Journal of Wuhan University of Technology-Mater. Sci. Ed. Feb.

2009 127

DOI 10.1007/s11595-009-1127-3

Flame-retardant Mechanism of Magnesium

Oxychloride in Epoxy Resin

QIN Linqing1,2, HUANG Zhixiong3, ZHANG Lianmeng1, WANG Yanbing3

(1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China;
2. Center for Material Research and Analysis, Wuhan University of Technology, Wuhan 430070, China;
3. School of Materials Science and Enginecring, Wuhan University of Technology, Wuhan 430070, China)

Abstract: Flame-retardant mechanism of magnesium oxychloride （MOC） in EP was in-

vestigated by limiting oxygen index (LOI), XRD, SEM, TG-DTG and DSC. The results show that
MOC performed well as an inorganic flame-retardant in EP. When the content of MOC is 50%, the
LOI of EP reaches 29.6% and mass of residual char reaches 9.6%. The flame retarde mechanism of
MOC is due to the synergies of diluting, cooling, catalyzing char forming and obstructing effects.
Key words: magnesium oxychloride; epoxy resin; flame-retardant properties; flame retarded
mechanism

1 Introduction the flame-retardant mechanism of MOC flame-retarded

Epoxy resin(EP) is a very important polymer mate-
rial in the fields of machinery, wiring, electronics, avia-
tion, chemical, transportation, construction and so on.
Since EP is an inflammable material due to its limiting
oxygen index is only 19.8%[1,2], its application is greatly
restricted and the research of its fire-retardant properties
is very necessary.
At present, the developmental direction of the flame
retardants of polymer materials is high efficient, low
toxic and smokeless. The applied investigation of inor-
ganic flame retardants and their flame retardant mecha-
nisms is one of the most active parts in the domain of
flame-retarded polymer[3-9].
Magnesium oxychloride(MOC), Mg3(OH)5·Cl4H2O,
has outstanding mechanical and physical properties such
as excellent wearability, low density and high strength. It
is widely used in industrial flooring, wall materials,
fireproof products, protective layers against fire, foamed
heat-insulation materials, concrete, binder of grind-
ing(abrasive) tools, etc[10-14]. However, report about its
use as inorganic flame retardants in flame-retarded EP is
barely found. In this paper, advanced testing technologies
were used to analyze the flame-retardant properties and
(Received: December 13, 2006; Accepted: Sep. 28, 2007)
QIN Linqing (秦秦秦): Assoc. Prof; Ph D；E-mail：qinlqzg@163.com
Funded by the Defense Pre-research Project of the Eleventh-Five-Year-Plan of
China (No. 51312040404)
EP.
2 Experimental
2.1 Raw materials
Basic magnesium carbonate and polyethylene
polyamine were analytical grade. EP (CYD-127) was
purchased from the Baling Chemical Ltd of China Pet-
rochemical Corporation.
2.2 Preparation of MOC
The magnesium oxide used in the study was ob-
tained by heating basic magnesium carbon-
ate，4MgCO3 · Mg(OH)2 · 5H2O，in an electric
furnace at 900 ℃ for 2 h. The raw material basic mag-
nesium carbonate and resultant products MgO were con-
firmed by X-ray diffraction. MOC was fabricated by a
hydrating reaction of MgO/ MgCl2• 6 H2O/H2O at room
temperature for 7 d, and grinding the hydrating products. The
molar ratio of MgO∶MgCl2 • 6 H2O∶H2O was 5∶1∶8.3.
2.3 Preparation of flame-retardant EP
The EP and MOC powders were added into the
beaker under stirring. The weight ratios of MOC to EP
and MOC were changed from 16.7%, 28.6%, 37.5%,
44.4% to 50.0%. The polyethylene polyamine (15 wt%)
as a curing agent was added to the above mixtures, and
then mixed homogeneously. The mixture was filled into
the molds. The samples were taken out of the molds and
polished them by sanding machine.
128 Vol.24 No.1 QIN Lingqing et al: Flame-retardant Mechanism of Magnesium…

2.4 Performance test of flame-retardant tern，indicating that the flame retardant is a pure crys-
EP talline material.
The surface morphology of burned sample was ob-
served through JSM-5610LV scanning electron micro-
scope (SEM) made in Japan. Limiting oxygen in-
dex(LOI)s were measured by HC-2 oxygen index appa-
ratus made in Nanjing Jiangning Analytical Instrument
Factory, according to GB/T2406-93. The X-ray diffrac-
tometer(XRD) used is a rotating-target X-ray diffracto-
meter(D/Max-RB) made in Japan Rigaku Company. Cu
target was adopted and the X-ray tube voltage and current
were 40 kV and 50 mA respectively. The scanning speed
was 10°/min with the step of 0.02°, ranging from 5° to
70°. Comprehensive thermal analysis (TG-DSC-DTG)
was fulfilled with comprehensive thermal analysis ap-
Fig.1 Relationship between the LOI of EP and its MOC content
paratus (NETZSCH5) made in German NET Company.
The temperature ranged from room temperature to 700 ℃
with the heating rate of 10 ℃/min. Nitrogen was adopted
as a protective atmosphere and the current speed was
10 mL/min.

3 Results and Discussion

3.1 Flame retardant properties
There were droplets when pure EP was burning,
while no droplet dropped during the combustion of
EP/MOC composite. The burning residue of EP/MOC
was coked and the burning was slow without smoke.
Fig.2 XRD pattern of MOC
The impact that MOC acted on the LOI of EP is
Fig.3 shows the XRD patterns of the sample before
shown in Fig.1. The LOI of the samples increased and the
combustion and the different sections of the combustion
flame-retardant effect improved with the addition of
residue. Sample 0 is before combustion, and combustion
MOC, which was consistent with the results of combus-
residue sections are identified as samples 1, 2, 3 and 4
tion tests. When the MOC content was 28.6 wt%, the LOI
according to their distance from flame decreased. Sample
of the composite rose from 19.8 wt% (the LOI of pure EP)
0 contains crystalline MOC and amorphous EP, which
to 23.4 wt% and reached self-extinguishing standard
implies that there is no chemical reaction occured be-
(22.6 wt%). When the MOC content reached 44.4 wt%,
tween MOC and EP. Therefore, MOC is classed as an
the samples’ LOI reached 27.2 wt%, which exceeded the
additive oxygen flame retardant. MOC reduced the con-
flame-retardant standard (26.8 wt%)[15].When MOC
centration of EP by the diluting action, which makes EP
content was 50.0 wt%, the samples’ LOI reached almost
less inflammable. Samples 1, 2, 3 contain MgO and a
30 wt%. Fig. 1 shows that the samples’ LOI growth ac-
mesophase. That is to say, during the combustion, the
celeration increases with the growth of MOC content.
amorphous structure of EP was destroyed and MOC had
The investigation shows MOC is a good inorganic
not been decomposed completely and the mesophase is
flame retardant to EP and can reach a relatively good
weakened and MgO increased from sample 1 to sample 3.
flame-retardant effect while the adding ratio is not too
Sample 4 contained only MgO, impling that MOC had
much. been completely decomposed to MgO during the sample
3.2 X-ray diffraction (XRD) analysis combustion. It shows that in different sections, combus-
The X-ray diffraction of the flame retardant used in tion extents are different as well as the burning tem-
the experiment matches that of the PDF standard card perature, resulting in components of the residues differ-
(7-420) of magnesium oxychloride(Shown in Fig.2). No ent from each other. Samples 1, 2, 3 and 4 experienced
peaks of other phases appeared in the XRD pat- the temperature from low to high. In the samples’ com-
 Journal of Wuhan University of Technology-Mater. Sci. Ed. Feb. 2009
bustion process, MOC firstly dehydrate into a mesophase,
and ultimately decompose into MgO.
Fig.3 XRD patterns of the samples and the combustion residues
Based on above analysis, the added MOC was
heated and finally decomposed into MgO during the
EP-based samples’ combustions, HCl gas and water va-
por are released at the same time to dilutes the flammable
gas and oxygen; this obstructs the air diffusion and heat
radiation to reach the aim of preventing combustion.
3.3 DSC analysis
Fig.4 is the DSC curves of the samples. MOC
gradually decomposed in the heating process, corre-
sponding to the endothermic peak of the DSC curves.
When the temperature is between 100 ℃ and 260 ℃, it
releases crystalline water, corresponding to two endo-
thermic peaks at 134 ℃ and 189 ℃ respectively. An
endothermic peak at 335 ℃ appeared due to the sepa-
rating-out of a part of structural hydroxyl. There is an
endothermic peak at 426 ℃ because HCl is released at
this period and the heat is further absorbed. No endo-
thermic peak appeared after the temperature is higher
than 450 ℃ which indicated that the sample does not
decompose any more and the product is MgO, which is
shown in Fig.5(a).
Fig.4 DSC curves of MOC, EP and EP/MOC(50 wt%)
129
Fig.5 TG-DTG curves of MOC, EP and EP/MOC(50 wt%)
The EP is releasing heat during the heating process.
There is a smaller exothermic peak at 312 ℃, named
initial decomposition exothermic peaks, caused by
elimination reaction. An endothermic peak appears at
354 ℃ because EP melts thus absorbs heat at this tem-
perature. The exothermic peak at 595 ℃ is the termina-
tional decomposition exothermic peak, caused by the
cracking of the skeleton[16].
According to the DSC curve of EP/MOC samples,
there is a small endothermic peak caused by endothermal
dehydration of MOC at 107 ℃ and 180 ℃ respectively.
There is a small exothermic peak at 322 ℃, the initial
decomposition exothermic peak of EP, whose starting
temperature is 10 ℃ higher than that of pure EP. It shows
that MOC can enhance the thermal stability of EP at low
temperature and is conducive to flame retardance. No
obvious melting endothermic peak appears at 350 ℃,
which implies that MOC can enhance the anti-melting
capability of EP. The loose-bodied exothermic peak at
645 ℃ is cause by the frame cracking and its starting
temperature is 50 ℃ higher than the decomposition
temperature of pure EP. It shows that MOC can enhance
the thermal stability of EP under high temperature and
redound to flame retardance. During the temperature
130 Vol.24 No.1 QIN Lingqing et al: Flame-retardant Mechanism of Magnesium…

range of 645-700 ℃, heat releasing velocity of EP/MOC At 700 ℃, residue of EP/MOC was 28.8%, and
is slow, contrast to the high heat releasing speed of EP. deducting 19.2% which was the MgO generated by the
That indicates that MOC can form a stable compound decomposition of MOC, the residual char was 9.6%. The
during the thermal decomposition of EP. residual char might generate in the thermal-oxygen in-
Fig.4 shows that heat releasing is decreased with the duced crosslinking reaction of polymer catalyzed by the
addition of MOC and that the MOC reduced the releasing activity MgO generated by the decomposition of MOC.
heat during the sample decomposition. Because a large The residual char formed a protective film on the surface,
amount of heat is absorbed during the decomposing which weakens the transfer of heat and substance in order
MOC process, the steam generated can also absorb the to retard the combustion.
latent heat and take some heat away from the sample so 3.5 SEM analysis
as to restrain temperature becoming higher and decrease There are large amount of molten mass and holes on
heat. the surface of combustion residue of EP, as well as
3.4 TG-DTG analysis wrinkled topography, and the holes are smooth in
TG-DTG curves of MOC, EP, EP/MOC(50%) are Fig.6(a). This might be caused by the large amount of gas
shown in Fig.5. and molten materials during the combustion.
From 100 ℃ to 260 ℃, MOC released crystal water
and the weight reduced by 27.7%. From 260 ℃ to 380 ℃,
partial structural hydroxyl separated out and the weight
declined by 13.9%. HCl was generated between 380 ℃
and 450 ℃, and weight declined by 15.5%. Above 450 ℃,
weight declining almost ceased and the residue was
MgO.
Under 260 ℃, the weight of EP only reduces by
5.6% for the temperature was not high enough, and the
elimination reaction of EP was slow. When the tem-
perature reached 260 ℃, the elimination reaction speed
turned faster and reached its max value at 315℃, the
weight sharply declined. When above 420 ℃, the skele-
ton cracking speed became still faster and reached the
max at 596 ℃. At 700 ℃, the epoxy weight of residue
was almost 0%, which shows the EP was completely
decomposed.
The shape of EP/MOC composite’s TG-DTG curve
is about equal with that of EP. Weight declined by 8.0%
under 260 ℃, and elimination reaction of EP is occurred
and MOC is dehydrated in this period. When the tem-
perature reached 260 ℃, the weight declined sharply,
while the elimination reaction was fast and reached its
max value at 335 ℃, which is 20 ℃ higher than that of
pure EP, indicating that MOC can enhance the thermal
stability of EP under low temperature and is conducive to
flame retardance. When above 460 ℃, the weight decline Fig.6 SEM images of combustion residue of EP
became slow because the cracking speed of EP/MOC and EP/MOC(50 wt%)
skeleton was smaller than that of pure EP. Since the The combustion residue of EP/MOC(50.0 wt%) is
practical mass of EP/MOC thermal decomposition resi- three-dimensional reticulation with many small wrinkled
due was more than the calculated, a stable car- particles and irregular holes on the surface, as shown in
bon-containing residue was likely to be generated, Fig.6(b). Firstly, duing the sample burning, MOC de-
showing that MOC can enhance that MOC can improve composed, discharging gas, and generating activity ap-
the thermal stability of EP under high temperature and erture particles. Then, these particles with a strong ad-
redound to flame retardance[17]. sorbability adsorbed the melt EP and shaped as walnuts.
It shows that MOC can enhance the anti-melting capa-
 Journal of Wuhan University of Technology-Mater. Sci. Ed. Feb. 2009
bility of EP, as a result, there is no dripping during the
combustion of samples[18]. The loose three-dimensional
network structure contributes to the obstruction and iso-
lation of heat so as to retard combustion[3].
Comparing Figs.6(a) and (b), the combustion resi-
due of EP is of high desity and its gas permeability is
worse, therefoer deflagration phenomenon accured. The
combustion residue of EP / MOC(50%) is looser, and its
permeability is beller, so that there is no deflagration
phenomenon happened.
4 Conclusion
MOC can decline the decomposition heat of EP,
enhance the thermal decomposition stability and the
anti-melting capacity of EP, promote the mass of residual
char, and have a good flame-retardant effect. MOC,
possessing functions of diluting, cooling, catalyzing char
forming and obstructing, is a very promising flame re-
tardant.
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