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Toughening of Epoxy Adhesives by Nanoparticles

Article  in  Journal of Adhesion Science and Technology · January 2009

DOI: 10.1163/156856108X379209

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 Journal of
ADHESION

/// VS Pill Journal of Adhesion Science and Technology 23 (2009) 753-768

www.brill.nl/jast

Toughening of Epoxy Adhesives by Nanoparticles

A. Buchman % H. Dodiuk-Kenig"*, A. D o t a n R . Tenne" and S. Kenig

" Rafael Ltd., P.O.B. 2250, Haifa 31021, Israel
Shenkar College of Engineering & Design, 12 Anna Frank St., Ramat Gan 52526,
' Israel Plastics & Rubber Center, Ramat Gan 52526, Israel
Weizmann Institute of Science, P.O.B. 26, Rehovot 76100, Israel

Abstract
With the emergence and commercialization of nanoparticles, new opportunities have
ening of epoxy adhesives using nanoparticles without sacrificing strength, rigidi
temperature, as is the case with conventional elastomeric tougheners. Inorganic F
disulfide (IF-WS2) nanoparticles and functionalized nano-POSS (Polyhedral-Oligomeric
were used to study the effects of nanoparticles on the toughening and mechanical
high temperature curing epoxy systems. Experimental results indicated that IF-WS2 i
toughness by more than 10 fold in both epoxy systems at very low concentrations (
increasing its storage modulus and preserving its glass transition temperature. Epo
demonstrated an increase in toughness in addition to preserving rigidity and therm
concentrations (3 wt%). It was postulated that chemical interaction of the sulfide
the inherent properties of WS2 were the decisive factors with respect to the outsta
case IF-WS2.

© Koninklijke Brill NV, Leiden, 2009

Keywords
Nano-toughening, epoxy adhesives, POSS, WS2

1. Introduction

Toughening of epoxy adhesives and fiber composites without sacrifici

has been a long-time challenge. Conventionally, toughening is achiev
poration of elastomers (both reactive and non-reactive). Elastomers
terminators due to their energy absorption characteristic and promote
In addition, they may promote craze formation i n the highly stressed
ahead of a loaded crack, thus leading to additional energy absorption
cases plastic deformation is the decisive factor exhibited as shear b
tiple crazes i n the resulting fracture surface.

* To whom correspondence should be addressed. E-mail: hannad@shenkar.ac.il

© Koninklijke Brill NV, Leiden, 2009 001:10.1163/156856108X379209

754 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 7

Usually toughening by elastomers leads to rigidity and decrease o

erties. I n addition to elastomers, rigid microparticles and modifie
ployed for improving toughness without scarificing rigidity [2, 3 ] .
microparticles cannot effectively stabihze or stop crack propagatio
Toughening by nanoparticles has been studied i n the last few yea
anisms proposed include: (a) crack deflection, (b) crack pinning,
void growth. Crack deflection and crack pinning are unlikely to ta
the nanoparticles are smaller than the crack-opening displacement
ever, plastic void growth takes place following debonding of particl
debonding process absorbs a smaller amount of energy compared to t
formation of the matrix, i t is essential because it reduces the con
tip and hence allows the matrix to deform plastically via a void grow
Additionally, the presence of nanoparticles in the ligaments betwee
nanoparticles can increase the stiffness of the plastically deformi
hence increase the absorbed strain energy density of the ligaments
deformation [4, 5]. Shear bands were identified i n the fracture su
nanocomposites indicating that energy was absorbed prior to fractur
Recent developments i n polymer nanocomposite technology have dem
that under optimized chemical functionalization of nanoparticles m
erties such as rigidity and strength can be effectively enhanced
taneously increasing both thermal properties (glass transition t
elongation to break. Among the nanoparticles evaluated were nanosili
carbon nanotubes (CNTs) and Polyhedral-Oligomeric-Sil-Sesquioxane
[7-10].
The present investigation was aimed at studying the effect of Inor
like tungsten disulfide nanoparticles (IF-WS2) and POSS nanoparti
toughness properties (impact and crack-opening modes) of their res
composites.

2, Experimental

Two types of nanoparticles were included i n this study. The first wa

ganic multi-wall fullerene-like nano-sphere (product of NanoMateria
abbreviated as IF-WS2 [11]. The second type consisted of three kinds
POSS: epoxy terminated POSS, octaphenyl terminated POSS and amine t
POSS (products of Hybrid Plastics, U S A ) . The nanoparticles were fi
ized using Scanning Electron Microscopy (SEM).
Two epoxy resins served as matrices: The first comprised o f a low
system and the second of a high-temperature system. The low-temper
was di-glycidyl-ether of bisphenol-A (DGEBA, Epon 815C, product
Stephenson, USA) cured with amido amine (Versamide 140, product
Stephenson, U S A ) . The mixing ratio was 70:30 w/w. The high-tempera
was a tetraglycidyl diamino diphenyl methane ( T G D D M ) (MY-721, pro
 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

Ciba-Geigy Corp., U S A ) cured with polypropylene glycol diamine (J

T-403, product of Hunstman Co., U S A ) . The mixing ratio was 60/40 w/w
Thermal properties of the bulk adhesive with and without nanopart
evaluated using Dynamic Mechanical Analysis (DMA-7e, Perkin Elmer) a
to A S T M D-5023, i n three-point bending mode, at a frequency of 1.0 H
perature range from 0 to 170°C. Sample bars of dimensions 1 x 3 x
used.
The IF-WS2 powder was incorporated into the epoxy resin by ultrason
for 4 h. The concentration range was 0.3-5 w t % . The various POSS mat
incorporated into the epoxy resin by mixing for 1/2 h using a magnet
Adhesion properties of selected formulations were characterized in
impact and crack-opening modes. The adherends used for the specim
Aluminum 2024-T3 treated with unsealed chromic acid anodization acc
MIL-B-8625. Single Lap Shear (SLS) joints were prepared and tested a
A S T M D-1002 at a loading speed of 2 mm/min. T-peel joints (90°) were
and tested according to A S T M D-1876 at a loading speed o f 200 mm/mi
samples were prepared and tested according to A S T M D-950 using the C
pact tester with a hammer weight of 30 kg. Fracture toughness was ev
a double cantilever beam (DCB) loaded in the opening mode (Mode I)
to A S T M D-3433. The elastic energy release rate (fracture toughness
calculated using the following A S T M equation:

Gc = : ^ — , (1)
2B da
where PQ — the critical load for crack initiation, C — the specimen's
B — the width of the specimen and a — the crack length. Here dC/da is

dC
da EsB\h^ ' hj'
where is the elastic modulus of the beam and h is half the thick
bonded DCB specimen. These A S T M equations do not take into account t
sive parameters. Fracture toughness was also evaluated using Penado'

Gc =

h\ 3 /h'
(3)

where K= mjE^, k = [k;^^,,^^ + / ^ a ' d L s i v e ] " ' ' ^adherend = 4EiB/h

^adhesive = B/t • £ 2 / ( 1 ~ ^2^- E is Young's modulus, G the shear mod
V is the Poisson's ratio, h is the thickness of the adherend and t t
adhesive. Penado's model, as distinct from the A S T M equation, takes
the adhesive parameters.
756 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 75

Scanning electron microscopy (SEM) was used to investigate the na

dispersion i n the polymer matrix as well as the morphology of the fa
of the bonded joints.

3. Results and Discussion

The investigation into the effect of nanoparticles on the toughn

nanocomposites commenced with the study of the nanocomposite static
ical and thermal properties. I n a second stage the impact and crac
characteristics were investigated and an attempt was made to correl
(especially the peel strength) and dynamic properties of the epoxy na

3.1. Morphology of Nanoparticles

The nanoparticles studied were analyzed by SEM. Figures 1 and 2(a-c)

morphology of the various nanoparticles (WS2, POSS) before incorporat
in the adhesives. As can be observed the particles appear agglomerat
the nano-effect due to the high surface to volume ratio, the agglome
has to be broken down and uniformly dispersed. This was achieved by
mechanical energy by mixing the nanoparticles i n the relevant adhesi
long time before adding the curing agent. The criterion for good mixi
transparency of the nanoparticle/resin mixtures.

3.2. Mechanical and Thermal Properties

Tables 1 and 2 summarize the results of shear and peel adhesion str
low-temperature and high-temperature curing epoxies with IF-WS2 nano
can be seen, there is an optimal concentration of nanoparticles, a
both systems, where the shear strength and peel strength reach a m
The Tg of both high- and low-temperature curing systems did not ch
WS2 was incorporated i n the whole concentration range studied. The

Figure 1. SEM image of IF-WS2 nanoparticles ( x 10000).

 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

Figure 2. (a) SEM image of octaphenyl functionalised POSS (x8000), (b) SEM im
functionalised POSS (x 8000) and (c) SEM image epoxy functionalised POSS (x 8000

Table 1.
Shear (kg/cm-^) and peel (N/mm) strengths of low-temperature epoxy/rF-WS2 systems

Property/IF-WS2 cone. (wt%) Shear strength (kg/cm^) Peel strength (N/mm)

0 198 A 0.20 M/C

0.15 179 A 0.19 M/C
0.3 184 A 0.22 C
0.5 229 C 0.25 C
1.0 179 A 0.23 C

Failure mode: A adhesional or interfacial, C — cohesive, M — mixed.

peel strengths of epoxy adhesives containing POSS with various funct

concentrations are summarized i n Tables 3 and 4.
As evident, an increase of about 20% was obtained in shear str
optimal concentration compared with the neat epoxy. Furthermore, a s
758 A. Buchman et al. / Journal of Adhesion Science and Technology 23 (2009) 7

Table 2.
Shear (kg/cm^) and peel strengths (N/mm) of high-temperature epoxy/IF-WS2 system

Property/IF-WS2 cone. (wt%) Shear strength (kg/cm"^) Peel strengt

0 150 C 0.99 M/C

0.3 154 C 1.05 C
0.5 158 C 1.72 C
1.0 137 C 1.20 C

- A
Failure modes: adhesional
— or interfacial,
— cohesive,
C M — mixed.

Table 3.
Shear strength ^)
(kg/cm
of low-temperature epoxy resin/POSS systems

Cone, of POSS functionality

POSS (wt%) Octaphenyl Amino Epoxy

0.0 158±10M 158± lOM 158±10M

0.3 1 6 6 ± 18M 185± 1 M 148± lOM
0.5 172± lOM 171 ± l O M 142±12M
1.0 1 6 6 ± 12M 1 6 4 ± 18M 134± lOM
3.0 159 ± 12 M/C 193 ± 15 C 132±7C
5.0 1 8 0 ± 14C 156 ± 9 C 139± 14C

Failure mode: mixed,

M — C — cohesive.

Table 4.
Peel strength (N/mm) of low-temperature epoxy resin/POSS systems

Cone, of POSS type

POSS (wt%) Amino Octaphenyl Epoxy

0.0 0.57 ± 0 . 1 0 M/C 0.57 ± 0.10 C 0.57 ± 0.10 C

0.3 0.74 ± 0.03 C 0.66 ± 0.06 C 0.52 ± 0.08 C
0.5 0.56 ± 0 . 0 6 M/C 0.82 ± 0.05 C 0.61 ±0.03 C
1.0 0.48 ± 0 . 0 3 M/C 0.68 ± 0.10 C 0.50 ± 0.07 C
3.0 0.66 ± 0.06 C 0.46 ± 0.05 M/C 0.62 ± 0.06 C
5.0 0.75 ±0.05 C 0.44 ± 0.04 M/C 0.59 ± 0.05 C

Failure mode: M — mixed, C — cohesive.

crease i n peel strength (25%) was obtained at the optimal concentrat

with the neat epoxy. Higher shear and peel strength values were obtai
and octaphenyl functionahties. Epoxy functionahty of the POSS had ne
fect or only slight improvement was observed. This was due to agglome
epoxy-POSS especially at high concentrations. I n both systems both s
(shear strength) and toughening (peel strength) are evident i n addition t
 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

Table 5.
Shear (kg/cm^) and peel (N/mm) strengths for various high-temperature epoxy/POSS
timal concentrations

POSS functionality Optimal cone. (wt%) Shear strength Peel strength

None 0 142 ± 22 C 0.18 ±0.05 C

Epoxy 0.5 164±18C 0.23 ±0.02 A
Octaphenyl 5 184±20C 0.24 ± 0.04 C
Amino 0.3 145 ± 15 A 0.23 ±0.1 A

Failure mode: adhesional

A — or interfacial,
- mixed,
M —
C — cohesive.

Table 6.
Tg values of low-temperature epoxy resin with optimal concentrations of POSS

POSS functionality Optimal cone. (wt%) Tg (°C)

Neat epoxy 0 86.0

Amino 0 86.0
Epoxy 3 89.5
Octaphenyl 0.3 92.9

(see next section). It should be emphasized that in the case of th

functionalities the toughening effect, as manifested in increased p
obtained at relatively low concentrations ( < 1 w t % ) . Failure mode of
mens was cohesive i n the adhesive. I n shear specimens, low concentra
showed a mixed failure while only high concentrations showed cohesiv
Table 5 summarizes the results of shear and peel strengths for th
ature curing epoxy with POSS nano-fillers with various functionalit
concentrations.
As can be observed an increase of 30% was obtained i n shear str
optimal formulation concentration compared with the neat epoxy. Furt
increase in peel strength of 25% was obtained at the optimal formul
tration compared with the neat epoxy. The highest shear and peel s
were obtained for the octaphenyl functionality. As previously mentio
in both systems strengthening (shear strength) and toughening (peel
evident.
Table 6 depicts the variation of the Tg of the nanoparticle-epoxy
(low temperature) with various POSS functionality types and concentr
As can be observed the Tg increased up to the optimal concentrati
The increase i n the Tg takes place in the concentration range of
POSS. The maximum increase i n Tg was 6 ° C compared to the neat epoxy
tion. Higher amounts of POSS caused a reduction i n Tg. Furthermore, t
value of Tg depends on both the POSS concentration and the POSS func
760 A. Buchman et Journal of Adhesion Science and Technology 23 (2009) 753-

Table 7.
Tg (°C) values of high-temperature epoxy resin with POSS

POSS POSS cone. (wt%)

functionality
0 0.2 0.3 0.5 1 3 5

Octaphenyl 141 146 150 150 146

Amino 141 143 144 145 146 143 143
Epoxy 141 143 142 144 142

should be stated that Tg is not reduced, as is the case with elasto

and the phenyl group has the highest effect as expected due to it
acteristics. Table 7 depicts the variation of the Tg o f the high-t
formulation w i t h various POSS types.
As can be observed the Tg increased also i n this case of octaphen
maximum increase i n the Tg was 9 ° C compared to the neat epoxy fo
Higher amounts of POSS caused a reduction i n the Tg o f the adhesive
be due to agglomeration at high concentrations.

3.3. Impact Strength

The impact strength for low temperature curing epoxy with various co
and functionalities o f POSS and IF-WS2 are summarized i n Figs 3 and
seen that the impact resistance, at optimal concentration, increase
150% for POSS at 3 w t % and by more than 200% for IF-WS2 at 0.3 w
failures were cohesive i n the adhesive. The failure surface was roug
in appearance. For comparison, a set of impact adhesion samples w
using a toughened epoxy film adhesive ( F M 73, Cytec) cured at 120°
gave impact strength of 9.5 N m , which equals the results obtained w
IF-WS2 filled epoxy adhesives.

3.4. Fracture Toughness

DCB specimens were bonded with low-temperature epoxy adhesive with a

out POSS or IF-WS2. The bond thickness was 0.1 m m . The D C B specimen
loaded i n Mode I using a mechanical tester at a rate o f 2 mm/min
crack opened (signified by a reduction i n load). The tip o f the cr
(crack advance). When the load became constant, the crack tip was
(crack arrest) and the sample was further loaded. A n average o f fiv
taken for each specimen. A t the end of the test the adherends were
reveal the fracture mode. Already while testing, i t could clearly b
the cracks i n the epoxy which contained nano-POSS or nano-IF-WS2
only slightly compared to samples bonded with neat epoxy. GQ was ca
accordance with two methods ( A S T M equation and Penado model). The re
summarized i n Tables 8-10.
 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

Octaphenyl-POSS
Epoxy-POSS
Amino-POSS

3 1
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
POSS (wt%)

Figure 3. Impact strength of POSS/low-temperature epoxy nanocomposites.

10

3
2 "1 1 ' 1 1

0 0.5 1 1.5 2 2.5

(wt%)

Figure 4. Impact strength of IF-WS2/low-temperature epoxy nanocomposites.

Table 8.
(J/m^) of POSS/epoxy (low temp.) nanocomposites calculated with the ASTM equati
nado model

Cone, of POSS functionality

POSS (wt%) Octaphenyl Amino Epoxy
ASTM Penado ASTM Penado ASTM Penado

0 196 255 196 255 196 255

0.3 717 856 445 538 387 468
1.0 600 721 1308 1583 536 635
3.0 388 450 2757 3241 1146 1359
4.0 800 942 848 1100 941 1133
762 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

Table 9.
GQ (J/m^) of IF-WS2/epoxy (low temp.) nanocomposites, cal-
culated with the ASTM equation and Penado model

Cone, of WS2 (wt%) ASTM Penado

0 196 255
0.3 1276 1540
0.5 514 580
1.0 511 636
2.0 452 493

Table 10.
Gc (J/m^) of IF-WS2/epoxy (high temp.) nanocomposites, cal-
culated with the ASTM equation and Penado model

Cone, of WS2 (wt%) ASTM Penado

0 588 511
0.3 2903 2328
0.5 1098 965
1.0 433 403
3.0 493 452
5.0 1156 916

The resuhs indicate a remarkable improvement i n fracture toughnes

hesive when nano-IF-WS2 (0.3 w t % ) or nano-POSS (3 w t % ) were added e
small quantities. A t the optimal concentrations of POSS or IF-WS2 th
lease rate (Gc) increases by 3 to more than 10 times compared to
It should be emphasized that amino-POSS and epoxy-POSS containing
nanocomposites exhibited the highest values of fracture toughness at
tration. The IF-WS2/epoxy nanocomposite showed the highest fracture t
only 0.3 w t % . Furthermore, the optimal concentration for the static
properties is similar to the ones associated with the dynamic prop
toughness) — 3% for POSS and 0.3% for IF-WS2. However, the highest i
was for the fracture toughness followed by impact strength and the st

3.5. SEM Investigation of Failure Surfaces

Failure surfaces of various POSS/epoxy formulations were examined.

sion of the POSS/epoxy nanocomposites to the adherend was good as w
dispersion of the POSS i n the epoxy matrix (Figs 5-7).
Impact failure surfaces of various POSS/epoxy formulations were exa
micrographs indicated very good adhesion of the POSS/epoxy to the ad
level of adhesion depends on the POSS functionahty and its concent
A. Buchman et 2^./ Journal of Adhesion Science and Technology 23 (2009) 753-76

Figure 5. Fracture surface of the octaphenyl-POSS/epoxy system on A l adher

Figure 6. Fracture surface of the epoxy-POSS/epoxy on A l adherend.

- 1 0 ^im

Figure 7. Fracture surface of amino-POSS/epoxy system on A l adherend.

764 A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

best impact resistant formulations showed high roughness surfaces co

smooth surface o f the reference non-filled adhesive (Figs 8-12).
This roughness comprises of an array o f micro-cracks, which are t
nanoparticles (Fig. 12). While i n the case o f microparticle compos
caused and the fracture occurs as the critical crack length is reac
nanoparticle composites an array of micro-cracks is obtained and th
length is not reached. Thus fracture is inhibited.
Impact failure surfaces of various IF-WS2/epoxy formulations were
The fracture surfaces indicated very good adhesion o f the IF-WS2/
adherend. The level of adhesion depends on the IF-WS2 concentratio
impact resistant materials showed high surface roughness compared to
mre surface o f the reference non-filled adhesive (Figs 13-15).

100

Figure 8. Impact failure surface of neat epoxy.

20 lam

Figure 9. Impact failure surface of 4 wt% amino-POSS/epoxy system.

A. Buchman et al. /Journal of Adhesion Science and Technology 23 (2009) 753

I 1

Figure 10. Impact failure surface of neat epoxy.

I 1
1 \x.m

Figure 12. Crack tip of impact failure surface of 4 wt% amino-POSS/epoxy sy

 II
10

Figure 14. Impact failure surface for 0.3 wt% IF-WS2/epoxy (roughness).

Figure 15. Crack tip of 0.3 wt% IF-WS2/epoxy.

 A. Buchman et al. /Journal of Adhesion Science and Technology
76723 (2009) 753

This roughness consists of an array of micro-cracks, which were in

nanoparticles (Fig. 15).

4. Conclusions

Incorporation of nano-IF-WS2, and functionalized POSS increased both

and peel strengths of both low and high temperature curing epoxies
concentrations were used. The optimal value depended on the type o
IF-WS2 nanoparticles incorporated i n epoxy adhesives exhibited maxi
and peel strengths as well as impact and toughness properties at
centrations (0.3-0.5 w t % ) . Functionahzed POSS exhibited maximum pro
higher concentrations (3 w t % ) i n both epoxy systems.
SEM micrographs of fractured surfaces indicated that good dispers
nanoparticles were achieved i n most cases. Moreover, the adhesion
nanoparticles to the epoxy systems was excellent. This may be due
tivity of the sulfide and epoxy groups. I n the case of POSS, the amin
showed the best interfacial adhesion to epoxy. It should be emphas
addition of nanoparticles altered the morphology from smooth into r
surfaces.
Excess amounts of both IF-WS2 and POSS beyond the respective ma
values resulted i n decrease of adhesive properties and agglomeration
ticles. The type of the functional group (reactive/non-reactive) su
POSS is the dominant factor i n the formation of the molecular networ
effect on properties. I n all cases the glass transition temperature
even increased slightly with increased toughening. Though shear and p
increased when incorporating nanoparticles, the most significant e
the impact and fracture toughness, which increased by more than ten
concluded that incorporation of both IF-WS2 and POSS into matrices
composites could be beneficial. This is the subject for a forthcomin

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