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To cite this article: Huabo Duan , Weifeng Jia & Jinhui Li (2010) The Recycling of Comminuted
Glass-Fiber-Reinforced Resin from Electronic Waste, Journal of the Air & Waste Management
Association, 60:5, 532-539, DOI: 10.3155/1047-3289.60.5.532
Download by: [Athlone Inst of Technology] Date: 24 August 2017, At: 02:09
TECHNICAL PAPER ISSN:1047-3289 J. Air & Waste Manage. Assoc. 60:532539
DOI:10.3155/1047-3289.60.5.532
Copyright 2010 Air & Waste Management Association
Weifeng Jia
Civil and Environment Engineering School, University of Science and Technology, Beijing,
Peoples Republic of China
Jinhui Li
Department of Environmental Sciences and Engineering, Tsinghua University, Beijing, Peoples
Republic of China
Downloaded by [Athlone Inst of Technology] at 02:09 24 August 2017
532 Journal of the Air & Waste Management Association Volume 60 May 2010
Duan, Jia, and Li
combination of strength, durability, low weight, and cor- even lead to the release of dioxin into the atmosphere.26
rosion resistance that has made it increasingly feasible for Pyrolysis has the potential to produce chemical feedstocks
use in recycled composite products. This type of waste can from the polymer of fiber-reinforced plastic waste, but
also be used for energy recovery via pyrolysis. Several these may be difficult to refine from the mixture of prod-
material recovery technologies have been proposed and ucts produced because the operating cost is too high to be
developed for general glass-fiber-reinforced polymeric economically viable.2730 Chemical breakdown of poly-
materials. There are two categories of such processes: mer matrix materials using hydrolysis or dissolution has
those that use thermal or chemical processes to degrade seen some limited application to composites. Regrinding
the scrap down into materials and energy, and those that fiber-reinforced polymer waste into larger or smaller
involve mechanical techniques to reduce the size of the pieces to produce new composite reinforcement and filler
scrap to produce filler recyclate. Pickering et al.8 and Cun- materials is currently the most promising method that
liffe et al.5 have incinerated various glass-fiber-reinforced has actually been applied. However, to the authors
resins in a fluidized bed with the aim of recovering glass knowledge, little information is available on the reuse of
fiber and energy. The thermal process for recycling glass- comminuted GRE waste under molding conditions, with
fiber-reinforced polyester waste through pyrolysis at attention to the granularity and the bond mold. Previous
450 C resulted in the production of carbon monoxide studies have concluded that composites incorporating re-
(CO), carbon dioxide (CO2), hydrogen gas (H2), methane grinding methods tend to exhibit significantly superior
(CH4), and hydrocarbon gases, along with pyrolysis oil, mechanical properties, but no investigations into the rea-
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which has a high calorific value for use as fuels.5,9 Zheng sons behind this behavior have been conducted so far.
et al.10 reported on efforts to reclaim glass fiber from The work presented in this paper forms part of a
glass-fiber-reinforced composites by heating in a muffle major investigation into the potential for comminuted
furnace. Buggy et al.11 and Iwaya et al.12 have attempted GRE waste to be recycled into filler for thermoplastic
to extract fiber by dissolving the polymeric fraction using polymeric composite board. It aims to determine the fea-
various organic and inorganic solvents. Patel et al.13 in- sibility of closed-loop material recycling for fiber-rein-
vestigated various recycling technologies for sheet mold- forced thermoset composites. The use of prepreg residue
ing compound (SMC), including solvent dissolution, hy- (fiber-reinforced epoxy resin laminate) from printed cir-
drolysis, and pyrolysis. cuit manufacturing of GRE filling materials, the molding
There have also been several investigations into the process, and the feasibility of producing composite board
possible reuse of materials recovered from GRE. Methods were evaluated by considering the effects of mass propor-
for the reuse of long or short glass fiber (reinforced poly- tion and comminuted granularity. Interfacial-layer micro-
mer) as an additive for cement mortar or in cement con- graph and bond model analysis of composite material
struction products have recently been proposed.14,15 fracture surface were used to study the fiber breakage and
Moreover, several research projects have been conducted fracture mechanisms.
on the reuse of fiberglass recyclate as fillers into polymer
matrices. Schinner et al.16 recycled long carbon fiber, ther- MATERIALS AND METHODS
moplastic composite material by grinding the composite Materials
and using the material as a high-quality reinforcing ma- Prepreg residue, a common glass-fiber-reinforced resin
terial in injection molds or as press-molding compounds. composite used as reinforcement in composite board, was
Perrin et al.17 reported investigations into the recycling of obtained from Jinhua Printed Circuit Board Company
SMC waste as incorporation material for thermoplastic (Hebei province, China). Samples used in this study had
polymer matrices. The feasibility of recycling short-fiber an average length and width of 10 30 cm.
glass-reinforced polymer wastes into thermosetting matri- Prepreg is the FR4 laminate that is considered to be
ces (polyester or polycarbonate) was demonstrated in the backbone of the printed circuit industry. It consists
1996.18 20 Several studies have addressed the recycling of of layers of fiberglass cloth of approximately 60 wt %
nonmetallic fractions/powder from waste printed circuit impregnated with epoxy resin of 40 wt %. FR means
boards after noble metals or copper have been removed, flame retardant, and type 4 indicates woven glass-
making a polymer composite by using thermoplastic reinforced epoxy resin. This laminate is the most widely
polymer (polypropylene [PP]) as a bonding matrix.2124 used material for this purpose, providing the best com-
This type of reproduced composite probably contained promise between cost and electrical and mechanical
copper, lead, and even some heavy metals. However, requirements. A T30S grade of PP particle (0.51 mm),
none of these proposals developed any large-scale appli- obtained from SINOPEC Beijing Yangzi Petrochemical
cation that could represent a viable alternative to waste Company with a melting point of 167 C and a density
disposal in landfills or incineration. of 0.90 g/cm3, was used as the matrix material. Silane
Incinerationthe reclamation method used in devel- coupling agents (KH560), which are widely used as ad-
oping countries for the energy content of polymer has hesion promoters,31,32 were prepared to modify the
proved not useful for composites because of their high prepreg residue surface.
inorganic content. Moreover, during open burning or
incineration (in the presence of oxygen gas [O2]), approx- Methods and Equipment
imately 515% of the bromine (flame retardants) in fiber- Prepreg residues were crushed into less than 3-mm pieces
reinforced polymer wastes are difficult to separate or by a shredding machine (model HYP-250, Beijing) with
treat,25 contributing to the emissions of organic pollut- 8-screen mesh. The crushed prepreg residue was then
ants, which are rich in brominated aromatics and can comminuted by a pulverizing machine into particles with
Volume 60 May 2010 Journal of the Air & Waste Management Association 533
Duan, Jia, and Li
then granulated in a single-screw extruder (model SJ45, The impact specimens were fractured, and the ex-
Jiangsu) running at 15 rpm and at temperatures in the posed surfaces were observed with a scanning electron
range 170 200 C. A silane/ethanol mixture was pre- microscope (SEM; model JSM 7401 and JSM-6460LV). The
pared, using proportions of silane, ethanol, and water in surfaces of the fractured specimens were coated with gold
the ratio of 20:72:8 (wt %), by slowly dripping silane into to avoid charging under the electron beam. The mechan-
ethanol and continuously stirring. The silane concentra- ical properties of the new composite materials, including
tion in the final polymer mixture was kept to a level of 0.5 flexural, impact, and tensile strength and modulus, were
wt %. These concentrations are the empirical values that examined using the International Standardization Orga-
have been used in similar studies.4,6,10 nization (ISO) 527, ISO 180, and ISO 178 series standards.
During the injection and compression molding pro-
cess, all components were carefully dried at temperatures
in the range of 100 130 C for at least 4 hr to limit the
processing-induced hydrolysis and to reduce internal
voids caused by escaping water vapor. The resulting pel-
lets were fed into a three-phase injection molding ma-
chine, model CJ80-E (injection pressure 120 MPa; mold
temperature 170, 175, and 120 C) to produce ISO
527-2 dumbbell (GRE/PP composite board) specimens
(length 151 mm, gauge length 50 mm, gauge width
10 mm, thickness 4 mm) and rectangular test bars
(length 80 mm, width 12 mm, thickness 4 mm).
These specimens are shown in Figure 3. About 15 speci-
mens (dumbbell and rectangular test bars) were obtained
for each prepared PP-prepreg mixture. It can be seen here
534 Journal of the Air & Waste Management Association Volume 60 May 2010
Duan, Jia, and Li
Figure 4. Influence of mass fraction of GRE on flexural properties Figure 6. Influence of mass fraction of GRE on impact strength of
of a reproduced composite board (GRE/PP). a reproduced composite board (GRE/PP).
Volume 60 May 2010 Journal of the Air & Waste Management Association 535
Duan, Jia, and Li
536 Journal of the Air & Waste Management Association Volume 60 May 2010
Duan, Jia, and Li
An Analysis on the Microstructure of the It is known that to understand the mechanical prop-
Composite Boards erties of a composite material (e.g., strength and resis-
It is well established that the mechanical properties of the tance to fracture) one needs to be able to describe the
matrix-matrix/fiber interfaces are crucial because they dic- particle size distribution of the particulate component of
tate the mechanical behavior of the overall composite the composite.37 For the specimens of reproduced com-
structure. Hence the impact specimens were fractured, posite board at 30% loading of prepreg residue, which
and the exposed surfaces were observed with SEM. Figure were separated into subgroups on the basis of particle size
9 shows the SEM micrographs of the fracture surfaces of (ranging from 20- to 200-screen mesh), the fracture sur-
pure PP and of reproduced composite board samples con- faces were investigated by SEM.
taining 10, 30, and 50 wt % of prepreg residue. As seen in Figure 10, along with the decrease of the
The SEM of a composite board containing various granularity and fiber length of filled comminuted prepreg
mass fractions of prepreg residue shows a strong adhesion residue, the fillers in composite materials become more
between the PP matrix and the glass fiber and clearly evenly distributed as the particle size increases. Short glass
demonstrates the effect of fiber powder in the reproduced fibers of prepreg residue are prone to adhere strongly to
composite board. Whereas the fracture surface of pure PP the PP polymer, indicating excellent bonding between
matrix board presents a brittle fracture, in the composite the two. However, the larger particle-size fiber showed
board with added comminuted prepreg residue, the fibers even better adhesion, probably because of the continuity
reinforce the board significantly, although they are ori- and ductibility of the filler particles even at higher load-
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ented in various directions and their dispersion is almost ing. This phenomenon could explain why the strength of
random. However, it has also been reported that the composite board is almost unaffected by fiber length and
strength of the composite increases when the mass frac- fiber orientation, especially in the case of injection-
tion of additional resin, in the form of polymer-based molded composite board.
adhesives, is increased.35,36
On the other hand, overloading the boards with An Assessment on the Prospective Application of
prepreg residue can lead to a rapid reduction of the resin the Composite Boards
bonding agent, and the material blend becomes unman- GRE/PP composite boards are available for any potential
ageable, resulting in a mixture that is less amenable to applications that demand weight savings, precision engi-
fiber impregnation. For example, loading the fracture sur- neering, finite tolerances, and the simplification of parts
faces of a composite board with 50% mass fraction (Figure in production and operation. A molded polymer artifact is
9D) resulted in insufficient PP on the prepreg filler particle cheaper, faster, and easier to manufacture than a cast
surfaces, indicating that not enough chemical bond ex- aluminum or steel artifact and maintains similar and
isted between the matrix and the filler. This situation led sometimes even better tolerances and material strengths.
to the weakening of the composite rather than to its The current market for PP-based composites can be di-
reinforcement, proving that there is a limit on the in- vided into three sectors: (1) pallets, or flat transport struc-
crease in strength that can be gained by adding prepreg tures that support packaged goods in a stable fashion
residue. while being lifted by a forklift, pallet jack, or other jacking
Figure 9. SEM micrographs of fracture surfaces of (A) pure PP, composite board (GRE/PP) specimens containing (B) 10%, (C) 30%, and (D)
50 wt % of prepreg residue.
Volume 60 May 2010 Journal of the Air & Waste Management Association 537
Duan, Jia, and Li
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Figure 10. SEM micrographs of fracture surfaces of (A) pure PP, reproduced composite board (GRE/PP) samples filled by various particle size
of (B) 20- to 40-, (C) 40- to 80-, and (D) 200-screen mesh at 30 wt % loading.
device; (2) construction materials, such as steel lagging Although the mechanical properties of materials contain-
used in the molding construction of concrete; and (3) ing these recyclates do not always enhance properties
street furniture and accessories such as outdoor tables such as tensile strength, they may still be acceptable for
and chairs, artificial rockery, fences, railings, signs, and certain applications or could be improved with additional
dustbins. modifications.
With regard to the subsequent recyclability of these
materials, closed-loop material recycling for fiber-rein- ACKNOWLEDGMENTS
forced thermoset composites is an emerging technology. This study was funded by a project from the National
The newly reproduced composite board could be re- Key Technology Research and Development Program
ground and reused as filler in polymeric composite. Ther- (2006BAC02A18) and a special subject of the 2007 Na-
moplastics polymers (PP) are not crosslinked and can tional Environmental Protection Nonprofit Industry
easily be remelted, in contrast to thermosetting prepreg Scientific Research. The authors thank Ms. Marian Rhys
residue, which cannot be remolded. for her help in language editing.
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About the Authors
Reusing Nonmetals Reclaimed from Waste Printed Circuit Boards. In
Proceedings of the 2005 IEEE International Symposium on Electronics and Huabo Duan is a Ph.D. candidate in the Department of
the Environment; Institute of Electrical and Electronics Engineers: New Environmental Science and Engineering at Tsinghua Uni-
York, 2005; pp 205-209. versity in Beijing, China. Weifeng Jia is a M.Sci. candidate
23. Guo, J.; Rao, Q.; Xu, Z. Application of Glass-Nonmetals of Waste with the Department of Civil and Environment Engineering
Printed Circuit Boards to Produce Phenolic Moulding Compound; J.
Hazard. Mat. 2008, 153, 728-734. School at the University of Science and Technology in
24. Guo, J.; Rao, Q.; Guo, J.Y.; Xu, Z. A Plate Produced by Nonmetallic Beijing, China. Dr. Jinhui Li is a professor in the Department
Materials of Pulverized Waste Printed Circuit Boards; Environ. Sci. of Environmental Science and Engineering at Tsinghua Uni-
Technol. 2008, 42, 5267-5271. versity. He is also executive secretary at the Basel Conven-
25. Zhao, H.Y.; Peng, K.; Li, M.; Li, S.Q.; Song, Q.; Yao, Q. Distribution of
Bromine in the Pyrolysis of Printed Circuit Board Wastes. In Proceed- tion Coordinating Centre for Asia and the Pacific. Please
ings of the 8th Asia-Pacific International Symposium on Combustion and address correspondence to: Jinhui Li, Department of Envi-
Energy Utilization, Sochi, Russian Federation, October 10 12, 2006. ronmental Science and Engineering, Tsinghua University,
26. Lai, Y.C.; Lee, W.J.; Li, H.W.; Wang, L.C. Chang-Chien, G.P. Inhibi- 100084 Beijing, Peoples Republic of China; phone:
tion of Polybrominated Dibenzo-p-Dioxin and Dibenzofuran Forma-
tion from the Pyrolysis of Printed Circuit Boards; Environ. Sci. Technol. 8610-6279-4143; fax: 8610-6277-2048; e-mail: jinhui@
2007, 41, 957-962. tsinghua.edu.cn or duanhuabo@gmail.com.
27. Conroy, A.; Halliwell, S. Reynolds, T. Composite Recycling in the
Construction Industry; Composites A 2006, 37, 1216-1222.
Volume 60 May 2010 Journal of the Air & Waste Management Association 539