Estudio de Resinas Conductivas

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Electro-conductive resins filled with graphite for casting applications

Article  in  European Polymer Journal · July 2004


DOI: 10.1016/j.eurpolymj.2004.01.033

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EUROPEAN
POLYMER
JOURNAL
European Polymer Journal 40 (2004) 1417–1422
www.elsevier.com/locate/europolj

Electro-conductive resins filled with graphite


for casting applications
ak *, Igor Krupa
Igor Nov
Department of Composite Thermoplastics, Polymer Institute of the Slovak Academy of Sciences, Dubravska cesta 9,
842 36 Bratislava, Slovakia
Received 21 November 2003; received in revised form 21 January 2004; accepted 21 January 2004
Available online 6 March 2004

Abstract
Electro-conductive resins, convenient for casting and coating applications were investigated in this paper.
Electrical conductivity of epoxy and polyurethane resins, filled with two different grades of synthetic graphite
(different average size) was studied. It was found that all the investigated composites became electro-conductive when
filled with 22-vol% of the filler.
The impact strength of epoxy and polyurethane resins filled with graphite was also investigated. A decrease in impact
strength with an increase in filler content was observed in all cases. The highest values of impact strength were found for
polyurethane/graphite KS 6 composites.
The strength of adhesion of the filled resins to aluminum was also determined. A decrease in the strength of adhesive
joints to aluminum foils with an increase in filler content was observed in all cases. The strongest adhesive joints were
found for the epoxy/graphite KS 6 composites.
 2004 Elsevier Ltd. All rights reserved.

Keywords: Electrical conductivity; Impact strength; Strength of adhesive joint; Graphite; Antistatic properties; Discharging
characteristics

1. Introduction High performance antistatic or/and electrically


conductive materials, used for casting (plank, etc) or
A high electrical charge on the surface of plastics coatings, are usually designed by combining the ther-
causes some problems, like handling during transport, mosetting resin and efficient electrically conductive fillers
storage and packing, dust contamination, affecting both [12–14]. There are usually a few types of basic poly-
appearance and performance of end products, risk of meric matrices available for casting––acrylics, polyes-
electrical shocks to employees working at the machines, ters, polyurethanes (PU) and epoxies. The filling of the
as well as the risk of electrical discharge causing fire or system is usually focused only on the resin, and the
explosion [1–3]. To reduce the surface or/and volume cross-linking agent is unfilled. Resins can be cast as a
electric resistivity and hence dissipate high electric pourable liquid and/or are properly filled using various
charge density on the surface of plastics, either antistatic inorganic or organic fillers. Most resins can be cast in
agents or electro-conductive fillers are used [4–11]. properly separated flexible molds made of polysulfide
and PU. To work with PU requires usually some special
equipment. Casting acrylic resin means subjecting the
polymer/monomer ‘‘dough’’ to high pressure and tem-
*
Corresponding author. Tel.: +421-254773308; fax: +421- perature in an autoclave, using special molds. Because of
254775923. this, and because of the fact that uncured acrylic is
E-mail address: [email protected] (I. Novak). highly toxic, most users should avoid using this method
0014-3057/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2004.01.033
1418 I. Novak, I. Krupa / European Polymer Journal 40 (2004) 1417–1422

and rather cast PU resins that set at room temperature hardened 24 h at room temperature, and consequently
[15]. for 3 h at 100 C.
Graphite is frequently used as an electroconductive For measurements of electrical properties, circular
filler, due to its moderate cost and good conductivity discs with a diameter 30 mm and a thickness about 0.5
[16]. Graphite has also a positive influence on the mm were prepared by casting into silicone rubber forms.
mechanical properties, as well as thermal and dimen- The samples were tested after 7 days of adhesive hard-
sional stability. ening at room temperature.
This paper concentrates on a study of the electrical The volume electrical conductivity of adhesives was
properties (electrical conductivity, electrostatic parame- measured according to ASTM D-257. A three-electrode
ters) of epoxy and PU resins filled with two grades of electrometer arrangement was used for the DC-
synthetic graphite, as well as on the investigation of measurement of the electrical resistivity. The voltage
some mechanical properties such as impact strength and level varied in the range 0.1–500 V.
strength of the adhesive joint to aluminum foils. The specimens (80 · 10 · 3 mm) for determination of
impact strengths were prepared by casting in silicone
rubber forms. After 7 days of hardening at ambient
2. Experimental temperature, the samples were tested at room tempera-
ture using a Charpy pendulum working in the range 0–4
A two-component PU adhesive Veropal (Synpo, J/cm2 .
Czech Republic)––polyol with a viscosity at 25 C 800 The strengths of adhesive joints were measured by
mPa s and methylene diphenyl diisocyanate as a cross- tensile testing of aluminum single overlapped adhesive
linking agent having a viscosity of 1000 mPa s and two- joints, with dimensions 60 · 10 · 2 mm using an 5 kN
component epoxy adhesive consisting of the epoxy universal testing device Instron 4301 (Instron, England)
oligomer ChS Epoxy 531 (based on Bisphenol-A-di- at a constant cross-head speed of 10 mm/min. The
glycidylether) (Spolchemie, Czech Republic) modified by measured data were processed using computer software
the reactive solvent 1,6-hexanediol-diglycidylether (Sa- that enables the statistical evaluation of the results.
chem, USA), and having a viscosity at 25 C of 2.2 Pa s Antistatic properties of the composite adhesives were
and the curing agent Aminoamid DE 400 based on measured using an integrated electrometer Polystat PS-1
diethylene triamine (Bohemiachem, Czech Republic), (JZD Jizera, Czech Republic). The 1-mm thick discs
were used as the polymer matrices. were prepared with epoxy and polyurethane casting
The extra fine graphites Lonza KS 6 and KS 15 resin using a silicone rubber form. After hardening the
(Lonza, Switzerland) in the form of flakes were used as specimens were cleaned with n-heptane, fixed in a
the filler. The purity of the graphite powders analyzed stainless steel device holder and charged during 20 s in
for determination of carbon content was: C P 99.9%, 15 kV electric field using a corona discharge plasma. The
the ash content <0.1%. A large crystallite size [>100 nm] maximum surface potential of sample and its changes
as well as an ideal interlayer spacing smaller than 0.3354 with time were periodically measured.
nm are indicative of the high degree of graphitization of
graphite powders. The density (in Hg)––2.19 g/cm3 ,
specific surface––P50 m2 /g, particle size (determined by 3. Results and discussion
laser difractometry)––90% of particles were smaller than
15 lm (KS 15) or 6 lm (KS 6). 3.1. Electrical conductivity
The composition of the aluminum alloy AlMgSi0.5
was: 98.45-wt.% Al, 0.7-wt.% Mg, 0.5-wt.% Si, 0.2-wt.% The dependence of electrical conductivity of epoxy
Fe and 0.15-wt.% Mn. and PU resin, filled by synthetic graphite, is shown in
The electrically conductive materials were prepared Figs. 1 and 2.
by mixing both components of epoxy or PU resins with The concentration of the filler, when internal
the respective electrically conductive fillers at room conductive network of particles is formed within the
temperature for 20 min at a mixing speed 20 rpm using a polymeric matrix and the material becomes electrocon-
lab-scale mixer (Koba, SR). The components of epoxy ductive is called percolation concentration ð/c Þ. A num-
or PU resins, i.e. epoxy resin and hardener or polyol and ber of factors have been identified as being important for
hardener, were mixed together in the weight ratio 2:1. the formation of conductive networks in filled polymers,
The single overlapped adhesive joints were prepared including the morphology of the filler and its surface
after degreasing of the aluminum alloy slabs with tolu- activity, the wettability of the filler by the polymer,
ene and subsequent bonding. The dimensions of the solidification rates after mixing and post-processing the
aluminum slabs were 60 · 10 · 2 mm; the thickness of the rheology of the polymer during the mixing process, etc.
adhesive layer was 0.1 mm. The bonded area of each This complexity makes difficulties in prediction of per-
adhesive joint was 1 cm2 . All adhesive joints were colation concentration as well as the dependency of
I. Novak, I. Krupa / European Polymer Journal 40 (2004) 1417–1422 1419

0.0 0.1 0.2 0.3 0.4 0.5 0.6 B, a, n are adjustable parameters, rc is the electrical
12 12
conductivity of the composites, rm the electrical con-
ductivity of the polymeric matrix, and /f the volume
10 10
portion of the filler. A percolation point ð/c Þ has been
arbitrary identified as an inflexion point in this empirical
8 8
fitting curve.
m
logσ /σ

Epoxy/graphite KS15
An inflexion point ð/i Þ was calculated according to
c

6 Epoxy/graphite KS6 6
Eq. (2) [18,19]:
4 insulating region conductive region 4 /i  /c ¼ lnðnÞ=a ð2Þ
Φc= 22 vol % The reason, why percolation concentration was arbi-
2 2

trary defined is that in real situation, when only limited


0 0 number of experimental points is available, the unam-
biguous determination of exact percolation concentra-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 tion is difficult.
Φf It was found that the percolation concentration de-
pends on neither the grade of the graphite nor on the
Fig. 1. Electrical conductivity of epoxy resin filled with
graphite KS 15 (squares) and graphite KS 6 (circles). Solid
type of polymeric matrix. In all investigated cases,
line ¼ fitting according to Eq. (1). the value of 22-vol% of the filler was determined as
the concentration where material becomes conductive. It
was also found that the matrix (Epoxy, PU) as well as
0.0 0.1 0.2 0.3 0.4 0.5 0.6
the type of graphite has no significant influence on the
12
electrical conductivity of composites, as seen in Figs. 1
12
and 2.
10
10
3.2. Antistatic properties
8 PU/graphite KS15
8
PU/graphite KS6
Epoxy and PU resins are often used for coating of an
m
logσ /σ

inorganic or metallic surface. If they are filled with


c

6
6
insulating region conductive region conductive filler, the coatings become antistatic.
4
4 The antistatic properties, expressed by discharging
Φc = 22 vol % characteristics of epoxy and PU composite adhesives
2
2 filled with two grades of graphite are summarized in
Tables 1 and 2.
0 0 The discharging characteristics of the samples, i.e. the
maximum surface electrostatic potential ðVmax Þ and the
0.0 0.1 0.2 0.3 0.4 0.5 0.6
half-life of electrostatic discharging ðs1=2 Þ [18], were
Φf
investigated for epoxy resin (Table 1) and for PU (Table
Fig. 2. Electrical conductivity of polyurethane filled with
2). The results obtained from the measurement of the
graphite KS 15 (squares) and graphite KS 6 (circles). Solid antistatic properties of epoxy and PU composite adhe-
line ¼ fitting according to Eq. (1). sives showed that the antistatic properties were reached

Table 1
electrical conductivity on the filler content. The most Discharging characteristics of epoxy filled with graphite KS 6
prominent models were reviewed by Lux [17]. He con- and KS 15 (the values in the brackets)
cluded that currently no model exists which is able to Content of graphite KS 6 Vmax  101 s1=2 (s)
explain all the different experimental results as well as to (KS 15) (vol%) (kV)
able to account for the extensive influence of different 0 72 (76) –
parameters and processing methods on the percolation 2.5 68 (72) –
process. In the past, we have suggested the empirical 5.5 56 (60) –
function given by Eq. (1) [18,19], which appropriately 11.7 48 (54) 152 (166)
fits experimental dependencies electrical conductivity 18 36 (40) 94 (120)
versus volume filler content. 26 8 (12) 8 (10)
34 6 (8) 4 (8)
logðrc =rm Þ ¼ Bð1  ea/
f Þn ð1Þ 44 2 (2) 2 (2)
1420 I. Novak, I. Krupa / European Polymer Journal 40 (2004) 1417–1422

Table 2
9
Discharging characteristics of PU filled with graphite KS 6 and Epoxy/graphite KS15
Epoxy/graphite KS6
KS 15 8

Content of graphite KS 6 Vmax  101 s1=2 (s) 7

(KS15) (vol%) (kV)

Impact strength, MPa


6

0 76 (78) –
5
2.5 72 (74) –
5.5 64 (66) – 4

11.7 54 (62) 166 (196) 3


18 44 (50) 128 (138)
26 10 (10) 20 (36) 2

34 6 (10) 4 (8) 1
44 2 (2) 2 (2) insulating region conductive region
0

0.0 0.1 0.2 0.3 0.4 0.5 0.6

Φf
at the lower concentration of the graphite in the case of
Fig. 3. Impact strength of epoxy resin filled with graphite KS
epoxy composite adhesives in comparison with PU
15 (circles) and graphite KS6 (squares).
adhesives. Electrically conductive adhesives, having a
leakage half-life of electrostatic discharge lower than
10 s, are considered as antistatic materials. This goal
was reached for a graphite content in the epoxy-based
12
composites exceeding 22-vol%, e.g. for 26-vol% of gra- PU / graphite KS15
phite in the composite adhesive (Table 1 for epoxy and PU / graphite KS6
10
Table 2 for PU), and the half-life of electrostatic dis-
Impact strength, MPa

charge was 10 s or lower. The epoxy and PU composites


8
with graphite KS 15 (Tables 1 and 2, values in brackets)
give higher values of the surface electrostatic potential
6
and of the half-life of electrostatic discharge, compared
to the graphite KS 6. insulating region conductive region
4

3.3. Impact strength 2

The dependence of impact strength of epoxy and PU 0


resin filled with graphite KS 15 and graphite KS 6 on the 0.0 0.1 0.2 0.3 0.4 0.5 0.6

volume portion of the filler is shown in Figs. 3 and 4. A Φf


decrease in impact strength and toughness with an in-
Fig. 4. Impact strength of polyurethane filled with graphite KS
crease in filler content was observed in all cases. This
15 (squares) and graphite KS 6 (circles).
behavior is common for polymers filled with particulate
filler. The particulate filler initiates a crack formation via
stress concentration on the filler surface [20–22]. As far
investigated composites, the impact strength of materi- adhesive joints created by two aluminum slabs were
als, filled with graphite KS 6 is higher than the impact bonded together by the filled resins, and then mechani-
strength of materials filled by graphite KS 15 (Fig. 3), cally strained. The dependence of the strength of adhe-
probably due to its higher specific surface. This behavior sive joint on the filler content is shown in Figs. 5 and 6.
was observed for both epoxy and polyurethane matrix. It is seen that the strength of adhesive joint decreases
It was found that the impact strength of PU/graphite with an increase in filler content in the whole concen-
composites is higher than that of impact strength of tration range, for all investigated resins. Despite the fact
epoxy/graphite composites for both grades of graphite. that the strength of the adhesive joints decreases with an
This behavior is the result of the higher elasticity of PU. increase in the filler content, the composites can be
successfully used as electrically conductive adhesives,
3.4. Adhesion of epoxy/graphite and PU/graphite resins to since the improvement in the electrical properties of
aluminum adhesives, through the dispergation of the conductive
filler in the polymeric matrices, is much more signifi-
The adhesion of epoxy as well as PU resin filled with cant than the deterioration of strength of the adhesive
graphite particles to aluminum was investigated. The joints.
I. Novak, I. Krupa / European Polymer Journal 40 (2004) 1417–1422 1421

14 4. Conclusions
Epoxy/graphite KS15
Epoxy/graphite KS6 A percolation concentration of electrically conduc-
Strength of adhesive joint, MPa

12
tive resins, filled with different grade of graphite, was
determined to be 22-vol% for all the investigated com-
10
posites. The grade of graphite, as well as type of poly-
meric resin, had no significant influence on either
insulating region conductive region
8 percolation concentration, or electrical conductivity.
These results were confirmed by measurements of anti-
6
static properties because the electrostatic material was
obtained after reaching the percolation concentration of
graphite in the composite adhesive.
4
A decrease in impact strength with an increase in
0.0 0.1 0.2 0.3 0.4 0.5 0.6
filler content was observed in all cases. The highest im-
Φf pact strength was observed for PU/graphite KS 6 com-
posites.
Fig. 5. Strength of adhesive joint formed by epoxy resin filled A decrease in the strength of the adhesive joint to
with graphite KS 15 (circles) and graphite KS 6 (squares).
aluminum with an increase in filler content was observed
in all cases. The highest adhesive joint strengths were
observed for adhesives based on epoxy/graphite KS 6.
10

PU / graphite KS15 Acknowledgements


9
PU / graphite KS6
The authors are grateful to the Slovak grant agency
Strength of adhesive joint, MPa

VEGA (grant no. 2/1060/23) for financial support of this


7
research.
6

5
References
4
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