
in the depth and the lateral dimension. For the
combination of microscope objective ( X 100) and
confocal pinhole ( 150/ ~m) used, a lateral resolution
of ca. 0. 7/ z m and a depth resolution of ca. 2 /xm
can be obtained. For further comments on depth of
focus actually attainable we refer to Tabaksblat et al.
[1]. By moving the sampled line in a direction per-
pendicular to its expansion using a stepping sam-
piing stage, a matrix of spectra is obtained for the
scanned area of the sample. Subsequent data manipu-
lations were applied in order for the spectral infor-
mation to be transformed into an image. For a more
detailed description of the experimental set-up, the
reader is referred to [2].
2.3. Computational details
The calculation of the vibrational frequencies was
accomplished by the DISCOVER version 2.2.0
molecular mechanics program using a recently de-
veloped force field for melamine [3], which was
incorporated in the CFF91 force field. The structures
were displayed using INSIGHTII version 2.2.0 [4].
Force field calculations in their present form are not
capable of handling Raman intensities. It is possible,
however, knowing the eigenvectors (displacement
vectors of the atoms during normal mode vibration)
as obtained from the force field frequency calcula-
tion, to calculate the IR and Raman activities from
the transformation properties of the eigenvectors un-
der the symmetry operations of the symmetry group
[5]. Using these rules, from the list of calculated
frequencies, the appropriate frequencies could be
identified.
3. Results and discussion
In this investigation Raman spectroscopy was used
to determine the free melamine content in MF resins.
As a reference method, the determination of free
M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146 141
, --? .
r~
v
E
b
0
1200 10'00 8[)0 660 500
Wovenurnber ( c r n - 1)
Fig. 1. FT-Raman spectra from 500 to 1800 cm - I of (a) melamine
and (b) a cured MF resin.
mel ami ne contents of solvable MF resins was carried
out by LC after wat er extraction [6].
In the Raman spect rum of mel ami ne intense, sharp
bands at 676 and 975 cm -1 are observed (Fig. l a).
Both these bands have been attributed to deforma-
tions of the triazine ring [7]. Surprisingly, the 676
cm -1 band is al most absent in the spectra of MF
resins, whereas the band at 975 cm - t remains (Fig.
l b). The Raman spectra of well-characterized MF
adducts and resins (LC, NMR) with varyi ng
f or mal dehyde/ mel ami ne ( F / M) ratio, indicate that
the 676 cm- 1 band vanishes as the mel ami ne ring is
substituted. For MF resins that contain free melamine,
as was determined by LC, the 676 cm- 1 band is still
present.
These data suggest that it might be possible to use
the intensity of the 676 cm- 1 band for determination
of the free mel ami ne content in MF resins. In a
preceding paper [8] we have shown that the band at
975 cm -1, assigned to the triazine ring breathing
vibration, can be used for quantification of the total
0
g
1100 Iooo 9 6 o 8 6 0 7 6 0 6 6 0 5 S o
Wovenumber (cm- I)
Fig. 2. FT-Raman spectrum of an MF resin, base-line configura-
tion.
mel ami ne content of an MF resin. This suggests that
the ratio R,
A676
R = / R M x 1 0 0 % ( 1)
A975
can be used to quantify the percentage of mel ami ne
that is present in the unsubstituted form. A676 and
A975 a r e the areas of the band at 676 cm -a assigned
to the in-plane ring deformation and the band at 975
cm -a assigned to the ring breathing vibration, re-
Table 1
Determination of free melamine content in partially cured
melamine formaldehyde resins (still soluble) by LC and Raman
spectroscopy (calibration samples)
Resin no. % Free mel ami ne
Liquid chromatography Raman spectroscopy
1 19.5 19.4
2 13.0 11.6
3 13.5 12.8
4 16.3 15.9
5 10.8 8.9
6 40.6 39.2
142 M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146
Fig. 3. Eigenvectors belonging to the 675 cm-1 (left) and the 984
cm-1 (right) mode of melamine as revealed from the force field
calculations.
s pect i vel y; R M - M M
- - A 6 7 6 / / A 9 7 5 , whi ch wa s cal cul at ed
f r om t he Ra ma n s pect r um of pur e mel ami ne.
For t he cal i br at i on r esi ns, st i l l sol ubl e, Ra ma n and
LC anal ys es wer e per f or med. The r egi on ar ound
(8) 676 mr ' (b) 670 c m"
1000 c m- 1 i n t he Ra ma n s pect r um consi st s of sev-
er al ove r l a ppi ng bands. I n or der t o ext r act t he i nt en-
si t y of t he 975 c m- 1 me l a mi ne band, spect r al decon-
vol ut i on has been car r i ed out on t hi s cl ust er of
bands. Lor ent zi an band shapes wer e used t o des cr i be
t he band pr of i l es. The 676 cm - 1 band i s s uper i m-
pos e d on a br oa d band st r uct ur e ext endi ng over t he
5 5 0 - 8 0 0 c m - 1 r ange. As i l l ust r at ed i n Fi g. 2, t he
ar ea of t he 676 c m- 1 is det er mi ned by cal cul at i ng
t he ar ea of t he s haded area. Tabl e 1 s hows t he
c ompa r i s on of t he per cent age of f r ee me l a mi ne ob-
t ai ned by LC and t hat obt ai ned by Ra ma n spec-
t r os c opy of s ome t ypi cal s ol ubl e MF r esi ns. The
per cent age of f r ee me l a mi ne obt ai ned f r om Eq. 1 by
IrRQ 033
F~Q 03S
( I)
(d) So4 c m" (e) s e e m- , (J)
( h) 6 4 9 c m"
(C) dlGO c m"
( k
f f l
Fig. 4. Eigenvectors representing vibrations of methylolated melamines showing the various relevant vibrations. The indicated frequencies
are the force field calculated frequencies. For further explanation see text. (a-e) Vibrations around 645 cm -1 in monomethylolmelamine;
(f-i ) vibrations around 645 cm-2 in N,N',N"-trimethylolmelamine; fj -m) vibrations around 645 cm-1 in hexamethylolmelamine.
M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146 143
Raman spect roscopy is in good agreement with those
obtained by LC. The accuracy of the Raman met hod
is about 10% (relative), whereas the accuracy of the
LC met hod is about 2- 3%.
The above met hod was used to determine the free
mel ami ne content of three cured MF test resins, as
described in the experimental section. For these sys-
tems, it was impossible to use LC because of their
insolubility. Using Raman spectroscopy, the free
mel ami ne content could be measured quite easy
without any sampl e preparation. For the cured resin
with F / M = 1.7 no free mel ami ne was detected; for
the cured resin which was made using F / M = 1.0, a
free mel ami ne content of ca. 4% was found. For the
test resin, in which free mel ami ne was mi xed physi-
cally, a free mel ami ne content of 20% was mea-
sured.
Although the experimental results presented above
seem to be solid, it remains a surprising fact that the
676 cm -~ ring mode vanishes upon methylolation,
whereas the 975 cm- 1 band retains constant inten-
sity. In order to support the current interpretation of
the experimental data, force field calculations were
performed empl oyi ng a recently devel oped force fi el d
for mel ami ne and related compounds [3]. Both the
676 cm -1 and the 975 cm -1 Raman bands have
generally been assigned to ring breathing modes [7].
Thi s assignment was confi rmed by the current analy-
sis of the eigenvectors (displacements of atoms dur-
ing normal mode vibration), which have been dis-
pl ayed in Fig. 3. The force field calculations re-
vealed the corresponding frequencies at 645 cm- 1
and 966 c m- l , respectively. The symmet ry proper-
ties of these eigenvectors indicate the vibrational
modes to be Raman-act i ve rather than IR-active.
This is in agreement with the experimental findings,
and therefore lends support to the assignments made.
When the spectrum of monomet hyl ol mel ami ne
was calculated, the frequency at 645 cm- 1 was not
found. Since we do not know beforehand which
frequency to l ook for in the case of the substituted
mel ami ne, we have analysed all the normal modes in
the frequency range around 645 cm -1. In Fig. 4 a - e
the eigenvectors of the five nearest-by frequencies
calculated for monomet hyl ol mel ami ne have been
displayed, with calculated frequencies at 676, 670,
659, 595 and 568 cm -1. From Fig. 4 a - e we see that
all five modes of monomet hyl ol mel ami ne have
eigenvectors ent i rel y di ssi mi l ar to that of the 645
cm- 1 mode in melamine. For the higher substituted
melamines, similar behavi our is observed. The
eigenvectors related to the four nearest-by frequen-
MELAMINE
( a ) 9 6 6
MONOMETHYLOLMELAMINE
( b ) ~ 7 ~ - , ~ / ~
TRIMETHYLOL MELAMINE
_ _ _ ~ ( c ) 9 6 9 cm"
TRIMETHYLOLMEt,AMINE
HEXAMETHYLOLMELAMINE
Fig. 5. Eigenvectors representing vibrations of methylolated melamines showing the various relevant vibrations. The indicated frequencies
are the force field calculated frequencies. For further explanation see text. (a) Vibration around 975 cm- ] in melamine; (b) vibration around
975 cm -1 in monomethylolmelamine; (c-d) vibrations around 975 cm -1 in N,N',N'-tfimethylolmelamine; (e) vibration around 975 cm -1
in hexamethylolmelamine.
144 M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146
cies for N,N',N'-trimethylolmelamine and for hex-
amethylolmelamine have been displayed in Fig. 4f - i
and Fig. 4j - m, respectively. The change in character
of vibration and the loss of the symmetry properties
explain the drop in intensity of the 676 cm-1 Raman
band upon methylolation.
The 975 cm -1 band, however, shows no such
dependence on substitution. Scheepers et al. [8] ob-
served the 975 cm -1 band in all of their meth-
ylolmelamines in the range 975-980 cm -1 and
therefore attributed it to the triazine ring vibration. In
addition to the frequency of the band also its inten-
sity is found to be practically constant. Despite these
experimental observations, the character of this mode,
involving a vibration in the triazine ring which then
has to carry with it the substituents (methylols),
would seem to suggest that the higher mass on the
ring and the lowering of symmetry would seriously
affect both frequency and intensity of this band.
Therefore we calculated the frequencies for several
of the methylolated melamines, i.e. monometh-
ylolmelamine, the two different trimethylolme-
lamines, and hexamethylolmelamine. The frequen-
cies for the ring mode corresponding to the 984
cm -1 band in unsubstituted melamine are 966, 969,
972 and 981 cm -1 for the monomethylolmelamine,
the two types of trimethylolmelamine and hexameth-
ylolmelamine, respectively, the corresponding struc-
tures with eigenvectors being displayed in Fig. 5.
The force field calculations thus substantiate the
assignment of these bands to the ring breathing
mode, the frequency is practically constant, and be-
J
1 35
(b. )
1 0 8
61
5 4
2 7
1147
i
' i
9 9 9 . 2 4 8 5 1 . 4 5 7 0 3 . 6 7
1 0 8
1 35
t
i c )
0
1 1 4 7
J
9 9 9 . 2 4 8 5 1 . 4 5 7 0 3 . 6 7
Wavenumbers (cm-l)
( a ) 7
' - ' 1. gO ] ( d ) ' ' ' : : : : : : i
i 1. 06
i
1. 60
I 0 1 2 3 4 5 6 7 8 9 10 11
position along extracted profile (Raman pi xds - the
3.6pro width per pixel; position 0 corresponds to the
r i g h t hand side of the image)
Fig. 6. g a ma n i magi ng resul t s for a pr essed MF plate ( used resin: physi cal mi xt ur e of F / M = 1.7 resin and pure mel ami ne), showi ng (a) t he
2D- Raman i mage const ruct ed us i ng t he ratio of t he 676 and 975 c m- ] band, (b and c) t wo spect ra of t wo pi xel s and (d) an extracted profile.
M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146 145
cause the character of the mode is also unchanged
the Raman intensity is expected to be practically
constant as well.
In conclusion, we have shown that Raman spec-
troscopy can be used to determine the free melamine
content in MF resins. In contrast to the conventional
LC method, the Raman spectroscopic method can be
directly applied to cured resins and is relatively
quick, but has a lower accuracy. A theoretical analy-
sis of Raman frequencies has elucidated the fact that
the 676 cm-1 ring mode vanishes upon methylola-
tion whereas the 975 cm-1 ring mode is practically
unchanged upon methylolation, both in frequency as
well as in intensity. A more complete theoretical
analysis of the Raman spectra of the methylolated
melamines will be reported elsewhere [11].
Now that we have established the Raman spectro-
scopic method for the determination of the free
melamine content we will show an example of a
practical application. In many cases the MF resins
are used in a pressed-plate form. Question is to
determine the homogeneity of the free melamine
content in a cured, pressed MF plate. One of the
advantages of Raman spectroscopy is its potential to
be used for analysis on a small size scale. Using
confocal Raman microspectroscopy, one is able to
obtain spectral information from a small volume
element (/ . t m scale) [1,9]. The development of Ra-
man imaging instruments [10] allows to image the
free melamine content at /xm level in an MF resin
sample. Using the Dilor XY800 imaging spectrome-
ter, an area of 44 X 44 /zm 2 of a pressed MF plate
was studied. For this purpose we used the F / M = 1.7
resin and the F / M = 1.0 resin made from a mixture
of the F / M = 1.7 resin and pure melamine.
For the F / M = 1.7 resin, no indications for free
melamine were observed in the scanned area. For the
sample made with a deliberately high free melamine
content, the mixture of F / M = 1.7 and pure
melamine, important inhomogeneity is observed. The
results are shown in Figs. 6 and 7. The analysed area
was divided in 12 X 12 Raman pixels (each pixel
represents an area of 3.7 X 3.7 /xm2). For each of
these pixels (see Fig. 6A) a good (confocal) Raman
spectrum was obtained. Two spectra are shown in
Fig. 6, one corresponding to a pixel with a low free
melamine content (low 676 cm-1 band, Fig. 6B) and
one corresponding to a pixel with a high free
melamine content (high 676 cm -1 band, Fig. 6C).
The free melamine content was quantified by calcu-
lating the 676/ 975 cm -1 intensity ratio (in the
present Dilor Spectrimage software it was not possi-
ble to calculate real band area ratios). The grey scale
in the Raman image represents this ratio, i.e., the
Fig. 7. Pseudo-3D representation of Raman image present ed in Fig. 6, the intensity ratio of the 676 and 975 c m- ~ band bei ng plotted in the
z-direction.
146 M.L. Scheepers et al. / Vibrational Spectroscopy 9 (1995) 139-146
darker t he pi xel , t he hi gher the i nt ensi t y ratio and
free mel ami ne content. By usi ng a ps eudo- 3D pre-
sent at i on in whi ch the i nt ensi t y ratio is pl ot t ed in the
z-di rect i on (see Fig. 7), it be c ome s cl ear that there
are regi ons o f high free mel ami ne cont ent o f ca. 10
/ zm di amet er. Fr om t he 2D- i mage in Fig. 6 al so a
line profi l e can be ext ract ed (Fig. 6D), s howi ng the
change o f t he 6 7 6 / 9 7 5 cm -1 band i nt ensi t y ratio
al ong a line in the Raman i mage.
The pr esent ed resul t s cl earl y s how that Raman
i magi ng is a usef ul t echni que to st udy t he i nhomo-
genei t y o f the free mel ami ne cont ent in cured
me l a mi ne - f or ma l de hyde resins. Thi s can be o f par-
ticular i mport ance si nce mechani cal propert i es of t he
cur ed resin can be sever el y i nfl uenced by het ero-
genei t i es on the / zm level.
Acknowledgements
The aut hors wi s h to acknowl edge t he DSM man-
agement for their permi ssi on to publ i sh this wor k.
Dr. P. M. Brandt s is grat eful l y acknowl edged f or his
critical remarks. Di l or SA France is t hanked f or
gi vi ng us t he oppor t uni t y to wor k on their XY800
i magi ng s ys t em and for hel pful di scussi ons.
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