Electrical properties polyacetylene conductivity

Nagels and Krikor143 studied the effect of y-irradiation on the electrical properties of fraws-polyacetylene. They reported a marked decrease of the conductivity and a slight increase of the thermopower after y-irradiation of 10 kGy (1 Mrad). Their study showed that no essential structural changes occur during irradiation. 

The first and most important event in the history of conducting polymers occurred in 1978 when it was announced that the electrical properties of polyacetylene could be dramatically changed by chemical treatment (Chiang et al, 1978). 

Polyacetylene attracts constant attention as an excellent simple model of the polyconjugated polymer on which the main optical and electrical properties can be verified. The possibility of achieving metallic conductivities by doping opens real perspectives of practical application of conducting polymers. The complication is the strong interaction with oxygen. The reproducibility of results strongly depends on the synthesis and measurement conditions. 

Experimental studies have established that for conducting polymers, the electrical properties and the mechanical properties improve together, in a correlated manner, as the degree of chain extension and chain alignment are improved. Polyacetylene remains the prototype example. 

The mechanical and electrical properties of polyacetylene (PA) were modified by blending it with polybutadiene (PB). Further enhancement of the electrical conductivity of the blends was obtained by stretch elongation of the blends prior to doping. 

As expected, the electrical conductivity of the doped blend is also a function of the polyacetylene composition of the material. (5) Furthermore, stretch induced elongation of the blends leads to a dramatic increase in conductivity subsequent to doping, further confirming that the electrical properties are also very sensitive to the arrangement of the respective phases. 

As described in Section II.B.l above, doping causes a drastic change in the electrical properties of polyacetylene. The initial values of electrical conductivity were of the order of 10 S cm" for unoriented materials d24-i30 when doped by iodine and AsFs, were enhanced to the order of 10 S cm, which was obtained in the parallel direction of the doped films oriented by mechanical stretching 31 Improvements in polymerization methods and in the catalyst systems also enhanced the electrical conductivity. Highly oriented films prepared in liquid crystal solvents (Section II.A.l.d.iii) exhibited a conductivity higher than 10 S cm, as did also a well stretch-oriented film prepared by Ti(OBu)4-EtsAl dissolved in silicon oil and aged at 120°C. In further studies Naarmann and Theophilou and Tsukamoto and coworkers attained a conductivity of ca 10 S cm k... 

The intractability of the early preparations of polyacetylene has severely hampered the establishment of clear-cut relationships between structure, morphology and (electrical) properties. An early example of an integrated approach to structure-property relations is a paper by Haberkom et al. [24], From a combination of x-ray data with NMR and IR investigations, these authors have found a relationship between the content of sp defects and crystallinity in polyacetylene prepared by the Shirakawa, Luttinger and other methods. Such defects are apparently expelled to the amorphous phase. The authors find a correlation with conductivity in both undoped and iodine-doped samples. 

A spectacular example of a clear relationship between chemical and stnictural homogeneity and improved electrical properties can be found in polyacetylene. C CP MAS NMR studies of initially synthesized polyacetylene [22,23] indicated the presence of a small fraction of sp hybridized carbons in addition to sp carbons expected for a perfect polyene chain. Drastic reduction in the number of these sp defects observed in polyacetylene prepared by the method developed by Naarman and Theophilou, resulted in an important improvement of the conductivity of this polymer in the doped state [24],... 

It is therefore essential to identify polymers that do not change their electrical properties within a broad range of temperatures. When electrical conductivity turns out to be desirable in a polymer, in some cases this can be obtained by using conductive fillers (carbon black or metallic powders). In these cases, the resistivity rises with temperature, while a sharp increase occurs around transition temperatures, such as T, . This phenomenon may be utilized in novel switching and control devices (PTC - positive temperature coefficient). Polyacetylene serves as an example of a conductive polymer. 

FIGURE 16.4 I-V characteristics of iodine doped PA nanofiber. Znsef shows scanning force microscope image of PA nanofiber on top of Pt electrodes (with 100 nm separation). Typical diameter of PA nanofiber is 16-20 mn (From Park, J.G., et al. Synth. Met., 119, 53, 2001 and Park, J.G., Electrical transport properties of conducting polymer nanostructures Polyacetylene nanofiber, polypyrrole nanotube/nanowire, Ph.D. thesis, Seoul National University, Seoul, 2003.). 

Park, J.G. 2003. Electrical transport properties of conducting polymer nanostructures Polyacetylene nanofiber, polypyrrole nanotube/nanowire. Ph.D. thesis, Seoul National University, Seoul. 

J. Tsukamoto, A. Takahashi, K. Kawasaki, Structure and electrical properties of polyacetylene yielding a conductivity of 10 S/cm, Jpru J. Appl. Phys., 29, 125-130 (1990). 

As with any prospective new application we reasoned that optimization of physical and chemical properties would be required in order to generate practically useful electrically conductive polymers. We were concerned about mechanical properties, flexibility, conductivity levels, solubility, processability, oxidative stability, etc. Based upon the perceived requirement of a conjugated polyene structure, substituted polyacetylenes were the obvious way to introduce substituents for the purpose of tailoring these characteristics. Unfortunately the literature provided ample evidence of the sluggish nature of substituted polyacetylenes toward polymerization. 

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