The Polymeric Heterogemeous Matrix for Carbon and Glass Reinforced Plastic

doi:10.4236/msce.2013.15005

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Journal of Materials Science and Chemical E ngineering, 2013, 1, 23-27

http://dx.doi.org/10.4236/msce.2013.15005 Published Online October 2013 (http://www.scirp.org/journal/msce)

The Polymeric Heterogemeous Matrix for Ca rb o n and

Glass Reinforced Plastic

Galina Malysheva1, Lianhe Liu2, Xiao Ouyang3, Oleg Kulakov1

1Department of Special Machinery, Bauman Moscow State Technical University, Moscow, Russia

2Qingdao Advanced Marine Material Technology Co., Ltd, Qingdao, China

3Department of Material Science and Chemical Engineering, Harbin Engineering University, Harbin, China

Email: [email protected]

Received August 2013

cense, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

ABSTRACT

This article presents the results of deformation -strength properties measurement and microstructural analysis of hetero-

geneous polymer matrix consisting of thermoset and thermoplastic polymers. Thermosetting material is a diamino-di-

phenil sulfon -cured epoxy oligomer. Polysulfone was used as thermoplastic material. Two different technological proc-

esses were used to obtain heterogeneous polymer matrix: the material was mixed in the block, or layered material was

produced in which a layer of thermoplastic material alternated with a layer of epoxy oligomer.

Keywords: Heterogeneous Matrix; Polysulfon; Epoxy Olygomer; Interphase Bou ndary; Microstructure; Polymer

Composite Materials

1. Introduction

Polymer composite material (PCM) matrix ensures the

material solidity and uniform load distribution between

the reinforcing elements, resulting in the growth of

cracks deceleration, as well as stress transfer and distri-

bution. The most widespread matrix used in production

of PCM construction products is epoxy-based binding.

The main advantages of epoxy bindings are high adhe-

sive durability, good technological effectiveness, small

swelling levels and very good technological properties.

This allows creating materials which can be cured at the

room temperature (cold-curing binding) and at increased

temperatures (hot-curing binding). However, epoxy po-

lymers are rather fragile, generally, their stretch ratio

does not exceed 1%, so the search of effective ways of

their modification for the deformation properties increase

is needed.

The purpose of this work is the development of the

epoxy binding with improved deformation properties. To

achieve this goal, thermoplastic polymers were used as

plasticizers.

2. Experimental Process

Traditional epoxy plasticizers, such as dibutylphthalate,

active diluents or rubbers, ensure molecular plasticization

and allow increasing the characteristics of impact strength

and crack resistance, yet their input results in elastic

modulus and gla s s-transition temperature decrease.

One of modern methods of drastic increase of epoxy

binding deformation characteristics that does not result in

deterioration of their heat resistance and other operating

specifications, is use of thermop lasts which relate to type

of structural plasticization. Using the se polymer mixes as

basis makes it possible to create new type of hybrid ma-

trix with high deformation, strength, thermal and physi-

cal properties, offering high chemical resistance and

good fabricating characteristics.

The most prevailing thermoplasts are polyetherketones,

polyest e ri mides an d polysul fones.

In this work the microstructure of the polymer mixes

prepared by two different technologies was researched:

first, epoxy oligomer and polysulfone mix was prepared,

second, the multilayered material consisting of alternat-

ing layers of epoxy oligomer and polysulfone was pre-

pared.

In accordance with the first technology, epoxy oli-

gomer and polysulfon mixing were performed using a

mechanical mixer at +180˚C. Afterwards this polymer

mixture was cooled, injected with a curing solution and

repeatedly mixed by the same mechanical mixer. Curing

was held at +180˚C during 3 hours. The produced ma-

G. MALYSHEVA ET AL.

terial was used for producing standard test samples.

Samples were used for bending (σbend

• 3 layers (2 polysulfone layers, 1 epoxy olygomer

layer);

, GOST 9626-90),

stretching (ε, GOST 11262-80) and impact strength (A.

GOST 14235-69) testing.

3. Results and Discuss ions

Values for polymer deformation and strength properties

in relation to the polysulfon amount injected are given in

Table 1.

As seen in Table 1 , thermoplast injection to the epoxy

matrix increases the bend durability and impact strength

more than twice. Also the stretch ratio shows magnitude

increase thus indicating fundamental positive influence

of thermoplast on deformation properties of system.

However, the value of adhesive power slightly decreases

depending upon the thermoplastic polymer increase. This

phenomenon probably occurs due to the overall viscosity

growth, resulting in the lbinding layer thickness being

slightly higher than the optimum. Yet such an insignifi-

cant reduction of adhesive power is not fundamental and

will not lead to the deterioration of fabricating chara cter-

istics of PCM based on this polymer matrix.

In accordance with the second technology, epoxy oli-

homer and polysulfone joint mixing was not performed.

Multilayered material with epoxy oligomer and polysul-

fone layers alternated among themselves was made.

This multilayered binding production technology in-

cludes several stages. Compression-molded polysulfone

thin films were produced. The film thickness reached 100

- 140 microns. The epoxy oligomer preliminarily mixed

with a curing compound was manually coated on the

polysulfone film surface. Afterwards the next polysul-

fone layer was coated. Three types of multilayered sam-

ples were produced:

• 5 layers (3 polysulfon e layers, 2 epoxy olygomer lay-

ers);

• 7 layers (4 polysulfon e layers, 3 epoxy olygomer lay-

ers) (see Table 2).

Table 1. Influence of the thermoplastic material content on

the properties of heterogemeous matrix (epoxy resin + po-

lysulfone).

Properties The content of polysulfone, %

0 5 10 20 30 40

Adhesive strength,

τ, МPа 24 24 25 26 22 17

Bending test, σbend., МPа 28 32 42 49 54 58

Elongation at stretching,

ε, % 0.2 1.2 1.5 1.9 2.2 2.8

Impact toughness,

А, Kj/m2 4.8 10.4 19.5 28.2 37.4 46.2

Table 2. Influence of the quantity of layers on the properties

of multilayer heterogemeous polymer.

Properties Polymer

Polysulfone Epoxy resi n

Quantity of layers 2 1

Elongation at stretching, ε, % 2,5

Impact toughness А, Kj/m2 32,4

Quantity of layers 3 2

Elongation at stretching, ε, % 1,3

Impact toughness А, Kj/m2 24,7

Quantity of layers 4 3

Elongation at stretching, ε, % 1,2

Impact toughness А, Kj/m2 25,3

Structure analysis of the produced hybrid bindings was

conducted by the means of scanning electronic micro-

scope FEI Phenom with the image resolution up to 50

nanometers.

The material of the samples’ surface consisted of 30

polysulfone mass fractions and 70 epoxy oligomer mass

fractions produced in accordance with the first technol-

ogy. The frontal surface (Figure 1(a)) was initially

analyzed. Afterwards the surface of the same samples

was investigated at various magnifications after the

bending test was conducted (Figure 1(c)). The acquired

data analysis allows to draw a conclusion that the mate-

rial microstructure is not homogeneus and polymeric

phases are mutually distributed chaotically (epoxy matrix

is shown in white in Figure 1). Mixing mode change

towards the mixing duration increase did not result in

structure improvement. We assume that polymer mixture

inhomogenous structure is related to the errors in mixture

preparation technology, so its further improvement is

required. Nevertheless, even this imperfect structure de-

monstrated the fundamental increase in polymer binding

deformation parameters (see Table 1).

The structure of layered hybrid binding, produced by

the second method with 4 polysulfone and 3 epoxy oly-

gomer alternating layers is shown in Figur es 2-4.

On Figure 2 there are visible characteristic cracks that

always appear on a layer of an epoxy oligomer while

bending tests being performed. On Figure 2(a) the epoxy

olygomer layer destruction №1 (from the sample frontal

surface) took place. On Figure 2( b) the destruction of

the 3rd epoxy oligomer layer took place. The surface

distraction microstructure at bending tests (Figure 3) and

impact strength tests (Figure 4) is different, however in

both cases epoxy material destruction took place, while

polysulfone layers have kept the integrity.

G. MALYSHEVA ET AL.

(a) (b) (c)

Figure 1. Fracture surfaces of epoxy matrix, content of 30% polysulfobe for different microscope approach ((a) ×800, (b), (c)

×2060).

(a) (b)

Figure 2. Multilayer polymer consist of 4 layers of polysulfone and 3 layers of epoxy resin (a) and 3 layers of polysulfone and

2 layers of epoxy resin (b).

(a) (b)

G. MALYSHEVA ET AL.

Figure 3. Fracture surfaces of multilayer polymer consist of 3 layers of polysulfone and 2 layers of epoxy resin after bent test

((a), (b), (c), (d))—different samples).

(a) (b) (c)

Figure 4. Fracture surfaces of multilayer polymer consist of 3 layers of polysulfone and 2 layers of epoxy resin after impact

strength test ((a), (b), (c))—different samples).

After-destruction surface analysis indicates that frac-

ture pattern depends on binding fabrication techniques.

For the material manufactured via method № 1(mixing in

the block), despite nonuniform polysulfone mixture in

the epoxy material, interphase fracture does not happen.

For the material manufactured via the second method

(multilayered polymer) the layer of an epoxy material

and interphase boundary between polysulfone and epoxy

material layers destruct in the first place.

4. Conclusion

Results based upon this experiment indicate that injecting

polysulfone as plasticizer in the epoxy binding signifi-

cantly improves its deformation parameters. This devel-

oped material can be recommended as a matrix at pro-

duction of various three-layer sandwich panels for air-

craft interiors, such as catering blocks, fuselage trim

elements, various passenger luggage accommodation

equipment of various design which experiences impact

stress.

5. Acknowledgements

This work was supported by the Chinese international

science and technology program (No. S2012HR0080L).

REFERENCES

[1] A. Muranov, G. Malysheva and A. Pilyugina, “The Po-

G. MALYSHEVA ET AL.

lymeric Heterogeneous matrix for Composites,” ACM-

TAA-2012, Werxham, 2012. [2] M. Kerber and I. Gorbunova, “Binders for Polymeric

Composite Materials,” Plastics, No. 12, 2010, pp. 14-21.