Superhard superconducting materials are of considerable interest for the creation of high pressure devices for investigating electrical and superconducting properties of various materials. The superconducting composites consisting of superconductors and superhard materials that are in thermal and electrical contacts may satisfy very conflicting requirements imposed on superconducting materials for special research cryogenic technique, wear-resistive parts of superconductor devices, superconducting micro-electro-mechanical systems (MEMS), etc. The design of materials combining such properties as superconductivity, superhardness, and high strength is an interesting task for both scientific and applied reasons. Superconducting composites may be used for the production of large superconducting magnetic systems (Gurevich et al., 1987).
The discovery of superconductivity in heavily boron-doped diamonds (Ekimov et al., 2004; Sidorov et al., 2005) has attracted much attention. Superconducting diamonds are the hardest known superconductors. The potential applications of superconducting diamonds are broad, ranging from anvils in research high-pressure apparatus to supecronducting MEMS. However, the highest value of the superconductivity onset temperature in boron-doped diamonds was found just about 7 K in thin CVD-grown ﬁlms (Takano et al., 2004) and at about 4 K in bulk diamonds grown at high-pressure and high-temperature (Ekimov et al., 2004; Sidorov et al., 2005). In these pioneering works bulk polycrystalline diamonds with micron grainsize have been synthesized from graphite and B4C composition (Ekimov et al., 2004) and graphite with 4 wt% amorphous boron (Sidorov et al., 2005). The synthesis have been carried out at 8-9 GPa pressure and 2500-2800 K temperature in both cases. Later Dubrovinskaya et al., 2006, carried out synthesis of graphite with B4C composition at much higher pressure value 20 GPa but the same temperature of 2700K and found the superconducting state transition at lower temperature 2.4 - 1.4 K in the obtained doped polycrystalline diamonds. Due to the sharpening of the temperature interval of the superconductivity transition in magnetic field they suggested that superconductivity could arise from filaments of zero-resistant material. An alternative method for the creation of composite diamond superconductors was suggested by one of the authors of the present article, G. Dubitsky, who used sintering of diamond powders with molybdenum to fabricate special research high-pressure anvils with
By sintering diamond micropowders with metal powders (Nb, Mo) and using metal-coated diamond micropowders at high static pressure and temperature we obtained superhard superconductors with
The alternative route is the sintering of superconductor powders with superhard fullerites - new carbon materials produced from C60 and C70 fullerenes (Blank et al., 1998, 2006). Under high pressure and temperature treatment soft C60 and C70 powders transform into fullerene polymers and other carbon structures with various hardness including superhard and even superior to diamond. There are known many alkali metal-fullerene superconductors with relatively high
The highest critical temperature of superconductor transition among known "regular" superconductors has magnesium diboride MgB2 with
Using high-pressure-high-temperature sintering method we manufactured the following composite superhard superconducting materials: diamond-Nb, diamond-Mo, diamond-MgB2, cubic boron nitride-MgB2, fullerite C60- MgB2, diamond-Ti34Nb66, diamond-Nb3Sn, what will be described in this chapter.
2. Experimental section
Experimental samples of the target materials were obtained by treatment at high static pressures and temperatures. The experiments were carried out using modified “anvils with cavity”-type high-pressure apparatus (Blank et al., 2007). Pressure value was calibrated by electrical resistance jumps in reference metals Ba (5.5 GPa), Bi (2.5, 2.7, 7.7 GPa), Pb (13 GPa) and ZnSe (13.7 GPa) at known phase transitions. The temperature graduation of the chambers was performed using Pt/Pt-10%Rh and W/Re thermocouples. The initial components were placed into a tantalum-foil shell of 0.1 mm thickness. Samples were heated by ac current through a graphite heater with a tantalum shell as a part of the sample system. The materials have been obtained at pressures in the range of 7.7 - 12.5 GPa and temperatures of 1373 - 2173 K. The heating time was 60 – 90 s. The samples were quenched under high pressure with a rate of 200 K per second. After pressure release the samples were extracted from the high-pressure cell. Small cylinder-shaped samples with a diameter of 4.5 mm and a height of 3.5 mm were obtained. The parallelepiped samples 3.9×2.51×1.54 mm3 size were made by laser cutting and polishing. The examples of optical images of polished surfaces for 2 different samples are presented in Fig. 1.
The pictures show grains of superhard compound like diamonds and superconducting compounds like metal alloys in between the grains. The X-ray diffraction analysis revealed formation of metal carbides on the boundaries of diamond micro- and nanocrystals and nanocarbon phases originated from C60 fullerene in the samples synthesized with C60 powder. The carbide phases provide strong chemical bonding of superconductor matrix with superhard carbon grains, thus the target composites possess very high strength.
We investigated the phase content of the samples by the powder X-ray diffraction method using an ARL X’TRA diffractometer with Si-Li semiconductor detector and Cu Kα radiation (λ = 0.1541 nm) source. The electrical resistance of the resulting samples was measured by the conventional four probe method. Electrical contacts were made using conducting silver paste. The temperature dependence of the resistance was measured in the interval 1.7 < T < 300 K. We applied the magnetic field up to 5T to determine the effect of magnetic field on the superconductivity transition temperature.
The Vickers microhardness was measured using PMT-3 device at an indenter load of 5.5 N. Sound velocities in 3 samples were measured using a wide-ﬁeld pulse scanning acoustical microscope (WFPAM) in reflection mode (time-of-flight method) at a driving frequency of 50 MHz. The mean diameter of the acoustic beam in the specimen was about 0.1 mm. This experimental procedure was described in detail in (Prokhorov et al., 1999).
3. Superhard material-superconductive metal-systems
3.1. Diamond-niobium system
Synthetic diamond powder with 80 – 100 µm crystallites covered with a niobium ﬁlm by vacuum sputtering was used as the initial material. The total amount of niobium in the initial material was 24 wt %. The experiments were carried out at a pressure of 7.7 GPa and a temperature of 1973 K for 60 s. The diffraction patterns exhibited peaks associated with diamond and NbC monocarbide (Fig. 2 ). A small fraction of NbO2, practically traces, was also found. The NbC monocarbide synthesized at the boundaries of the crystallites had a face-centered cubic lattice with the cubic parameter
The critical temperature of the transition to the superconducting state in all the measurements was ﬁxed at the onset of the transition. According to an analysis of the temperature dependence of the resistance, the critical temperature of the transition of the synthesized samples to the superconducting state was equal to
The microhardness values varied in the range of 35 –95 GPa depending on the actual place of indentation (Dubitski et al., 2005, 2006). According to (Toth, 1971), the Vickers microhardness of NbC is approximately equal to 17 GPa. This value is signiﬁcantly lower than the results obtained in our work for microdomains enriched in NbC The hardness of
|Diamond-Nb||4.1Â± 0.1||12.1Â± 0.5||6.9Â± 0.25||490Â± 95||340Â± 30||195Â± 14||0.26Â± 0.04|
|3.74Â± 0.05||16Â± 0.5||9.6Â± 0.3||850Â± 120||490Â± 30||340Â± 24||0.22Â± 0.04|
such microdomains is high apparently due to the effect of the of diamond crystallites, which have much higher hardness (100 – 150 GPa along different faces, depending on the quality of the crystals). The velocities of sound and the elastic modules are 30 – 40% less than in pure bulk polycrystalline diamond (Table 1). Nevertheless they are comparable with the values for the next very strong superhard material: cubic boron nitride (c-BN).
3.2. C60-diamond-niobium system
High-pressure - high-temperature treatment of C60 and C70 fullerenes leads to polymerization and transformation into new metastable carbon structures (Blank et al., 1998, 2006). Among various polymeric forms, the 3D-polymeric ones are the hardest
(Blank et al., 1998). The density of superhard (
3.3. Diamond-molybdenum system
In this system, a synthetic-diamond powder with a granularity of 40 – 100 µm and a molybdenum powder with a particle size of 1 – 5 µm were used as the initial materials consisting of 60 wt % of diamond and 40 wt % of molybdenum. A compact material was obtained by holding at a pressure of 7.7 GPa and a temperature of 2173 K for 90 s. The phase content of the samples was determined by the same method as for the diamond-Nb system. The following phases were identiﬁed in the samples: the diamond, the α-MoC phase with a cubic lattice with the parameter
The composites obtained in the reaction of diamonds with molybdenum are superconductors with characteristic features. First, the onset of the transition to the superconducting state is
4. Superhard material-MgB2-systems
4.1. Diamond-MgB2 and cubic boron nitride-MgB2-systems
Magnesium diboride, whose superconductivity was discovered 10 years ago (Nagamatsu et al., 2001; Zenitani & Akimitsu, 2003) has much higher critical temperature
As the initial material, we used industrial MgB2 powders in which the content of the basic product was equal to 98.5%. The particle size was reduced to 5 – 10 µm by additional powdering. The prepared mixtures consisted of 80 wt % of the superhard component and 20 wt % of MgB2. The granularity of the diamond and cubic boron nitride powders was equal to 40 – 100 and 28 – 40 µm, respectively. The assembly of the high-pressure cells and the experimental procedure were the same as those used for the diamond-molybdenum system. In one of the experiments, a niobium-coated diamond powder was used. The samples were obtained by sintering at a pressure of 7.7 GPa and a temperature of 1373 K for 60 s.
Using XRD analysis, diamond, MgB2 and MgO were identified in the system diamond-MgB2 after the synthesis.
The temperature dependence of the resistance of the samples shows that the temperature of the transition to the superconducting state is
The microhardness of the samples indicates that the composite matrix (consisting of cubic boron nitride or diamond) occupying the major part of the body of the samples has a
microhardness of 57 – 95 GPa. Such microhardness values are characteristic for superhard compact polycrystalline materials based on cubic boron nitride and diamond that are used to produce various abrasive and cutting tools (Shul’zhenko et al., 1987). The specific gravity and velocities of longitudinal and transverse sound waves were measured and elastic modules evaluated (Table 2). Though the elastic modules are not very high, such materials have good potential for applications.
4.2. Polymerized fullerite C60-MgB2- system
We synthesized and investigated a set of composite materials obtained from MgB2 superconductor and C60 fullerite mixed in various bulk ratios (Kulbachinskii et al., 2010). The same commercial MgB2 powder with 98.5% of MgB2 and commercial C60 powder with 99,8% C60 and the rest 0,2% of other carbon components were used as the initial compounds for the synthesis. The superconducting superhard composite possesses superconductivity due to MgB2 fraction and superhardness due to polymerized C60 part (Blank et al., 1998).
The particle size was reduced to 5–10 µm by additional powdering. We prepared polycrystalline composite MgB2:C60 with different wt. content of C60 up to 60%. The samples of the materials were obtained at high static pressures 7.7 GPa and temperatures 1273 - 1373 K. The Vickers microhardness values of composites MgB2-C60 were in the range of 18 – 59 GPa. The lowest value has been measured at the local point with dominating MgB2 grains and the highest ones at the point with dominating superhard compound. According to (Prikhna et al., 2002), the Vickers microhardness
MgB2:C60 we identified MgB2, MgO and superhard 3D-polymerized C60. MgO was revealed in the initial magnesium diboride, its content increased with the increasing of sintering temperature. In Fig. 7 diffraction data are shown for two samples with different MgB2:C60 ratio.
It was found that up to 20 wt. % C60 the composite MgB2:С60 is a superconductor. The superconducting transition temperature of composite MgB2:С60 – 80%:20% is
The resistivity of the superconducting composite MgB2:С60-80%:20% increases near the transition to the superconducting state (39<T<80 K). It is not typical for the host MgB2. We suppose that in this temperature range C60 clusters play a significant role in the temperature dependence of the resistivity. For clusters of C60 the resistivity increases when temperature decreases (Buga et al., 2000, 2005).
When the content of C60 increases above 20 wt. %, the superconductivity disappears and the temperature dependence of the resistivity changes. Mott variable range hopping conductivity was observed, following the law:
Fig. 8b. shows the relative change of resistivity in logarithmic scale on T-1/4. The linear dependence is clearly visible in the temperature range 4.2- 60 K. When the content of С60 is >60 wt. % the resistivity slowly increases with the temperature decrease as it is shown in Fig. 8 for sample MgB2:С60-40%:60%. This takes place because the main superhard carbon component which appeared after C60 transformation has graphite-like cross-linked layered structure with semimetallic type of conductivity (Buga et al., 2000).
MgB2 has hexagonal crystal structure ((Nagamatsu et al., 2001). This structure (Fig. 9) consists from a sequence of hexagonal closed packed layers of Mg and graphite-like layers of B. In such structure atoms of Mg have ionic bonding with atoms of B. Inside the boron layer B atoms have covalent 2D bonding.
The critical field value
4.3. Superconductivity of heterofullerides
Recently a method has been developed for synthesizing superconducting heterofullerides of the Fe and Cu groups with the composition K2MC60 (Bulychev et al., 2004). For example, Fig. 11a shows the temperature dependence of the magnetic susceptibility
the heterofullerides studied is smaller than that of K3C60, apparently because substitution of the potassium ion by an ion of smaller diameter decreases the lattice constant. Thus there is a correlation between the superconducting transition temperature and the crystal lattice constant: a decrease of a leads to a decrease of T
Fullerides RbCsTlC60 and Rb2TlC60 have superconducting transition temperature T
5. Ti34Nb66- and Nb3Sn-diamond micropowder-systems
5.1. Ti34Nb66-diamond system
The NbTi alloy is a superconductor which has one of the best strength and high critical magnetic field. A set of new composite materials were synthesized from Ti34Nb66 and Nb3Sn superconductors mixed with microcrystalline diamond and nanodiamond powders in various bulk ratios. The particle size of superconductors was reduced to 5–10 µm by powdering.
The initial Ti34Nb66 alloy (Fig. 12) has a body-centered cubic crystal structure with I m͞ 3 m space group and the unit cell parameter а = 0.328 nm. The superconducting temperature T
The crystal structure of Nb34Ti66 is a homogeneous solid solution with statistical distribution of elements in a unit cell. Figure 13 shows diffractograms of samples obtained after sintering of the mixture of diamond powder and superconductor under pressure of 7.7 GPa at temperatures 1373 K and 1623 K. The lower diffractogram No. 4 (Fig. 13a) was obtained from the initial alloy, the next one (No. 3) of the sample obtained after sintering at 1373 K. No reflections of TiC or NbC appeared at this synthesis temperature.
The next two samples were sintered at 1623 K. The diffractogram No. 2 corresponds to the sample Nb34Ti66 (50%) mixed with 45% diamond micropowder covered by Nb and 5% of nanodiamond is added in this composition. The diffractogram No. 1 corresponds to the sample Nb34Ti66 (50%) mixed with 50% diamond micropowder. We will discuss in detail the difference of diffraction patterns of these samples and how it may affect on the superconductive transition temperature.
At the dffractograms of samples No. 1 and 2 the diffraction peaks from Nb34 Ti66 alloy are easy visible because they have maximal amplitude. They are slightly shifted one to another and the shift is larger at wide angles (2θ ∼ 90 ÷ 1000). A cubic unit cell parameter of Тi34Nb66
alloy calculated with the wide angles (see fig. 13) а=0.329 nm of sample No. 1 is slightly less than а = 0.330 nm of sample No. 2. The intensities of the main peaks are different in these two samples. The intensities of TiC and NbC peaks are different in these samples as well. In sample No. 1 the intensity of TiC-reflections is higher than NbC-reflections while in sample No 2 the intensity of NbC-reflections is higher than TiC-reflections. As for example, at 2θ = 70÷750 and 85÷900 regions (Fig. 13b) NbC-reflections of diffractogram No. 1 disappear. The additional Nb covering diamond crystals in sample No. 2 leads to higher quantity of NbC in this sample. Apparently, 5% of nanodiamond in sample No. 2 increases a separation of Nb. Taking into account that the atomic radius of Ti (0.146 nm) is higher than the atomic radius of Nb (0.145 nm) and that the intensities of NbC – reflections increased, we suppose that the concentration of Nb in sample No. 1 is higher than in sample No. 2. That is why the cubic parameter is smaller. This leads to higher Т
The appearance of NbC and TiC evidences partial decomposition of Nb34Ti66 alloy during the synthesis. Carbides were synthesized under high pressure 7.7 GPa without melting of metals though temperature of synthesis 1625 K is less than the necessary for direct synthesis of carbides. Their melting temperatures exceed 2000 K. The large part of carbon (50%) in samples promotes formation of carbides. However, the content of carbides is not sufficient to rise the T
Table 3 shows the Vickers microhardness of Ti34Nb66 –diamond composite samples No's 1 and 2. The value of microhardness has a wide range as well as in the other composites: the lowest value of hardness has been measured for the Ti-Nb-alloy located in superconductive channels (35 GPa in sample No. 1 and 42 GPa in sample No. 2) and the highest ones in superhard matrix (93-98 GPa). We suppose that the higher hardness of channels (42 GPa) in sample No. 2 has place due to nanodiamond fraction in this sample.
No. 1: 50% Ti34Nb66 + 50% diamond micropowder, T
No. 2: 50% Ti34Nb66 + 45% diamond micropowder covered by metallic Nb + 5% nanodiamond, T
(b) X-ray diffractograms of samples No's. 1 and 2.. D – diffractional reflections of diamond, NbC and TiC – diffractional reflections from Nb and Ti carbides. TiNb and the wide angles of 2θ0 are denoted for Ti34Nb66 reflections.
|Composite||Component ratio, wt.%||Vickers microhardness,|
|1||Ti34Nb66 –diamond micropowder||50:50||35-93||8.9|
|2||Ti34Nb66 –(diamond micropowder covered by Nb + 5% nanodiamond)||50:50 (45:5)||42-98||6|
An intermetallic Nb3Sn compound crystallizes in cubic structure type A-15. Tin atoms are located in body-centered cubic positions, pairs of Nb atoms located on the cubic faces parallel to the coordinate axes (fig. 15). The unit cell contains 8 atoms: 2 Sn + 6Nb; the space group Pm3n, acub. = 0.529 nm. Nb-atoms generate cross-cut chains (fig. 15a). The interatomic distance for Nb-atoms in one chain is appreciably less than the distance in the different chains. The chains of Nb-atoms respond for the generation of quasi one-dimensional electronic spectrum of d-state in this structure.
Nb3Sn was mixed with micropowdered synthetic diamond and sintered at P = 7.7 GPa, T=1623 K. The diffraction pattern in Fig. 16 shows that under high temperature and pressure Nb3Sn partially decomposes to atoms of Nb and Sn. Metallic Nb creates NbC, while Sn in sample is in metallic state. It is worth to note that the temperature of synthesis 1623 K is much less than the melting temperature of Nb3Sn (2400 K). It means that niobium carbide was synthesized in solid state without melting of metal. The content of metallic Sn is very
small. Positions of diffractions peaks of Nb3Sn correspond to the diffraction database (ICDD database PDF-2, card № 19-0875). Thus the decomposition of Nb3Sn is insignificant in spite of high parameters of sintering. The composite Nb3Sn with diamond powder is a superconductor with T
The superhard superconducting composites are the new large family of materials for cryogenic electro-mechanical tools and devices. We employed high-pressure-high-temperature technique for synthesis of various superconducting composites on the basis of the hardest known materials: diamond, cubic boron nitride, C60-fullerites. The best traditional superconductor alloys and relatively new, like MgB2 have been used for synthesis to provide a superconductivity of the target materials. The structure and properties of the synthesized composites have been investigated. The highest values of microhardness up to 98 GPa and the highest elastic moduli have been found in diamond-based composites. Among them diomond-niobium composite is the hardest and it possesses 12.5K superconductor transition temperature. The highest T