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Materials Letters 58 (2003) 154 – 158


A novel ultrasonic transducer backing from porous epoxy resin–titanium–

silane coupling agent and plasticizer composites
Farid El-Tantawy a,*, Yong Kiel Sung b
Department of Physics, Faculty of Science, Suez Canal University, Ismailia, Egypt
Department of Chemistry, Dongguk University, Seoul 100-715, South Korea
Received 6 January 2003; received in revised form 5 May 2003; accepted 9 May 2003


In this paper, a new composite for ultrasonic attenuation backing has been successfully fabricated from porous epoxy resin containing
titanium (Ti), silane coupling agent and plasticizer composites. The effect of Ti particles on the network structure and mechanical properties
of epoxy resin has been analyzed in detail. The ultrasonic parameters in epoxy composites have been measured by a conventional pulse-echo-
overlap technique at a frequency of 1 – 5 MHz. The effect of Ti content and temperature on the longitudinal sound velocity and attenuation of
epoxy resin composites were investigated. Precise in situ observations of the acoustic properties such as attenuation and acoustic impedance
of epoxy composites are expected to be useful for ultrasonic transducer systems for new as well as for backing application with high
D 2003 Elsevier B.V. All rights reserved.

Keywords: Epoxy resin; Titanium; Materials composite; Microstructure; Mechanical properties; Ultrasonic properties; Backing; High attenuation

1. Introduction ized by a hardener to obtain composite materials. This

method allows one to achieve simultaneously a low initial
This study is part of an on-going research project aiming viscosity, a high attenuation and a high stiffness. The
to develop a high performance composite material for ultra- second uses a reactive liquid rubber, which is initially
sonic transducer backing with high acoustic impedance, soluble in epoxy resin and the phase separation occurs
attenuation and toughness. Epoxy resins are commonly during the vulcanization of the epoxy. This method does
used as polymeric matrices in high-performance composites not increase significantly the mixture viscosity of the
due to their good thermal stability, environmental resistance composite [6]. To overcome this shortcoming and to fulfill
and good mechanical properties and in the manufacture of the above stated needs, the epoxy resin has been modified
backings because of its low initial viscosity and its high by adding plasticizer, coupling agent and Ti powder. To the
adhesion [1 –5]. In fact, the need for transducer suitable for best of the author’s knowledge, porous epoxy filled with Ti
use in attenuation backing under high hydrostatic conditions particles, silane coupling agent and plasticizer for ultrasonic
is increasing in industry. Typically, backings are composed backings are still unavailable in publications. The target of
of epoxies loaded with metallic filler such as tungsten, iron, the study is the fabrication of a novel attenuation backing
copper, magnesium and aluminum are used to obtain high based on porous epoxy – Ti – silane coupling agent and
acoustic impedance for the backing material, whereas fillers plasticizer composites. The effect of Ti content on the
of wood dust, glass and cork are used for low impedance structure and mechanical properties of the epoxy compo-
backings [4,5]. It is well known that there are two methods sites was interpreted in detail. Also, the temperature depen-
to modify epoxy resin: the first consists of adding rubber dence of attenuation and sound velocity of epoxy
particles in the initial liquid resin, which is then polymer- composites were tested. For ultrasonic transducer backing,
the effect of Ti content and frequency on the attenuation
was investigated. Furthermore, the effect of Ti content on
* Corresponding author. Fax: +20-81-025-262-6265. the acoustic impedance of epoxy composites was also
E-mail address: faridtantawy@yahoo.com (F. El-Tantawy). tested.

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
F. El-Tantawy, Y.K. Sung / Materials Letters 58 (2003) 154–158 155

2. Experimental work 3. Results and discussion

With the above aim in mind, the polymer used in this 3.1. Network structure and mechanical properties of the
investigation was a commercial epoxy resin (type 828) and composite
hardener (type B002W) supplied by (Yuka shell epoxy
chemical, Tokyo, Japan). A stoichiometric resin/hardening Knowledge of the network structure and mechanical
ratio 100:20 by weight was used according to the manu- properties of thermosetting resins is essential in order to
facturer’s data sheets. Titanium powder with particle size 20 be able to choose a proper set of processing parameters and
Am was used as reinforcing and attenuation scattering agent. type of fillers, which give good material properties. The
Glycerol (Gly, analytical grade) and g-glycidoxy propyl SEM was used to investigate the morphology of the cured
trimethoxy silane (A-188) were used as the plasticizer and epoxy – Ti composites. Fig. 1a presents the SEM for sample
coupling agent, respectively. The amount of glycerol was 15 Ti5 of epoxy composites. It is shown that the Ti particles are
wt.% and silane was 2 wt.% in the composite. Several homogeneously distributed and sink into the porous epoxy
batches of epoxy – Ti weight ratios were considered: matrix. Closer inspection shows that there is big amount of
99.8:0.2, 99.6:0.4, 99.4:0.6, 99.2:0.8 and 99:1, respectively epoxy matrix adhered and Ti particles are coated by an
and abbreviated as Ti1, Ti2, Ti3, Ti4 and Ti5, respectively. epoxy resin, indicating a strong interface within epoxy
The green epoxy-hardener with different content of filler composites. The cross-link density (CLD) = qE NA/Mw,
was prepared by centrifuging mixer for 2 min at room where qE is the density of epoxy, NA is Avogadro’s number
temperature. The bulk samples of composite were obtained and Mw is the molecular weight between cross-link’s. The
by casting the green composites on alumina mould and extent of filler reinforcement (g) is given by: Vr0 /
placed in an electrical oven that was preheated to 60 jC for Vrf = 1  c(f/1-f), where Vrf is the volume fraction of
30 min. Then, the epoxy-filler composites were cured under swollen epoxy in the fully swollen filled sample and f is
hot uniaxial pressure 150 KN/m2 at 100 jC for 2 h. the volume fraction of Ti. The dependence of cross-linking
Morphology study of the epoxy composites was conducted density, extent of filler reinforcement and molar volume
on Scanning Electron Microscopy (SEM, JSM-5310 LVB, (Vm) on Ti content of epoxy composites is shown in Fig. 1b.
JEOL). The molar volume of the composites (Vm) was It is observed that the CLD, c and Vm increase linearly and
measured by a pycnometer using a mixture of carbon strongly depend on the Ti content. The reason is considered
tetrachloride and toluene as a medium [2]. Before the to be due to the chemical cross-linking to increase the
measurements were made, the specimens were cut into entanglement contribution in the network structure of epoxy
fragments and vacuum dried for 1 day. The mechanical composite. It is worthy that the positive value of c refers that
properties of the epoxy composites were measured using an a reinforcing filler has good polymer –filler interaction. This
Instron materials testing machine. The samples were pre- implies that Ti acts as a reinforcing effect and reacts with
pared according to ASTM DIN53557 standard [1]. The epoxy molecules and increases the interfacial adhesion
dielectric properties of the composites were measured at within epoxy composites as confirmed by the glass transi-
frequency 1 kHz by using RLC Bridge (3541 Y-Hitester, tion (Tg), viscosity (g), surface tension (ST) and packing
Hioki, Japan). Silver paste was used to ensure a good factor PF = qb/qt (where qb and qt are the particle bulk and
contact of the sample surface with copper electrodes. The true densities, respectively). The results shown in Fig. 1c
glass transition temperature (Tg) and specific heats (Cp) are relate to the effect of Ti content on the Tg, g, ST and PF of
measured by differential scanning calorimeter as described epoxy composites. It is found that Tg, g and PF increase with
elsewhere [2]. Viscosity (g) was measured by viscometer increasing filler content in the epoxy composites. The
model (VM-A, Japan). Surface tension (ST) was measured increase in Tg is most likely due to the increase of cross-
by using a surface tension-meter model (GPYP-A3, Japan). linking density [8]. The viscosity and packing factors
The ultrasonic measurements were performed using an support this claim; a greater cross-link density tends to
ultrasonic flaw detector of type Krautkramer-Branson correlate with less free volume into epoxy composites.
USD-10. The adopted technique is the pulse-echo immer- Indeed, the surface tension increases remarkably with in-
sion technique [2]. The tested sample was sandwiched creasing Ti content due to the increase of the action force
between two piezoelectric ceramics operating at about among the epoxy chains and cross-link reaction of the
8 MHz used as transducer. Sound velocity was determined epoxy. Therefore, the filler and matrix might reach the good
with reference to its velocity in distilled water at 20 jC wettability. Considering this observation, it is reasonable to
(1483 m/s). The accuracy of the sound velocity was esti- believe that the adhesive force among filler and matrix
mated to be better than 0.3%. The sound velocity in water increases, and hence there is a molecular structural change.
(in m/s) was found to vary with the absolute temperature (T) However, the mechanical properties of epoxy composites
according to linear relation in the form: were examined in order to figure out and understand how
the Ti particles influenced the performances of epoxy
matrix. Fig. 1d presents the plots of the breaking strength
Vw  2:55T þ 2230 ð1Þ (Eb), Young’s modulus ( Ym), hardness (shore A) and frac-
156 F. El-Tantawy, Y.K. Sung / Materials Letters 58 (2003) 154–158

Fig. 1. (a) SEM photographs for sampleTi5, (b) Cross-linking density, extent of filler reinforcement and molar volume as a function of Ti content of epoxy
composites. (c) The relationship between Tg, g, ST, PF and Ti content of epoxy composites. (d) Breaking strength, Young’s modulus, hardness and fracture
toughness as a function of Ti content for epoxy composites.

ture toughness Tg = 0.0824( P/C1.5) where P is the indenta- to enhance the network structure stability within the epoxy
tion load and C is the crack length, as a function of Ti matrix. This result provides another indication that the
content for epoxy composites. It is seen that all the me- dispersed particles within the epoxy matrix are easily dis-
chanical property improves as the Ti content increases in the placed under the applied load at low Ti content.
composite. This indicate that the Ti particles acts as a
reinforcing agent as confirmed by network structure results 3.2. Temperature dependence of longitudinal wave velocity
before. The breaking strength increases with increasing Ti and attenuation
particles. This is ascribed to a good ductility of epoxy matrix
and a strong interphase adhesion between Ti and epoxy The ultrasonic parameters like longitudinal velocity and
matrix. Also, it is seen that Young’s modulus increases with attenuation of polymer are strongly affected by their net-
an increase in a Ti content in the composites. This is work structure, and thereby the measurement of these
attributed to the integrated interfacial bonding and good parameters can provide useful information about the mod-
wettability between filler and matrix due to the higher ification of the architecture of molecular structure when the
surface area of the Ti particles. In the author’s opinion, filler, temperature, pressure or frequency of the simulation
the fracture toughness in these composites is due to the changes. The longitudinal sound velocity (V) and attenua-
generic characteristics of plasticizer and coupling agent tion (a) was calculated by the following equations [7,8]:
modified epoxy resin: the higher the plastic deformability
and the lower the crack pinning, the greater the fracture 2LVw
toughness. Thereby, we conclude that the plastic deform- VE ¼ ð2Þ
ð2L  Vw ðt1  t2 ÞÞ
ability of bulk epoxy adhesive was enhanced with inclusion
of filler, plasticizer and coupling agent. Lastly, the hardness  
increased with increasing Ti content. The reasons are that Ti qw Vw q VE 1
expð2aE LÞ ¼ Rð2Law Þ þ E þ ð3Þ
particles reduced the creep of epoxy matrix and therein led 4qE VE 4qw Vw 2
F. El-Tantawy, Y.K. Sung / Materials Letters 58 (2003) 154–158 157

where the subscripts E and w stand for epoxy and water,

respectively, L is the specimen thickness, t1 and t2 are the
times of flight of ultrasonic waves in a round trip with the
specimen removed and immersed, respectively, qw is the
density of water and R is the ratio of the received amplitudes
when the sample removed and immersed.
The variation of ultrasonic velocity and attenuation on
temperature for epoxy composites is presented in Fig. 2a
and b, respectively. It is seen that the ultrasonic velocity
and attenuation value increase with increasing Ti content
in the epoxy composites. This is ascribed to the strong

Fig. 2. (a) The variation of ultrasonic velocity on temperature for epoxy

composites. (b) The variation of attenuation on temperature for epoxy Fig. 3. (a) The attenuation versus frequency for epoxy composites. (b) The
composites. (c) The variation of a, Cp, Ka and Ki as a function of Ti content acoustic impedance, dielectric constant and dissipation factor versus Ti
for epoxy composites. content for the epoxy composites.
158 F. El-Tantawy, Y.K. Sung / Materials Letters 58 (2003) 154–158

adhesion force between neighboring chains and filler the dielectric constant (e) and dissipation factor (tan d)
matrix interactions into epoxy matrix. On the other hand, with Ti content are shown in the same Fig. 3b. Both the
the ultrasonic velocity and attenuation decrease with dielectric constant and dissipation factor increases with
raising temperature. This ascribed to the dilatation effect increasing Ti content in the epoxy composites. One pos-
due to the increases of the thermal expansion of epoxy sible reason for increase e and tan d is considered to be the
chains at high temperature. The temperature coefficient of reduction of average distance between Ti particles. Fur-
ultrasonic velocity b=(  1/V)(DV/DT), as a function of Ti thermore, the average interfacial polarization associated
content is plotted in Fig. 2c. The adiabatic compressibility with a cluster of Ti particles is coarser than that of an
Ka=(qcV2s )  1 and the isothermal compressibility Ki = individual particle because of the increase in the dimen-
Ka + Tqch2/Cp, where Cp is the specific heat of the sions of the metallic inclusion within epoxy matrix.
composite. The values of Cp as a function of Ti content
are plotted in Fig. 2c. It is seen that the Cp increases with
increasing Ti content. This is another clue confirming that 4. Conclusions
the inclusion of Ti particles enhances the network struc-
ture and thermal stability of epoxy matrix. However Fig. (1) The porous epoxy, Titanium, Silane coupling agent and
2c presents the variation of b, Ka and Ki as a function of plasticizer composites has been fabricated for transducer
Ti content. In Fig. 2c, it is clearly that b decreases while attenuation backing applications. The macromolecular
Ka and Ki increases with increasing Ti content in the network of epoxy resin is modified considerably by the
composite. The decrease of b and increases of Ka and Ki inclusion of Ti powder, coupling agent and plasticizer as
gives an indication of good interface adhesion between confirmed by network structure and mechanical ana-
epoxy and Ti in the composite. As the temperature is lyzes.
raised, the expansion of epoxy is restricted by the Ti (2) The ultrasonic sound velocity and the attenuation
phase, which has lower b, resulting in a decrease of decrease with raising temperature due to the dilatation
overall b in the composites. This suggested again that effect of the epoxy matrix.
the incorporation of Ti particles enhances the thermody- (3) The attenuation increases with increasing Ti content and
namic stability and molecular structure of epoxy matrix as frequency in porous epoxy composites. Also, the
confirmed before. acoustic impedance increases with increasing Ti content.
The high attenuation and acoustic impedance values
3.3. Applicability of composites in ultrasonic backing reflect that the porous epoxy –Ti composites are useful
for transducer backing applications.
To test the applicability of epoxy composites for ultra-
sonic backing application, the attenuation and acoustic
impedance was investigated. Fig. 3a represents the atten- Acknowledgements
uation versus frequency plot for neat epoxy and epoxy –Ti
composites. It is seen that there is a considerable increase This research was supported by Dongguk University,
in attenuation with increasing the frequency. This is Department of Chemistry, Seoul, Korea.
ascribed to the cross-linking density and the contribution
of Ti particles to acoustic scattering and multireflecting
within porous epoxy matrix. Also, the increment in atten- References
uation with increasing Ti content can be accounted for by
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[4,6]. To obtain more information about the applicability Science 87 (2003) 97.
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for backings, the acoustic impedance as a function of Ti (2002) 665.
contents were computed. The relationship between the [4] N.T. Nguyen, M. Lethiecq, B. Karlsson, F. Patat, Ultrasonics 34 (1996)
acoustic impedance Z = Vqc as a function of Ti concentra- 669.
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impedance with addition of Ti is due to the increase in [6] N.T. Nguyen, M. Lethiecq, J.F. Gerard, Ultrasonics 33 (1995) 323.
[7] N.H. Youssef, S.H. Mansour, S.Y. Tawfik, Polymer 41 (2000) 7815.
the chain connectivity and interfacial polarization associ- [8] W.P. Mason (Ed.), Physical Acoustics, Part A, vol. 1, Academic Press,
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dielectric properties that has resulted. The variation of