UDK 678.

7 ISSN 1580-2949
Professional article/Strokovni ~lanek MTAEC9, 49(5)821(2015)

V. RUSNÁK et al.: FLAME RESISTANCE AND MECHANICAL PROPERTIES OF COMPOSITES ...

821–824

FLAME RESISTANCE AND MECHANICAL PROPERTIES OF

COMPOSITES BASED ON NEW ADVANCED RESIN SYSTEM
FR4/12
NEGORLJIVOST IN MEHANSKE LASTNOSTI KOMPOZITOV NA
OSNOVI NOVIH NAPREDNIH SISTEMOV SMOL FR4/12

Vladimír Rusnák1, Soòa Rusnáková2, Ladislav Fojtl2, Milan @aludek2,

Alexander ^apka2
1Faculty of Metallurgy and Materials Engineering, V[B-Technical University of Ostrava, 17. listopadu 15, 708 33 Ostrava-Poruba, Czech
Republic
2Faculty of Technology, TBU in Zlín, Nad Stranemi 4511, 760 05 Zlín, Czech Republic
[email protected]

Prejem rokopisa – received: 2014-09-10; sprejem za objavo – accepted for publication: 2014-11-24

doi:10.17222/mit.2014.223

Composite materials used in the transport industry and also in other sectors must have a certain degree of flame resistance. For
this purpose, commonly used flame retardants are based on halogen compounds in the liquid state or aluminum hydroxide in the
solid state. Solid flame retardants have a negative effect on the processing and mechanical properties. Low viscosity and rapid
wettability of fibers are very important, especially in an resin transfer molding (RTM) process.
Therefore, a new advanced matrix system based on phosphorus flame retardants was developed. The flame resistance and
mechanical properties of the composite materials produced from the new resin system were tested. Furthermore, the processing
parameters and tests are described in the article.
Keywords: flame-retardant composites, phosphorus, RTM, vacuum infusion

Kompozitni materiali, ki se uporabljajo v industriji transporta in tudi v drugih sektorjih, morajo ustrezati dolo~eni stopnji
negorljivosti. Za ta namen so splo{no uporabljani zaviralci gorenja, ki temeljijo na osnovi spojin halogenov v teko~em stanju ali
na aluminijevem hidroksidu v trdnem stanju. Zaviralci gorenja v trdnem stanju imajo negativen vpliv na izdelavo in mehanske
lastnosti. Posebno majhna viskoznost in hitra omo~ljivost vlaken sta pomembni, posebno {e pri RTM-procesu.
Zato je bila razvita nova napredna matri~na zasnova na podlagi fosfornega zaviralca gorenja. Preizku{ene so bile odpornost proti
v`igu in mehanske lastnosti kompozitnega materiala, izdelanega iz novega sistema smol. V ~lanku so opisani parametri izdelave
in preizkusi.
Klju~ne besede: negorljivi kompoziti, fosfor, RTM, vakuumska infuzija

1 INTRODUCTION Flame retardants are the materials that prevent or

retard the burning of a material and are indispensable for
Composite materials based on a polymer matrix and plastic products, electrical applications, construction
glass reinforcement are often used in transport vehicles. materials, textiles, etc. Generally, they can be divided
The main reasons for their utilization are their low mass, into two main groups: the reactive organic and non-reac-
excellent formability and relatively low production costs tive inorganic compounds (additives). The reactive orga-
for low and medium manufacturing series. nic compounds include molecules of halogens (bromine
When composite and sandwich structures are used in and chlorine), melamine compounds, phosphate com-
train applications, they have to fulfill different require-
pounds and many others.2 Their main advantage is that
ments. The first (or the main) requirement is the fire
they do not change the physical properties of the resin.
safety.1 In addition to the fire safety of these materials,
Generally, the amount of the flame retardant in a poly-
relatively high mechanical properties, dimensional and
thermal stabilities and health safety are required. For mer matrix depends on the retarding effect. However, it
example the French standard NF F01-28: Fiber rein- is necessary to take into account the possibility of a
forced plastic in railway rolling stock requires a mini- negative effect influencing the mechanical and pro-
mum bending strength of reinforced plastics of up to 150 cessing properties of the polymer.
MPa, while maintaining the self-extinguishing properties The reactive inorganic compounds include aluminum
according to another French standard, NF F16-101. hydroxide (ATH) and magnesium hydroxide, red phos-
Polyester matrices reinforced with fiber reinforce- phorus, ammonium compounds, antimony compounds of
ments in various forms are primarily used for these antimony or boron, graphite, etc.3,4 These compounds are
applications. In these composite systems self-extinguish- insoluble in a polymer matrix and need to be added in
ing properties are primarily achieved with additions of higher concentrations (30–150 %) to achieve the right
flame retardants to the synthetic matrices. fire-retardancy level. They have a very negative influence

Materiali in tehnologije / Materials and technology 49 (2015) 5, 821–824 821

V. RUSNÁK et al.: FLAME RESISTANCE AND MECHANICAL PROPERTIES OF COMPOSITES ...

on the viscosity of the resulting mixture, thus limiting Table 1: Mechanical and processing properties of FR4/12 matrix
their use in the preparation of a composite with the Tabela 1: Mehanski in procesni parametri osnove FR4/12
vacuum infusion or RTM technology. And, last but not Matrix
least, they negatively influence the mechanical properties Material description
FR4/12
– the composites become less stiff and brittle. Viscosity (Brookfield LV 2/12, 20 °C) (mPa s) 6 475
They slow down the combustion process in different Tg/°C 105
ways, physically or chemically. The physical processes HDT/°C 68
include cooling the material, creating a protective layer Acid number, the KOH content (mg g–1) 2.5
(that continues to protect the remaining material, block- Hydroxyl number, the KOH content (mg g–1) 50
ing the combustion by limiting the access of air) or Tensile strength (MPa) 63
diluting the gas flame with retardant components. Tensile modulus (MPa) 3400
With respect to the chemical processes, flame Elongation (%) 2.2
retardancy is a reaction in the gaseous phase, leading to a Flexural strength (MPa) 3600
Flexural modulus (MPa) 130
release of significant amounts of water or carbon dio-
Oxygen index 32–34
xide. Thus, a reaction at this stage limits and slows down
a burning process. This group includes the flame
2.1.2 Reinforcements, coatings
retardants based on halogens. These compounds create
carbon ash on the polymer surface or a swelling under A multiaxial nonwoven fabric (bidiagonal and tri-
the protective layer of the ash to provide a better thermal axial fabric) was selected as the reinforcement. A
insulation.5 nonwoven fabric guarantees a high proportion of glass in
Some flame retardants based on halogens, such as a composite (hence, better mechanical properties). It also
polychlorinated biphenyls (PCB), or various brominated has a suitable drapability. In line with the requirements
flame retardants (polybrominated diphenyl ethers, poly- of the process technology, mats with the trade name
brominated biphenyls) may pose a health risk. The fire UNIFILLO ® were used for the RTM technology.
retardancy of a halogenated flame retardant is based on To determine the effect of the coating on the com-
the formation of a volatile-combustion hydrobromic or bustibility, two samples of the BÜFA gelcoat layer were
hydrochloric acid in the presence of hydrocarbons (e.g., provided.
toxic dioxins) at a temperature of around 350 °C.
Flame retardants based on phosphorus are the com- 2.2 Production methods and testing
pounds that are more environmentally friendly and their
The testing of the resin system was carried out at two
consumption is slowly growing. Phosphor flame retard-
levels. One level was the production of the test samples.
ants are already applied in matrices with phosphorus
These samples were produced on a simple plate or in a
amounts of about 5–8 %. They work very well for the
simple RTM mold. The second level of the matrix testing
polymers containing oxygen in the chain.
consisted of a production of real products (prototypes).
Production methods were chosen with respect to the
2 EXPERIMENTAL WORK environmental, health and economic aspects (producti-
vity), including two closed-production technologies –
2.1 Materials VIP (vacuum infusion process) and RTM (resin transfer
molding).
2.1.1 Matrix In addition to the newly produced matrix, a total of
An unsaturated polyester resin diluted with styrene, five composite materials (Table 2) of various com-
containing a phosphorus flame retardant incorporated positions as well as other polymer systems were
into the chain molecules was developed under the work- produced (Sample D was made from a phenolic prepreg,
ing title FR4/12 (Table 1). The goal was to prepare a Sample E was based on a commercial matrix). Samples
resin, which enables, due to its viscosity, a preparation of B and E were provided with a gelcoat. Firstly, the
the composite parts for rail vehicles using the RTM flexural test was realized according to ISO 178.7 With
method or the vacuum infusion method. Pure resin respect to the fire retardancy the oxygen index was
would also meet the requirement for a flame resistance recorded, and the tests of the flame spread and the
without the additives – the limited oxygen index (LOI) (partial) heat release were performed using the cone
must be higher than 30. The requirement for the maxi- calorimeter method.8,9
mum viscosity was 600 mPa s.6 The amount of phospho-
rus in the polyester chain is naturally limited since it 3 RESULTS AND DISCUSSION
greatly affects the mechanical properties. The resulting
formulation is designed in such a way that the mecha- The measured values of the mechanical properties
nical properties of pure resin match the mechanical and fire behavior are shown in Figure 1. As can be seen,
properties of the halogenated resins, normally used for the highest values for both flexural properties of the
the production of the composite parts for rail vehicles. samples prepared with the wet technology were obtained

822 Materiali in tehnologije / Materials and technology 49 (2015) 5, 821–824

 V. RUSNÁK et al.: FLAME RESISTANCE AND MECHANICAL PROPERTIES OF COMPOSITES ...

Table 2: Material characterization of composite materials

Tabela 2: Karakterizacija materialov v kompozitu

Material description Sample A Sample B Sample C Sample D Sample E

1 × BIDI glass 1 × BIDI glass 1 × BIDl glass 10 × 1 × BIDI glass
fabric* fabric* fabric* phenolic/glass* fabric*
Reinforcement lay-up 1 × CGM ** 1 × CGM** 1 × CGM** prepreg 1 × CGM**
1 × BIDI glass 1 × BIDI glass 1 × BIDI glass 1 × BIDI glass
fabric* fabric* fabric* fabric*
Matrix matrix FR4/12 matrix FR4/12 matrix FR4/12 phenolic matrix Norester 880
ATH
Additive – – – –
(100 % to matrix)
Coating – gelcoat BÜFA – – gelcoat BÜFA
Production technology RTM RTM VIP prepreg RTM
(*bidiagonal glass fabric, **continuous-filament glass mat)

for Sample C. Sample D prepared from prepregs showed

excellent flexural performance and fire properties
compared to the samples prepared with RTM and VIP;
however, these materials are very expensive.
Moreover, comparing FR4/12 to the commercial ma-
trix, it is obvious that the obtained mechanical properties
are almost twice as high as for the samples prepared
from FR4/12.
The tests of the fire properties (Figure 2) showed that
the gelcoat layer also influences the flame spread and the
heat release. Further, the oxygen index of Samples B
(matrix FR4/12) and E (the commercial matrix) was the
same for both samples. Sample C exhibited the lowest Figure 2: Fire properties of prepared samples
oxygen index of all the produced composites. Regarding Slika 2: Po`arne lastnosti pripravljenih vzorcev
the requirement for the oxygen index (higher than 30),
all the samples passed the test. The heat-release
parameter (Figure 3) was measured only for Samples A,
B and C, where individual values were 211.6, 154.7 and
37.7. The curves in Figure 3 show the heat release
during the combustion of the samples. The flame spread
(Figure 4) for Samples A and C is the same (due to the
same material composition).

4 CONCLUSION
The main objective of the mechanical testing was to
determine whether the strengths of the material combi-
nations reached 150 MPa (this value is the requirement

Figure 3: Heat release during the flame test of composite materials: a)

sample A, b) sample B
Figure 1: Flexural properties of prepared samples Slika 3: Spro{~anje toplote pri preizkusu kompozitnega materiala v
Slika 1: Upogibne lastnosti pripravljenih vzorcev plamenu: a) vzorec A, b) vzorec B

Materiali in tehnologije / Materials and technology 49 (2015) 5, 821–824 823

V. RUSNÁK et al.: FLAME RESISTANCE AND MECHANICAL PROPERTIES OF COMPOSITES ...

Table 3: Table guide to selecting the test classification1

Tabela 3: Tabelarni napotek za izbiro klasifikacije preizkusa1

UK: FRANCE:
ASTM 2863: LIMITED GERMANY: USA: ASTM E84 EUROCLASS: SINGLE
BS 476
OXYGEN INDEX (LOI) 4102 5510 NF P 92-501 UL94 BURNING ITEM (SBI)
PART 6,7
41– 50 Class 0 Class A2 S4 M1 25 5V 0 B
34.5–41 Class 1 Class B1 S4 M2 50 0 1 B/C
28.5– 34.5 Class 2 Class B2 S3 M3 100 0 2 C/D
22–28.5 Class 3 Class B3 S2 M4 >100 1 3 D/E

The developed matrix exhibits excellent processing

properties, good and fast fiber wetting, adjustable reac-
tivity and curing times. Another advantage is that the
used promoter is based on iron compounds.
From the overview of the properties of all the sys-
tems, it is clear that the polyester systems do not reach
the same fire-resistance values as the phenolic systems.
On the other hand, due to other advantages (surface
quality, price and processing methods) the development
of the composite systems based on polyester systems
will dominate.

Acknowledgement

This work and the project were realized with the

financial support of the Ministry of Industry and Trade
of the Czech Republic, project number FR-T13/433.
Figure 4: Composite samples after the flame-spread test
Slika 4: Kompozitni vzorci po preizkusu {irjenja ognja Further, this study was also supported by an internal
grant of TBU in Zlín, No. IGA/FT/2015/001, funded
from the resources for specific university research.
of French standard NF F01-281). All the material com-
binations met this requirement with a certain safety
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