1. Field of the Invention
The present invention relates to superconductors, and particularly to a superconductive nanocomposite formed from nanoparticles of a high temperature superconductor disposed in a natural rubber-polyethylene polymer matrix.
2. Description of the Related Art
Superconductors exhibit the unique property of having zero electrical resistance below a certain critical temperature, usually designated as Tc. Type I superconductors include tin, aluminum, certain alloys, and other materials that have a critical temperature of about 30 degrees Kelvin. The superconductive phenomenon exhibited by such materials can be explained by quantum mechanical theory.
More recently, it has been found that certain ceramic materials, known as Type II superconductors, also exhibit superconductive behavior, but have higher critical temperatures. Some of these Type II superconductors have critical temperatures above 90 degrees Kelvin, which potentially expands possible applications for superconductors, since their critical temperature is above the boiling point of liquid nitrogen (about 77 degrees Kelvin), making them easier to work with. The superconductivity of Type II superconductors has not been fully explained on a theoretical basis, since they exhibit magnetic effects that are somewhat different than Type I superconductors.
One such high temperature superconductor is ceramic oxide material containing bismuth, lead strontium, calcium, and copper (BSCCO), sometimes referred to as a bismuth oxide or cuprate oxide superconductor. However, like other metal oxide superconductors, the range of applications for bismuth oxide superconductors has been limited, since the oxide is brittle and difficult to draw as a wire. Consequently, there is a need for a matrix for high temperature, metal oxide superconductors, and particularly for bismuth-based superconductors.
Thus, a superconductive nanocomposite solving the aforementioned problems is desired.
The superconductive nanocomposite is a composition formed by nanoparticles of a high temperature superconductor blended with a polymer matrix containing natural rubber and polyethylene. The high temperature superconductor is preferably a bismuth-based superconductor (BSCCO) having a particle size of about 21 nm, but may be any other high temperature or Type II ceramic, metal oxide superconductor. The superconductor nanoparticles comprise about 15% of the about 15% of the weight of natural rubber in the composition. The polyethylene is preferably low density polyethylene and may comprise between 0% up to about 40% of the weight of natural rubber in the composition. The nanocomposite may be prepared by blending the components and roll milling the rubber. Depending upon the percentage of polyethylene present in the matrix, the nanocomposite has useful applications as a double thermistor (both positive and negative coefficients of electrical resistivity), for antistatic charge dissipation, and for electromagnetic shielding in the microwave region.
These and other features of the present invention will become readily apparent upon further review of the following specification and drawings.
Similar reference characters denote corresponding features consistently throughout the attached drawings.
The superconductive nanocomposite is a composition formed by nanoparticles of a high temperature superconductor blended with a polymer matrix containing natural rubber and polyethylene. The high temperature superconductor is preferably a bismuth-based superconductor (BSCCO) having a particle size of about 21 nm, but may be any other high temperature or Type II ceramic, metal oxide superconductor. The superconductor nanoparticles comprise about 15% of the weight of natural rubber in the composition. The polyethylene is preferably low density polyethylene and may comprise between 0% up to about 40% of the weight of natural rubber in the composition. The nanocomposite may be prepared by blending the components and roll milling the rubber. Depending upon the percentage of polyethylene present in the matrix, the nanocomposite has useful applications as a double thermistor (both positive and negative coefficients of electrical resistivity), for antistatic charge dissipation, and for electromagnetic shielding in the microwave region.
The superconductive nanocomposite is best understood by reference to the following example.
Samples of nominal compositions Bi1.93PbO0.33Sr2Ca2.5Cu3.5Oy, were prepared by the acetate-tartrate gel precursor technique. Stoichiometric amounts of analytical grade Bi2O3, PbO, Ca(NO3)3, Sr(CH3COO)2 and Cu(CH3COO)2. H2O were used as starting materials. First, in the sol-gel process, an appropriate amount of the Bi2O3 and PbO was dissolved in 0.2 M H2COOH. After stirring for 2 hours at 90° C., a clear solution was obtained. Next, copper acetate, calcium nitrate, and strontium nitrate were all dissolved in small amounts of distilled water and were added to the bismuth acetate solution with adequate intermediate stirring. Finally, after concentrating for 20 hours at 90° C. in an open beaker, the acetate/tartrate solutions turned into blue or slightly greenish gels. The obtained Bi1.93PbO0.33Sr2Ca2.5Cu3.5Oy, gels were dried in air at 100° C. for 1 day. The mixtures so obtained were pressed into 20 mm disk-shaped pellets at a pressure of P=200 KN/m2 and then calcined at 820° C. for 3 hours in air. The product was then subjected to grinding, re-pelletized, and then sintered at 855° C. for 20 hours in air. Bismuth-based powder with a particle size of about 21 nm was received from the above method.
A blend of natural rubber (NR) and low density polyethylene (PE) was used as a polymer matrix. Bismuth-based superconductor ceramic (labeled as BSCCO) was used as conductive filler and was prepared by sol-gel technique to obtain nanoparticles, as reported above. Other ingredients, such as commercial grades of zinc oxide (ZnO); stearic acid (SA); zinc-diethyldithiocarbamate (ZDC), 1,2-mercaptobenzothiazole (MBT), and sulfur (S) were used without further purification. A typical formulation of NR/PE blend compound is presented in Table I.
The mixing was accomplished in an open two-roll mill under identical conditions of time, temperature and nip gap, with the same sequence of mixing of all compounding ingredients to avoid the effect of processing on physical properties. The vulcanization process of the polymer compounds was carried out in an electrically heated hydraulic press using a special homemade mold at a temperature of 1600° C. and under pressure of 300 KN/m2 for 30 minutes. Then, the blends were cured under hot, uniaxial pressure of 200 KN/m2 at 150° C. for 2 hours.
The morphology development in the blends with increasing PE loading may be followed from the SEM images shown in
To gain more insight on the above assumption, the crosslinking density CLD, bound rubber BR, and Mooney viscosity M100 were evaluated, and the results are presented in
Higher M100 values are observed by increasing the fraction of PE up to about 10 wt %. One possible explanation for the increase of the Mooney viscosity can be ascribed to facile mobility carriers and polymer-polymer interactions, which induces rigidity of the polymer chains. The increase of M100 for sample PE10 is a strong clue that PE≦10 wt %, enhances crosslinking efficiency and restricts polymer chain mobility. Therefore, rigidity of the polymer chains increases in the blend system.
The mechanical properties in filled rubber vulcanates can be explained in view of the bound rubber concept, which is a result of the interaction between elastomer and filler. Bound rubber is formed in filled elastomer compounds by physical absorption, chemisorption, and mechanical interaction, and depends on various factors, such as polarity, the microstructure of the polymer, structure, surface activity of the filler, and interface adhesion between filler and matrix.
Tensile strength TS, hardness Hand elongation at break EB as a function of PE content of the blend is illustrated in
Tensile strength of the sample decreases with increasing the PE content to more than 10 wt % in the blend. This behavior may be explained by the fact that segregation along the polymer-filler interface is due to weak adhesion between filler and matrix when increasing the PE content to more than 10 wt %. In addition, when PE>10 wt %, the intermolecular forces within the rubber matrix decrease, which leads to more flaws in the rubber matrix, and to lower crosslinking density and bound elastomer. It is worthy to note that the PE10 sample gave a higher hardness compared to other samples, which indicates that there is some sort of interaction between polymer and filler. The highest hardness of the PE10 sample is ascribed to the complete compatibility of polyethylene with the NR matrix so that the polymer blend molecules are very compact. This makes the dispersion of PE in the NR matrix better, so that PE works as a compatibility agent and/or wet agent to give the polymer blend. This is reflected in the chain connectivity and interfacial adhesion increase in the blends with increasing PE content up to 10 wt %, as confirmed above.
In
The variations at room temperature of bulk electrical resistivity (ρ=R·(A/l) where ρ is resistivity in Ω-cm, R is resistance in ohms, A is cross-sectional area in cm2, and l is length in cm) of the blend samples with PE loading ranging from 0 to 40 wt % is shown in
As the PE content increased to 10 wt %, more PE-containing liquid phases had formed, i.e., built barriers to decrease the transport or hop of charge carriers by tunneling, which contributes to a higher resistivity. One may be therefore inclined to conclude that PE content up to 10 wt % is directly involved in forming the conducting network. Again, to confirm the above facts, charge carrier mobility μ and number of charges per volume (N per cubic centimeter) as a function of PE content has been measured, and the results are also presented in
In
Some conducting composites or blends show a sharp resistivity increase and/or decrease at relatively high temperature, which reflects both positive and negative temperature coefficients of resistivity (PTCR and NTCR). Materials that exhibit both PTCR and NTCR phenomena are said to exhibit a double thermistor effect. Because of a sharp increase or decrease in electrical resistivity, the PTCR and NTCR materials have a wide range of technological applications, such as self-regulating heaters, current limiters, overcurrent protectors, and resettable fuses.
Starting from the laboratory room temperature, the number of BSCCO contacts only gradually diminished and, as a result, a slight increase in resistivity occurred. With increasing temperature, the resistivity rapidly increases. This behavior is due to thermal expansion of the matrix, which causes an increase in the interatomic distances between BSCCO particles and their disconnection. In contrast, however, at the percolation temperature, interruption of the last conductive paths through a sample caused a sudden decrease in resistivity (i.e., the NTCR effect appears). At the percolation temperature, as the particles in the blend are fully separated, the semiconducting character of the blend prevails, and a slight decrease in resistivity with temperature is controlled by charge transport between BSCCO particles through non-conducting elastomer barriers. In addition we believe that the NTCR effect is due to flow of elastomer chains at high temperature.
It is interesting to mention that with decreasing PE content in the blends, the percolation temperature shifts to higher values, and a drop in resistivity is observed. This indicates that the inclusion of PE up to 10 wt % improves the thermal stability and the skeletal molecular structure of the blend.
However, PTCR thermistors can be used as thermal sensors. Therefore, high resistance jumping and temperature coefficient of resistance are necessary for high sensitivity of this kind of sensor for practical use.
It is clear that PTCR intensity increases with increasing PE content up to 10 wt %, then decreases. The improvement in the PTCR intensity effect up to 10 wt % PE can be attributed to an increase in surface acceptor state with the increasing PE content. However, further addition of PE led to a weaker PTCR intensity effect due to the poor quality of grain boundaries arising from the occurrence of more PE-containing liquid phases during vulcanization.
In
Static charge is immovable, and so the generated static charges localized on the surface of the materials cannot be removed. In case of conducting materials, the charges may conduct to some place else and leak to the air, thereby creating a serious static problem. In some extreme cases, a sufficient amount of static charges may generate sparks and cause a fire explosion. For antistatic applications, surfaces with a resistivity of 103-108 Ohm-cm are needed.
Another interesting aspect of this work is the influence of PE content on static energy (SE) of the blend, as shown in
The discharge voltage of the blends as a function of time is plotted in
Electromagnetic interference (EMI) is one of the major factors for malfunction of electronic and electrical equipment. To control (EMI), the housing cabinet of electronic equipment is provided with a conductive shield made up of either metallic enclosures or carbon composites. The effectiveness of such shields is essentially a function of surface resistivity. Shielding effectiveness is described as the attenuation of an electromagnetic wave produced by its passage through a shield and is measured as the ratio of the shield strength before and after attenuation.
The relationship between EMI and conductivity as a function of PE content is plotted in
The measured and calculated values of EMI as a function of frequency are plotted in
It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.