B03120609

I

Research Inventy : International Journal of Engineering and Science is published by the group of young academic and industrial researchers with 12 Issues per year. It is an online as well as print version open access journal that provides rapid publication (monthly) of articles in all areas of the subject such as: civil, mechanical, chemical, electronic and computer engineering as well as production and information technology. The Journal welcomes the submission of manuscripts that meet the general criteria of significance and scientific excellence. Papers will be published by rapid process within 20 days after acceptance and peer review process takes only 7 days. All articles published in Research Inventy will be peer-reviewed.

Research Inventy: International Journal Of Engineering And Science
Vol.3, Issue 12 (December 2013), PP 06-09
Issn(e): 2278-4721, Issn(p):2319-6483, Www.Researchinventy.Com

Effects Of Doping With Iron Ill Chloride On The Electrical And
Thermal Conductivities Of The Polymer Polystyrene
Uleanya1 Kelechi .O , Eboatu2 Augustine.N
1

Chemistry Programme, School of Science and Technology, National Open University of Nigeria, 14/16
Ahmadu Bello Way, P.M.B. 80067 Victoria Island, Lagos, Nigeria
2
Department of Industrial Chemistry Faculty of Natural Sciences Nnamdi Azikiwe University, P.M.B. 5025
Awka, Anambra State Nigeria

ABSTRACT : This work on effects of doping with FeCl3 on the electrical and thermal conductivities of the
polymer polystyrene was conducted. The idea behind this experiment is to find a means of reducing the cost of
making conductive polymers since it is evident that tailor-made conductive polymers such as poly aniline, poly
acetylene etc. do not actually have readily available starting materials and are quite expensive.
Five grams of poly styrene was mixed with
eight different concentrations of the FeCl3
(0.00%,0.05%,0.1%,0.5%,0.75%,1.00%,1.25%,1.5%) after melting with heat application and compressed in a
wooden mould into tablets of doped polystyrene materials.
On testing for the electrical and thermal conductivity of the doped polymer, it was observed that its electrical
and thermal conductivities were actually enhanced by the potentiating capacities of the dopant.

KEYWORDS: polystyrene, thermal conductivity, dopant, FeCl3, electrical conductivity
I.

INTRODUCTION

Most commercially produced organic polymers are electrical insulators. Conductive organic polymers often
have extruded delocalized bonds (often composed of aromatic units).When charge carriers (from the addition or
removal of electrons) are introduced into the conduction or valence bands, the electrical conductivity increases
dramatically. Technically almost all known conductive polymers are semi-conductors due to the band structure
and low electronic mobility. However, so called zero band gap conductive polymers may behave like metals.
The most notable difference between conductive polymers and inorganic semi-conductors is the mobility, which
until very recently was dramatically lower in conductive polymers than their inorganic counterparts though
recent advancements in molecular self- assembly are closing that gap [1].
The world electronic market has shifted its interest and concern to the use and application of
conductive polymers in its production developments because of their simplicity and compactness. All hands
therefore must be on deck to evolve highly conductive yet cheap polymers from readily available, easily sourced
materials in our environment. This work was gingered by the above premise and its concerned was based on
how the readily available polymer, polystyrene could be electrically enhanced by doping with Iron III chloride
to help its conductivity, such that it can be employed for this essential function since it is evidently clear that
already made conductive polymers are not readily available and are of low cost efficiency. Conductive
polymers are generally not thermoplastics i.e. they are not thermo formable although like insulating polymers
they are organic materials. They have an advantage over other polymers because of their processability which is
mainly by dispersion [2]. The electrical properties of conductive polymers can be fine-tuned using the methods of
organic synthesis [3] and by advanced dispersion techniques [4]. The conductivity of polymers is the result of
several processes. In the traditional polymers such as polyethylene, the valence electrons are bound in sp3
hybridized covalent bonds such sigma-bonding electrons have low mobility and do not contribute to the
electrical conductivity of the material.
However in conjugated materials the situation is completely different .Conducting polymers have
backbone of contiguous sp2 hybridized carbon centers [5]. Conductive polymers are organic polymers that
possess electrical, electronic, magnetic, and optical properties of a metal while retaining mechanical properties
processibility commonly associated with a conventional polymer [6]. It can also be defined as any system that
contains an additive to lower resistivity. The resistivity of unmodified polymers or plastics is 1016 Ωm while
conductive additives can lower resistivity level in steps down to 104 Ωm resistivity range [7]. This work is
focused primarily on the enhancement of their crucial properties: electrical and thermal conductivities that are
required of a polymer for it to be accepted for all good uses especially as a semiconductor.

6
Effects Of Doping With Iron Ill Chloride On The…
Commonly discarded polymer and material from the environment were used as a means of waste
control. Cost management was considered since this has served as a strong limitation for their use. These desired
polymers were achieved by doping with FeCl3 to help lower the resistivity of the polymers thus increasing their
conductivities. Hence the doping process is the introduction of very small amounts of impurities example FeCl3
to generate charge carriers since concentrations of dopants cause certain electrons to become unpaired. Doping
also lead to the formation of polarons and bipolarons have extended p-orbital system that have more (n-type) or
fewer (p-type) valence electrons to increase the conductivity of a semiconductor [ 8]

II.

MATERIALS AND METHODS

All the materials and equipment used for this research were sourced from the chemistry and physics
research laboratories of Nnamdi Azikiwe University Awka, Cutix Nigeria Plc Nnewi and Electronic shops in
Onitsha Nigeria.
2.1 Procedure
Polymer polystyrene was prepared by doping it with fecl3 to enhance the electrical and thermal
conductivity, considering the fact that it has some intrinsic properties. The changes and differences in the rate
of increase in electrical and thermal conductivities of the polymer was also reported. White brittle pack used for
protecting electronic gadgets which is pure polystyrene. Electrical weighing balance from Mettler Toledo 2007
mode serial no 021-64852350 ENGLAND, Stirring rods, Beakers (PYREX). Electro-thermal Heater of about
250oc from Barnstaed 2006 model, serial no 10714483 England, Thermometer - 360oC thermometer, Iron III
chloride from BDH Prole, England, Wooden mold, ELMER 2AK Karthrometer, 500 mega ohms MASTECH
multimeter No. 005-1349 5g of the polymer were weighed into a 250 ml beaker and heated at a regulated
temperature of 130 o C - 250 o C to melt it using a thermometer and on continuous stirring to maintain a uniform
temperature. During the process care was taken not to allow degradation. The dopant of known different
percentage concentrations 0.00, 0.05, 0.10, 0.50, 0.75, 1.00, 1.25, 1.50 was added into the beaker containing the
polymer and the two mixed thoroughly while heating respectively. The mixture was then poured immediately
into the mold and compressed to form a doped tablet of polystyrene. Their electrical conductivities were
measured using 500 mega ohms MASTECH multimeter No. 005-1349 .Electrical conductivity is the reciprocal
of resitivity ,K =1/R
Where K –Electrical conductivity, R- Resitivity
The thermal conductivity was measured with ELMER 2AK Kathrometer
TABLE 1:Formulation of doped polystyrene
Polystyrene (g)
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00

% concentration of Fecl3
0.00
0.05
0.10
0.50
0.75
1.00
1.25
1.50

III.

RESULTS & DISCUSSION

The results of electrical and thermal conductivities of the polystyrene doped with FeCl3 are shown in tables 2&3
TABLE 2:Electrical conductivity of polystyrene doped with fecl 3
% concentration of dopant
0
0.05
0.10
0.50
0.75
1.00
1.25
1.50

Polystyrene doped with fecl3 (x 10-6 S/cm)
0
0.08
0.56
0.67
0.83
0.90
1.00
1.11

Iron III chloride is a transition element with a half filled d- orbital thus it is highly reactive. FeCl3 is a
deliquescent salt that on exposure at laboratory ambient conditions absorbs water from the atmosphere thus has

7
Effects Of Doping With Iron Ill Chloride On The…
its nature turned to be wet and will encourage ionization of the salt and thus leaving the dopant with a lot of free
electrons. One can also deduce that the movement of electron from the valence band of the polymer into the
partially filled conductive band of Fe3+ would also be efficient in explaining the excellent performance of the
polymer doped with fecl3. The nature of FeCl3 explained above results in formation of ‘metallic island’ concept
in which case the islands of FeCl3 would have conducted electricity through its own intrinsic property as a
metallic conductor. It is important to note that in doping with fecl 3 there is a spiking from 0.05wt % - 0.10wt %,
from which one can deduce that the rate of increase in electrical conductivity of polystyrene at lower
concentration tend to be doubled and the rate decreases as the dopants concentration increases. It therefore
appears like the electron conductive band gets saturated at a given concentration thus further addition of dopants
results in marginal electron transfer activity which results in a reduction. On the other hand polystyrene has a
dielectric constant determined by the additive effects of electronic and dipolar polarizabilities the latter is due to
the presence of permanent electric dipoles. Polystyrene is essentially non polar with an effective dipole moment
of 6.7- 10 x 10-31cm per repeating unit [9] .these effects of the electronic and dipolar polarizabilities is increased
by the presence of the dopant thereby creating dipole moments that improve electrical conductivities through
polaron assisted tunneling.
TABLE 3 :Thermal conductivity of polystyrene doped with FeCl3
Polystyrene doped with FeCl3 (x 10-2 Cal/cm/s)
0.00
0.10
0.20
2.72
3.07
3.85
4.23
5.3

% concentration of dopant
0.00
0.05
0.10
0.50
0.75
1.00
1.25
1.50

The thermal conductivities of the doped polystyrene were increased with increase in the concentration
of the dopants. The increase may be due to compactness provided by increase in concentration of the dopants
which increase heat transfer through phonon. The intrinsic dipolarity property and amorphous nature of
polystyrene made a negligible contribution to the thermal conductivity of its parent form but could be said to
have made significant contribution to the thermal conductivity of the doped polystyrene due to its interaction
with the delocalized electron in the FeCl3. The density contributes to the thermal property of polystyrene. The
free electrons in the FeCl3 could have improved the dipolarity thereby increasing significantly the contribution
of electron mobility in conduction through the FeCl3 doped polystyrene. The half – filled orbital structure of
FeCl3 would have contributed to the improvement of the polystyrene density which will improve thermal
conductivity by wave movement (phonon) or inter atomic heat transfer.

IV.

CONCLUSION

The electrical and thermal conductivity of the polymer polystyrene were enhanced and this
enhancement is dependent on the nature and properties of the polymer and the dopant. It is also evident that
since this is possible, discarded polymers can be employed for some industrial use when improved to the
required standard.

REFERENCES
[1]
[2]
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[5]
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[10]

.N. Biodun, conducting polymers, 3rd Ed. Blackwell publishers London ISBN978 – 3674, 1997, pp 1-4.
G. Inzelt , Conducting polymers, A New Era in Electrochemistry Monographs ,Electrochemistry Springer ,2008, pp 265 – 267.
H. Naarman , Polymers Electrically conducting, (Ullman’s Encyclopedia of Industrial Chemistry, 2000)
H.S Nalwa, Handbook of Nano structured and materials Nano Technology, Academic press .New york, NY USA.Volume 5
,2000, 501 -575
N.S Saricifici, Handbook of Organic Conductive Molecules and Polymers , World Scientific, Singapore, 1997, vol.1-4 wiley
&sons Ltd Chichester Edited by H.S Nalwa
A.G MacDiarmid, Conductive polymer, Epstein American Journal Synthetic metal (65), 1994,103
S. J Dahman. ,synthesis ,characterization and application of inherently conducting polymers, Journal of polymer engineering and
science, vol. 39,1999,11
L.T Brown, E. H Lemay, Jr., .E.B Brusten, Chemistry, The central science, modern materials 11ed.( Prentice-Hall Inc.,2009)
A.K Wanekaya. Y. Lei, E. Bekyarova,.W. Chen, .R Haddon., fabrication and properties of conducting polypyrrole,
Electroanalysis 18, No 11. ( wiley publishers wiley-VCH weinhem U.S.A., 2006) 1047-1054
.S. Noel , .N. Hush,,N. Ann., An Overview of the First Half Century of Molecular Electronic vol. 1006, (Academic Science Inc.
New York, 2003) 1 – 20

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Effects Of Doping With Iron Ill Chloride On The…
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W.J Feast, Synthesis of conducting polymers, in Skotheim T.A (ed) ,Hand book of Conductive polymers , 1 (Marcel Dekker ,lnc.
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R. Bing , W. Yen, Semiconducting Polymers Applications Properties and Synthesis, American Chemistry Society vol.735 ,1999

9

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B03120609

  • 1. Research Inventy: International Journal Of Engineering And Science Vol.3, Issue 12 (December 2013), PP 06-09 Issn(e): 2278-4721, Issn(p):2319-6483, Www.Researchinventy.Com Effects Of Doping With Iron Ill Chloride On The Electrical And Thermal Conductivities Of The Polymer Polystyrene Uleanya1 Kelechi .O , Eboatu2 Augustine.N 1 Chemistry Programme, School of Science and Technology, National Open University of Nigeria, 14/16 Ahmadu Bello Way, P.M.B. 80067 Victoria Island, Lagos, Nigeria 2 Department of Industrial Chemistry Faculty of Natural Sciences Nnamdi Azikiwe University, P.M.B. 5025 Awka, Anambra State Nigeria ABSTRACT : This work on effects of doping with FeCl3 on the electrical and thermal conductivities of the polymer polystyrene was conducted. The idea behind this experiment is to find a means of reducing the cost of making conductive polymers since it is evident that tailor-made conductive polymers such as poly aniline, poly acetylene etc. do not actually have readily available starting materials and are quite expensive. Five grams of poly styrene was mixed with eight different concentrations of the FeCl3 (0.00%,0.05%,0.1%,0.5%,0.75%,1.00%,1.25%,1.5%) after melting with heat application and compressed in a wooden mould into tablets of doped polystyrene materials. On testing for the electrical and thermal conductivity of the doped polymer, it was observed that its electrical and thermal conductivities were actually enhanced by the potentiating capacities of the dopant. KEYWORDS: polystyrene, thermal conductivity, dopant, FeCl3, electrical conductivity I. INTRODUCTION Most commercially produced organic polymers are electrical insulators. Conductive organic polymers often have extruded delocalized bonds (often composed of aromatic units).When charge carriers (from the addition or removal of electrons) are introduced into the conduction or valence bands, the electrical conductivity increases dramatically. Technically almost all known conductive polymers are semi-conductors due to the band structure and low electronic mobility. However, so called zero band gap conductive polymers may behave like metals. The most notable difference between conductive polymers and inorganic semi-conductors is the mobility, which until very recently was dramatically lower in conductive polymers than their inorganic counterparts though recent advancements in molecular self- assembly are closing that gap [1]. The world electronic market has shifted its interest and concern to the use and application of conductive polymers in its production developments because of their simplicity and compactness. All hands therefore must be on deck to evolve highly conductive yet cheap polymers from readily available, easily sourced materials in our environment. This work was gingered by the above premise and its concerned was based on how the readily available polymer, polystyrene could be electrically enhanced by doping with Iron III chloride to help its conductivity, such that it can be employed for this essential function since it is evidently clear that already made conductive polymers are not readily available and are of low cost efficiency. Conductive polymers are generally not thermoplastics i.e. they are not thermo formable although like insulating polymers they are organic materials. They have an advantage over other polymers because of their processability which is mainly by dispersion [2]. The electrical properties of conductive polymers can be fine-tuned using the methods of organic synthesis [3] and by advanced dispersion techniques [4]. The conductivity of polymers is the result of several processes. In the traditional polymers such as polyethylene, the valence electrons are bound in sp3 hybridized covalent bonds such sigma-bonding electrons have low mobility and do not contribute to the electrical conductivity of the material. However in conjugated materials the situation is completely different .Conducting polymers have backbone of contiguous sp2 hybridized carbon centers [5]. Conductive polymers are organic polymers that possess electrical, electronic, magnetic, and optical properties of a metal while retaining mechanical properties processibility commonly associated with a conventional polymer [6]. It can also be defined as any system that contains an additive to lower resistivity. The resistivity of unmodified polymers or plastics is 1016 Ωm while conductive additives can lower resistivity level in steps down to 104 Ωm resistivity range [7]. This work is focused primarily on the enhancement of their crucial properties: electrical and thermal conductivities that are required of a polymer for it to be accepted for all good uses especially as a semiconductor. 6
  • 2. Effects Of Doping With Iron Ill Chloride On The… Commonly discarded polymer and material from the environment were used as a means of waste control. Cost management was considered since this has served as a strong limitation for their use. These desired polymers were achieved by doping with FeCl3 to help lower the resistivity of the polymers thus increasing their conductivities. Hence the doping process is the introduction of very small amounts of impurities example FeCl3 to generate charge carriers since concentrations of dopants cause certain electrons to become unpaired. Doping also lead to the formation of polarons and bipolarons have extended p-orbital system that have more (n-type) or fewer (p-type) valence electrons to increase the conductivity of a semiconductor [ 8] II. MATERIALS AND METHODS All the materials and equipment used for this research were sourced from the chemistry and physics research laboratories of Nnamdi Azikiwe University Awka, Cutix Nigeria Plc Nnewi and Electronic shops in Onitsha Nigeria. 2.1 Procedure Polymer polystyrene was prepared by doping it with fecl3 to enhance the electrical and thermal conductivity, considering the fact that it has some intrinsic properties. The changes and differences in the rate of increase in electrical and thermal conductivities of the polymer was also reported. White brittle pack used for protecting electronic gadgets which is pure polystyrene. Electrical weighing balance from Mettler Toledo 2007 mode serial no 021-64852350 ENGLAND, Stirring rods, Beakers (PYREX). Electro-thermal Heater of about 250oc from Barnstaed 2006 model, serial no 10714483 England, Thermometer - 360oC thermometer, Iron III chloride from BDH Prole, England, Wooden mold, ELMER 2AK Karthrometer, 500 mega ohms MASTECH multimeter No. 005-1349 5g of the polymer were weighed into a 250 ml beaker and heated at a regulated temperature of 130 o C - 250 o C to melt it using a thermometer and on continuous stirring to maintain a uniform temperature. During the process care was taken not to allow degradation. The dopant of known different percentage concentrations 0.00, 0.05, 0.10, 0.50, 0.75, 1.00, 1.25, 1.50 was added into the beaker containing the polymer and the two mixed thoroughly while heating respectively. The mixture was then poured immediately into the mold and compressed to form a doped tablet of polystyrene. Their electrical conductivities were measured using 500 mega ohms MASTECH multimeter No. 005-1349 .Electrical conductivity is the reciprocal of resitivity ,K =1/R Where K –Electrical conductivity, R- Resitivity The thermal conductivity was measured with ELMER 2AK Kathrometer TABLE 1:Formulation of doped polystyrene Polystyrene (g) 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 % concentration of Fecl3 0.00 0.05 0.10 0.50 0.75 1.00 1.25 1.50 III. RESULTS & DISCUSSION The results of electrical and thermal conductivities of the polystyrene doped with FeCl3 are shown in tables 2&3 TABLE 2:Electrical conductivity of polystyrene doped with fecl 3 % concentration of dopant 0 0.05 0.10 0.50 0.75 1.00 1.25 1.50 Polystyrene doped with fecl3 (x 10-6 S/cm) 0 0.08 0.56 0.67 0.83 0.90 1.00 1.11 Iron III chloride is a transition element with a half filled d- orbital thus it is highly reactive. FeCl3 is a deliquescent salt that on exposure at laboratory ambient conditions absorbs water from the atmosphere thus has 7
  • 3. Effects Of Doping With Iron Ill Chloride On The… its nature turned to be wet and will encourage ionization of the salt and thus leaving the dopant with a lot of free electrons. One can also deduce that the movement of electron from the valence band of the polymer into the partially filled conductive band of Fe3+ would also be efficient in explaining the excellent performance of the polymer doped with fecl3. The nature of FeCl3 explained above results in formation of ‘metallic island’ concept in which case the islands of FeCl3 would have conducted electricity through its own intrinsic property as a metallic conductor. It is important to note that in doping with fecl 3 there is a spiking from 0.05wt % - 0.10wt %, from which one can deduce that the rate of increase in electrical conductivity of polystyrene at lower concentration tend to be doubled and the rate decreases as the dopants concentration increases. It therefore appears like the electron conductive band gets saturated at a given concentration thus further addition of dopants results in marginal electron transfer activity which results in a reduction. On the other hand polystyrene has a dielectric constant determined by the additive effects of electronic and dipolar polarizabilities the latter is due to the presence of permanent electric dipoles. Polystyrene is essentially non polar with an effective dipole moment of 6.7- 10 x 10-31cm per repeating unit [9] .these effects of the electronic and dipolar polarizabilities is increased by the presence of the dopant thereby creating dipole moments that improve electrical conductivities through polaron assisted tunneling. TABLE 3 :Thermal conductivity of polystyrene doped with FeCl3 Polystyrene doped with FeCl3 (x 10-2 Cal/cm/s) 0.00 0.10 0.20 2.72 3.07 3.85 4.23 5.3 % concentration of dopant 0.00 0.05 0.10 0.50 0.75 1.00 1.25 1.50 The thermal conductivities of the doped polystyrene were increased with increase in the concentration of the dopants. The increase may be due to compactness provided by increase in concentration of the dopants which increase heat transfer through phonon. The intrinsic dipolarity property and amorphous nature of polystyrene made a negligible contribution to the thermal conductivity of its parent form but could be said to have made significant contribution to the thermal conductivity of the doped polystyrene due to its interaction with the delocalized electron in the FeCl3. The density contributes to the thermal property of polystyrene. The free electrons in the FeCl3 could have improved the dipolarity thereby increasing significantly the contribution of electron mobility in conduction through the FeCl3 doped polystyrene. The half – filled orbital structure of FeCl3 would have contributed to the improvement of the polystyrene density which will improve thermal conductivity by wave movement (phonon) or inter atomic heat transfer. IV. CONCLUSION The electrical and thermal conductivity of the polymer polystyrene were enhanced and this enhancement is dependent on the nature and properties of the polymer and the dopant. It is also evident that since this is possible, discarded polymers can be employed for some industrial use when improved to the required standard. REFERENCES [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] .N. Biodun, conducting polymers, 3rd Ed. Blackwell publishers London ISBN978 – 3674, 1997, pp 1-4. G. Inzelt , Conducting polymers, A New Era in Electrochemistry Monographs ,Electrochemistry Springer ,2008, pp 265 – 267. H. Naarman , Polymers Electrically conducting, (Ullman’s Encyclopedia of Industrial Chemistry, 2000) H.S Nalwa, Handbook of Nano structured and materials Nano Technology, Academic press .New york, NY USA.Volume 5 ,2000, 501 -575 N.S Saricifici, Handbook of Organic Conductive Molecules and Polymers , World Scientific, Singapore, 1997, vol.1-4 wiley &sons Ltd Chichester Edited by H.S Nalwa A.G MacDiarmid, Conductive polymer, Epstein American Journal Synthetic metal (65), 1994,103 S. J Dahman. ,synthesis ,characterization and application of inherently conducting polymers, Journal of polymer engineering and science, vol. 39,1999,11 L.T Brown, E. H Lemay, Jr., .E.B Brusten, Chemistry, The central science, modern materials 11ed.( Prentice-Hall Inc.,2009) A.K Wanekaya. Y. Lei, E. Bekyarova,.W. Chen, .R Haddon., fabrication and properties of conducting polypyrrole, Electroanalysis 18, No 11. ( wiley publishers wiley-VCH weinhem U.S.A., 2006) 1047-1054 .S. Noel , .N. Hush,,N. Ann., An Overview of the First Half Century of Molecular Electronic vol. 1006, (Academic Science Inc. New York, 2003) 1 – 20 8
  • 4. Effects Of Doping With Iron Ill Chloride On The… [11] [12] [13] W.J Feast, Synthesis of conducting polymers, in Skotheim T.A (ed) ,Hand book of Conductive polymers , 1 (Marcel Dekker ,lnc. New York,1999) 1-2 R.K Monika Synthesis of conducting polymers and their characterization, Indian Journal of Pure and Applied Physics. vol.48,July2010, 524 R. Bing , W. Yen, Semiconducting Polymers Applications Properties and Synthesis, American Chemistry Society vol.735 ,1999 9