Method of Recovering the Fibrous Fraction

of Glass/Epoxy Composites

LIU YUYAN,* MENG LINGHUI, HUANG YUDONG AND LIU LIXUN

Department of Applied Chemistry
Harbin Institute of Technology, Harbin 150001, P.R. China

ABSTRACT: This study reports the method of recovery of glass fibers from glass/epoxy composites
through the solvent method. It is possible to decompose epoxy resin with a yield of more than
99 wt% soluble products in a nitric acid solution (8 M) at 90
C for 5 h. The decomposition rate of
epoxy resin increases with an increase in temperature and concentration of acid solution. The glass
fibers can be recovered with very little contamination and they have a tensile strength reduction of
3.5% under decomposition conditions of T 70
C, t 250 h, C 6 M and
6 g/100 mL. These
fibers can be used as reinforcement to prepare new composites. The interlaminar shear strength
(ILSS) of recovered short fiber-reinforced composites produce strength reductions of only 2.5%
compared with pristine composites.

KEY WORDS: composites, glass fiber, epoxy resin, recycling.

INTRODUCTION

LASS FIBER/EPOXY COMPOSITES are attractive materials for the automotive and
G aircraft industry, but one barrier to their increased use is the recycling difficulty. The
epoxy resin in the cast-off cannot be melted down and remolded as is done in the
thermoplastic industry. With the increasing landfill casts, there is an urgent need to
develop recycling technologies for composite materials.
The majority of work on composite recycling is concerned with grinding the composites
into a suitable size to be used as fillers in new composite materials [13]. Masatashi [4]
found that using glass/epoxy composites as fillers for epoxy resin could yield products
with better strength and thermal expansion properties when compared to those made with
conventional fillers. Other recycling processes based on pyrolysis have also been
considered [5,6]. This process breaks polymeric waste into reusable fuel oils and
hydrocarbon gasses in the absence of air. A sheet molding compound (SMC) of glass/
polyester composites was pyrolyzed by Torres et al. [7]. The liquid obtained can be used as
petrol. Combustion with energy recovery is another means of recovering some value from
scrap composites [8]. In these processes, carbon- and aramid-reinforced composites
destroy valuable materials and can be a source of pollution.
A solvent recycling method in which valuable carbon fibers can be recovered has
already been described [9]. In this study, this method is further described, the recycling

*Author to whom correspondence should be addressed. E-mail: liuyy@hit.edu.cn

Figure 6 appears in color online: http://jrp.sagepub.com

Journal of REINFORCED PLASTICS AND COMPOSITES, Vol. 25, No. 14/2006 1525
0731-6844/06/14 15259 $10.00/0 DOI: 10.1177/0731684406066748
2006 SAGE Publications

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1526 L. YUYAN ET AL.

process conditions of glass/epoxy composites are examined, the properties of recovered

glass fibers are presented, and the mechanical properties of composites prepared with
recovered fibers are compared with those of virgin composites.

EXPERIMENTAL

Materials

The epoxy composites with 67 wt% unidirectional glass fiber were prepared in a
laboratory. The bisphenol A type epoxy resin (E-44) and curing agent (IPDA) were used as
a matrix. The curing conditions were 80
C for 2 h and 150
C for 4 h. The composites were
cast to 200 mm  6 mm  2 mm bar.

Decomposition Conditions

Each composite specimen was put into a specially designed glass vessel (D 100 mm,
L 300 mm) and then immersed in 100 mL nitric acid solution. The decomposition
temperature was controlled in a water bath. The feedstock ratio is defined as the ratio of
resin weight in composite to the volume of the nitric acid solution. The insoluble
composites were separated from the solution at a specific decomposition time and washed
with acetone. After drying at 60
C, the composites were weighed.

Preparation of New Composites

The recovered glass fibers were incorporated into epoxy matrices to produce two
different composites. The first sample was made of recovered unidirectional continuous
glass fibers with E-44/IPDA at a content level of 65%w/w. The next sample was 45 mm
short glass fibers which were cut from recovered fibers with E-44/MeTHPA at a content
level of 20%w/w. These two types of composites were prepared again by utilizing virgin
glass fibers, for use as reference samples.

Measurement Methods

The decomposition rate of epoxy resin in composites was determined in each experiment
by weighing the amount of solid residue. The decomposition rate is given by
 
weight of composites  weight of solid residue
Decomposition rate %  100:
weight of resin in composites

The reclaimed fibers were subjected to visual scrutiny via optical and scanning
electron microscopy (SEM) to determine the extent of contamination of the residual
surface. The surface of the glass fiber was also observed and pictured by electron probe
microscopy using a JEOL JCXA-733 instrument.
In order to verify the effect of the recycling process on fiber properties, the tensile
strength of the single fiber was measured according to ASTM-D3379 specification. The
cross-head speed of the MTS materials testing system was 10 mm/min. The interlaminar

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Method of Recovering Fibrous Fraction of Glass/Epoxy Composites 1527

shear strength (ILSS) testing of new composites was carried out using an Instron 5569
machine with a cross-head speed of 2 mm/min.

RESULTS AND DISCUSSION

Decomposition of Composites

First, the decomposition experiment of glass/epoxy composites was carried out in

concentrated sulfuric acid. A flake of glass/epoxy composite, approximately
200 mm  6 mm  2 mm in size, was put into a 6 M sulfuric acid solution. The solution
was transparent even after 20 h of immersion at 6090
C and the composite appeared swollen
and distorted. After removing from the sulfuric acid solution, the composite increased in
mass. The fibers were fixed in the matrix and could not be separated. The results showed that
concentrated sulfuric acid was not effective in decomposing glass/epoxy composites.
The glass/epoxy composite was then immersed in a 6 M nitric acid solution at 6090
C.
The composite started to decompose at an immersion time of about 5 h. The solution
became yellow and a red-brown decomposed compound with a high viscosity could be
observed in the bottom of the solution. The color of the solution became deep and the
viscous red-brown solid products gradually decreased with the increase in the duration of
immersion. When fibers in the composites separated from each other, the solution was
cooled down and the insoluble residue was collected. After washing with acetone and
drying at 60
C, the recovered fibers were obtained. The weight of recovered fibers was
about 67 wt% of the composites, which is close to the content of glass fibers in the
composites. It appeared that epoxy resin was completely removed from the glass fibers.
The stronger oxidation of nitric acid caused the CN bond in the network to break
and the benzene ring to be nitrated. In order to examine the effects of experimental
parameters on the decomposition rate of the resin matrix, the following experiments were
carried out.

Effect of Reaction Conditions on the Decomposition Rate of the Resin Matrix

TEMPERATURE
The decomposition curve for epoxy composites, in 8 M decomposition solution at
5090
C for 5 h, with a 2 g/100 mL feedstock ratio is shown in Figure 1. The increase
in temperature resulted in improvement of the decomposition rate of epoxy resin. The
decomposition rate was about 2.1, 24.9, and 96%, at 50, 70, and 80
C respectively. There
is a great increase in decomposition rate after 70
C. The epoxy resin kept for 6 h
completely disappeared at 90
C.

CONCENTRATION OF THE DECOMPOSITION SOLUTION

The effect of concentration of the decomposition solution on the degree of decompo-
sition of the resin matrix at 90
C for 5 h with a 2 g/100 mL feedstock ratio is shown in
Figure 2. The rate of decomposition increased rapidly with the increase in concentration of
the decomposition solution. The resin was entirely decomposed in 8 M decomposition
solutions kept for 5 h. This could be attributed to the stronger causticity of the
decomposition solution, which can open the thermosetting network of the epoxy resin
quickly with the increase in concentration of decomposition solution.

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1528 L. YUYAN ET AL.

100

80

Decomposition rate (%)

60

40

20

0
40 50 60 70 80 90 100
Reaction temperature (C)
Figure 1. Resin decomposition rate vs reaction temperature.

100

80
Decomposition rate (%)

60

40

20

0
0 2 4 6 8 10
Concentration (M)
Figure 2. Resin decomposition rate vs decomposition solution concentration.

FEEDSTOCK RATIO
The effect of feedstock ratio on the decomposition rate of the resin matrix in composites
under a set of experimental parameters (T 90
C, C 8 M, t 5 h) is presented in
Figure 3. The decomposition rate of the resin decreased slowly as the feedstock ratio
increased. It could be seen that the temperature and concentration of the decomposition
solution was much more effective than the feedstock ratio in increasing the decomposition
rate of the resin matrix. The feedstock ratio can be increased in theory to improve reclaim
efficiency. However, because the increase of feedstock ratio results in a decrease in acid
solution volume, the composites cannot be soaked and decomposed.

Glass Fiber Characterization

FIBER PROPERTIES
Table 1 shows the orthogonal experimental results of the decomposition of epoxy
composites in which the loss of fiber strength can be calculated by dividing the amount of
decrease of single fiber tensile strength of the recovered fiber by the tensile strength of a

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Method of Recovering Fibrous Fraction of Glass/Epoxy Composites 1529
100

Decomposition rate (%)

90

80

70
1 2 3 4 5 6
Feedstock ratio (g/100ml)
Figure 3. Resin decomposition rate vs feedstock ratio.

Table 1. Orthogonal experiment of decomposition of epoxy composites.

Level Results

Temperature Concentration Feedstock ratio Decomposition Strength

No. (
C) (M) (g/100 mL) time (h) loss (%)

1 90 8 6 12 5.2
2 90 6 4 22 10.3
3 90 4 2 82 14.7
4 80 8 4 17 10.4
5 80 6 2 95 11.7
6 80 4 6 240 15.1
7 70 8 2 45 9.1
8 70 6 6 250 3.5
9 90 8 6 710 11.3

single fiber of the original fiber bundle. The sample under decomposition conditions of
T 70
C, t 250 h, C 6 M, and
6 g/100 mL has a minimum fiber tensile strength loss
of 3.5%, while runs at 80
C with 4 M concentration for 240 h produced a maximum
strength reduction of 15.1%. These results are better than the results of the previous study
of the effects of recycling process on the strength of the glass fibers. Pickering et al. [10]
measured a 50% reduction in the strength of glass fibers after heating at 450
C in a
fluidized-bed process.

OBSERVATION OF RECOVERED FIBERS

The SEM was used to evaluate the fiber surfaces and the residual resin present on the
composites. Two samples were studied based on their varying extent reaction. The first one
was processed at 60
C for 5 h with 8 M concentration and 2 g/100 mL feedstock ratio.
Large flakes of residual resin appeared among the fibers and some fibers were surrounded
by a sheath of resin (Figure 4). The residual resin along the fibers could not be separated
from the fiber surface. The sample under decomposition conditions of T 70
C, t 5 h,
C 8 M, and
2 g/100 mL was evaluated with SEM (Figure 5). The resin can be
removed from the composites in large chunks and some of the fiber bundles were separate.

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1530 L. YUYAN ET AL.

(a) (b)
Figure 4. SEM micrographs of composites under T 60
C, t 5 h, C 8 M, and
2 g/100 mL (1000):
(a) cross section and (b) side.

(a) (b)


Figure 5. SEM micrographs of composites under T 70 C, t 5 h, C 8 M, and
2 g/100 mL (1000):
(a) cross section and (b) side.

An optical graph of recovered glass fibers is given in Figure 6. The fibers are free from
residues and arranged in an orderly manner. A careful recycling process could eliminate
fiber damage and have a highly regular orientation.
Figures 7 and 8 show the electron probe microscopic analysis of virgin fibers and
recycled glass fibers after washing and drying separately. When compared with virgin
fibers, the surface of the recycled fibers was smooth and showed little contamination.
The glass fibers were recovered undamaged and were reusable.

Reuse of Recovered Fibers

To obtain a high performance of recovered fiber-reinforced composites, the selection

of the decomposition process is necessary. Through orthogonal experimentation,
the recycling conditions for retaining the fiber strength were T 70
C, C 8 M, and

6g/100 mL [11]. But this process needed longer immersion time. In this study, the

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Method of Recovering Fibrous Fraction of Glass/Epoxy Composites 1531

Figure 6. Optical graph of the recovered glass fibers.

Figure 7. Electron probe micrographs of virgin glass fibers.

recovered fibers available from all of the recycling processes (Table 1) were employed as
reinforcement to prepare new composites.
Table 2 presents the ILSS of new composites. The composites were prepared by using
recovered glass fibers as reinforcement or virgin fibers as reference. The recycled
unidirectional continuous fiber-reinforced composites showed a reduction of 4.7% in
ILSS and recycled short fiber-reinforced composites produced a strength reduction of
only 2.5%.
Knowing the wettability of fibers is useful to predict their adhesion potential to the
matrices. The contact angle of the fiber can characterize its wettability by the contacting
liquid in a given environment. Using glycol as a contacting liquid, the contact angle of
virgin fibers was 59.4
and that of recycled fibers was 56.1
. After oxidation of nitric acid
in the recycling process, the contact angles of the fibers decrease and their adhesion to the
matrices improves. It is likely that acid digestion increases surface roughness of the

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1532 L. YUYAN ET AL.

Figure 8. Electron probe micrographs of recycled glass fibers.

Table 2. Interlaminar shear strength of the new composites.

ILSS (MPa)

Virgin fibers/epoxy Recycled fibers/epoxy Strength

Fiber types composites composites loss (%)

Unidirectional continuous glass fibers 58.53 55.76 4.7

4 mm short glass fibers 21.50 20.96 2.5

fiber and improves interfacial bond strength, thus annulling the negative effects of
loss in tensile strength of the single fiber.

CONCLUSIONS

Recycling of thermoset epoxy composite containing glass fibers was studied and the
following results were obtained.
1. Concentrated sulfuric acid was not effective for decomposing glass/epoxy composites.
2. When the reaction temperature was 90
C, the concentration of the acid solution was
8 M, the feedstock ratio was 2 g/100 mL, and the reaction time was 5 h, the
decomposition rate of epoxy resin reached 99%.
3. The temperature and concentration of the decomposition solution were much more
effective than the feedstock ratio in increasing the decomposition rate of the resin
matrix.
4. Glass fibers from reinforced epoxy composites can be recovered undamaged without
any residue left. The recovered glass fibers have a tensile strength reduction of
3.515.1% under a set of decomposition conditions considered in this study.
5. Interlaminar shear strength (ILSS) of the recovered short fiber-reinforced composites
produced a strength reduction of only 2.5% compared with pristine composites.

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Method of Recovering Fibrous Fraction of Glass/Epoxy Composites 1533

ACKNOWLEDGMENTS

The authors gratefully acknowledge the financial support of the Study Abroad Returnee
Foundation of Hei Longjiang Province under Project No. LC03C09.

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