Estudio de Resinas Conductivas
Estudio de Resinas Conductivas
Estudio de Resinas Conductivas
net/publication/223562650
CITATIONS READS
41 1,716
2 authors, including:
Igor Novak
Slovak Academy of Sciences
313 PUBLICATIONS 1,733 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
Investigation of surface, adhesive and antibacterial properties of selected medicinal polymers modified by low-temperature plasma View project
All content following this page was uploaded by Igor Novak on 19 March 2018.
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
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
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
0 76 (78) –
5
2.5 72 (74) –
5.5 64 (66) – 4
34 6 (10) 4 (8) 1
44 2 (2) 2 (2) insulating region conductive region
0
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
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
5
References
4
[1] Jagur-Grodzinski J. Polym Adv Technol 2002;13:615.
3
insulating region conductive region
[2] Thongruang W, Spontak RJ, Balik CM. Polymer 2002;43:
2279.
2
[3] Chodak I, Omastova M, Pionteck J. J Appl Polym Sci
0.0 0.1 0.2 0.3 0.4 0.5 0.6
2001;82:1903.
Φf [4] Hampl J, Bouda V. Synth Met 1994;67:129.
[5] Chen G, Wu C, Weng W, Wu D, Yan W. Polymer 2003;44:
Fig. 6. Strength of adhesive joint formed by polyurethane 1781.
filled with graphite KS 15 (squares) and graphite KS 6 [6] Zhu J, Uhl FM, Fawn M, Morgan AB, Wilkie CA. Chem
(circles). Mater 2001;13:4649.
[7] Pan YX, Yu ZZ, Ou YC, Hu GH. J Polym Sci, Part B,
Polym Phys 2000;38:1626.
[8] Chen GH, Wu DJ, Weng WG, Yan WL. J Appl Polym Sci
2001;82:2506.
It was found that the strengths of adhesive joints, [9] Pluta M, Alexandre M, Blacher S, Dubois P, Jerome R.
based on the epoxy resin, are significantly higher than Polymer 2001;42:9293.
those based on PU in the whole concentration region, [10] Zheng W, Wong SC. Compos Sci Technol 2003;63:225.
since epoxy matrix has a higher adhesion to aluminum [11] Mamunya EP, Davidenko VV, Lebedev EV. Compos Int
than PU (values of 12.5 MPa for neat epoxy resin and 8 1997;4:169.
MPa for PU). This effect is more pronounced at lower [12] Novak I, Krupa I, Chodak I. J Mater Sci Lett 2002;21:
filler content (Fig. 5), when the particles of the filler are 1039.
[13] Novak I, Krupa I, Chodak I. Eur Polym J 2003;39:585.
better wetted. Comparing the different grades of
[14] Li F, Qi L, Yang J, Xu M, Luo X, Ma D. J Appl Polym Sci
graphite shows that graphite KS 6 increases the strength 2000;75:68.
of adhesive joint more than graphite KS 15, probably [15] Novak I, Krupa I, Chodak I. Synth Met 2002;131:93.
due to its higher specific surface. [16] Beaucage G, Rane S, Schafer DW, Long G, Fischer D.
The highest strengths of the adhesive joints were J Polym Sci, Part B, Polym Phys 1999;37:1105.
found for epoxy/graphite KS 6 composites. [17] Lux F. J Mater Sci 1993;28:285.
1422 I. Novak, I. Krupa / European Polymer Journal 40 (2004) 1417–1422
[18] Krupa I, Chod ak I. Eur Polym J 2001;37:2159. [21] Manson A, Sperling LH. Polymer blends and composites.
[19] Chod ak I, Krupa I. J Mater Sci Lett 1999;18:1457. New York: Plenum Press; 1976.
[20] Nielsen R. Mechanical properties of polymers and com- [22] Lee MCH, Tensa SJ. J Adhes Sci Technol 1989;3:
posites 2. New York: Marcel Dekker Inc; 1974. 291.