Professional Documents
Culture Documents
Weathering Study of Epoxy Paints-Main
Weathering Study of Epoxy Paints-Main
Weathering Study of Epoxy Paints-Main
Abstract
The weathering characteristics of TiO2 -based paints of diglycidyl ethers of bisphenol A (DGEBPA), bisphenol F (DGEBPF), bis-2,6-xylenol
F (DGEBXF), bis-2,6-xylenol S (DGEBXS) and bis-2,6-xylenol (DGEBX) with various curing agents have been studied by subjecting them
to accelerated and environmental weathering. Of all the epoxy resins, the paint using DGEBPA gave the best weathering characteristics with
better chalk resistance, optimum yellowing and good gloss retention when cured with amine terminated dimer fatty acid-based polyamide.
The methyl substitutions on aromatic ring and presence of methylene and sulfone groups between the phenolic moieties caused enhanced
degradation of epoxy resins as evidenced by their faster chalking on exposure. When cured with an aminosilane compound all the epoxy
paints showed excellent improvement in chalk resistance but were associated with poor initial gloss and more yellowing during exposure. The
relationship between the two types of weathering was found to be approximately two and a half hours exposure in accelerated ageing being
equal to 1 day in environmental weathering in Mumbai (India), thus leading to a nearly 10-fold acceleration of weathering.
2004 Published by Elsevier B.V.
Keywords: Epoxy resins; Curing agents; Paint; Accelerated weathering; Environmental weathering; Chalk resistance
1. Introduction
Epoxy resins have tremendous applications in the polymer
field because of their range of attainable properties and versatility [1]. However, due to the presence of aromatic moiety
generally they absorb at about 300 nm and degrade in the presence of UV light and humidity. Weathering of epoxy resins is
fairly good for castings and laminates but for thin films and
epoxy paints, it is generally regarded only as fair, because of
discoloration and chalking. This is the major cause of concern for the polymer chemists limiting the use of epoxies for
outdoor applications.
Kelleher and Gesner [2] have studied the degradation of
high molecular weight epoxy polymer of bisphenol A. They
found that there was a decrease in intrinsic viscosity as well
as gel formation, indicating that chain scission and crosslinking occurred simultaneously. The irradiation of bisphenol A
based polymers viz., polysulfone, polycarbonate and epoxy
resin led to chain scission as indicated by the reduction in
Corresponding author.
E-mail address: vcmalshe@hotmail.com (V.C. Malshe).
268
(PMDA), cyanuric acid (CA), sodium hydroxide, all of synthetic grade, were procured from Ranbaxy Fine Chemicals
Ltd.
2.2. Preparation
DGEBXF with EEW 195, DGEBXS with EEW 245 and
DGEBX with EEW 190 were synthesized using the standard method of epoxy preparation. In a typical method,
bisxylenols and epichlorohydrin were charged in 1:10 molar ratio in a four neck cylindrical glass vessel fitted with a
mechanical stirrer, addition funnel, condenser and thermometer. The mixture was heated to about 70 C and then 2.1 mol
of 40% aqueous sodium hydroxide solution was added drop
wise over a period of 1 h, the temperature being allowed to
rise to 110 C. The mixture was continued to reflux at 110 C
for 1 h, cooled and allowed to separate. The organic layer was
separated after washing with water and then filtered using a
sintered crucible. The filtrate was distilled to remove the excess epichlorohydrin to get a clear pale yellow viscous liquid
epoxy resin.
Simple solvent-based white paints using epoxy resin, TiO2
and xylenebutanol (1:1) solvent mixture were prepared in
ball mill by milling for 24 h. The curing agents FPA, TETA
and AS were added at the time of application whereas DICY,
CA, PA, TMA and PMDA were mixed during paint preparation in the ball mill. The pigment volume concentration
(PVC) of the paints including the curing agent was optimized
at 17% and the total solid content was 60%.
2. Experimental
2.3. Evaluation
2.1. Materials
DGEBPA (GY250) with epoxy equivalent weight (EEW)
180 was supplied by Ciba Speciality Chemicals, DGEBPF
(LAPOX XR40) with epoxy equivalent weight 185 by Atul
Ltd. Valsad, bis-2,6-xylenol F, bis-2,6-xylenol S, bis-2,6xylenol and rutile grade TiO2 by Filtra Catalysts & Chemicals Ltd., amine terminated dimer fatty acid based polyamide
269
Table 1
Chalking characteristics of epoxy paints exposed to accelerated and environmental weathering
Curing agents
Diglycidyl ether of
Diglycidyl ether of
BPA
BPF
BXF
BXS
BX
BPA
BPF
BXF
BXS
BX
250
250
100
150
100
100
150
800
200
150
100
100
100
100
100
600
100
50
100
100
100
100
100
400
100
50
100
100
100
100
100
300
100
50
100
100
100
100
100
400
150
120
60
60
45
45
90
90
45
45
30
30
30
60
270
45
30
45
30
30
30
60
210
45
15
45
30
30
30
60
120
45
45
45
45
30
30
45
180
270
Fig. 1. Variation of yellowness index of various epoxy paints exposed to accelerated weathering.
environment being equal to 24 h in environmental weathering for the climatic conditions prevailing in Mumbai, thus
leading to a nearly 10-fold acceleration of weathering.
3.2. Evaluation of yellowness index
The variation of yellowness indices with the exposure time
for the paints cured with FPA and AS are the only ones being reported since the other curing agents led to much faster
chalking (Figs. 1 and 2). The yellowness index was more
or less the same for all the paints, the maximum being for
DGEBPF and DGEBX. All the AS cured samples showed
more yellowing than the FPA cured ones. For all the samples, the major yellowing occurred in the initial duration of
exposure, after which it showed a little change. This was due
to the fact that once chalking occurred, the chalked pigment
formed a protective layer on the surface preventing the further
Fig. 2. Variation of yellowness index of various epoxy paints exposed to environmental weathering.
Fig. 4. Variation of % gloss of various epoxy paints cured with FPA exposed to accelerated weathering.
Fig. 5. Variation of % gloss of various epoxy paints cured with FPA exposed to environmental weathering.
271
272
4. Conclusions
The above study shows that of the weak links hypothesized:
(A) The aromatic moiety plays the major role in the degradation of epoxy resin. This is confirmed by the fact that
methyl substitution on aromatic part causes faster and
increased chalking of the paint as observed in the case
with DGEBXF, DGEBXS and DGEBX.
(B) The sulfone group in DGEBXS, followed by absence
of any group in DGEBX and the methylene bridge in
Acknowledgement
The authors wish to thank Mr. T.N. Venkatesan, Managing
Director, Filtra Catalysts & Chemicals Ltd., for the support
to this project.
References
[1] H. Lee, K. Neville, Handbook of Epoxy Resins, McGraw Hill Book
Company, 1967.
[2] P.G. Kelleher, B.D. Gesner, J. Appl. Polym. Sci. 13 (1969) 915.
[3] B.D. Gesner, P.G. Kelleher, J. Appl. Polym. Sci. 13 (1969)
21832191.
[4] A. Rivaton, L. Moreau, J.-L. Gardette, Polym. Degrad. Stab. 58
(1997) 321332.
[5] A. Rivaton, L. Moreau, J.-L. Gardette, Polym. Degrad. Stab. 58
(1997) 333339.
[6] M. Lalonde, T.H. Chan, Synthesis (1985) 817845.
[7] G.A. Olah, G.K. Prakash, R. Krishnamurthy, Advances in Silicon
Chemistry, JAI Press, Greenwich, 1991.
[8] M. Markovitz, L.S. Kohn, Epoxy Resins, Advances in Chemistry
Series, American Chemical Society Publications, 1970.
[9] M. Ouyang, P.P. Klemchuk, J.T. Koberstein, Polym. Degrad. Stab.
70 (2000) 217228.
[10] B. Ranby, J.F. Rabek, Photodegradation, Photo-oxidation and Photostabilisation of Polymers Principles and Applications, Wiley, 1975.