Electrical properties of ternary Bi-Ge-Sb and Al-Cu-Sb alloys

Milena Premovica,*, Duško Minića, Milan Kolarevicb, Dragan Manasijevicc, Dragana Živkovićc, , Aleksandar Djordjevica, Dusan Milisavljevica

a University in Priština, Faculty of Technical Science, K.M. 7, 4000 Kos. Mitrovica, Serbia

b University of Kragujevac, Faculty of Mechanical and Civil Engineering, Dositejeva 19, 36000 Kraljevo, Serbia

c University of Belgrade, Technical Faculty, VJ 12, 19210 Bor, Serbia

*Corresponding author: milena.premovic@gmail.com

( Deceased 26th November 2016)



Electrical properties of ternary Bi-Ge-Sb and Al-Cu-Sb alloys. This paper presents review of electrical properties of two ternary systems based on Sb, ternary Bi-Ge-Sb and Al-Cu-Sb system. Beside electrical properties in paper are presented microstructures of both systems observed with light optical microscopy. On four samples microstructural analysis was carried out by scanning electron microscopy combined with energy dispersive spectrometry and X-ray powder diffraction technique. Moreover, micro hardness of selected alloys from the ternary Bi-Ge-Sb system was determined using Vickers hardness tests.



Propiedades eléctricas de las aleaciones ternarias Bi-Ge-Sb y Al-Cu-Sb. Este artículo presenta el estudio de las propiedades eléctricas de dos sistemas ternarios basados en antimonio, Bi-Ge-Sb y Al-Cu-Sb. Además de las propiedades eléctricas, en el artículo se presenta las microestructuras observadas por microscopía óptica. Se utilizaron cuatro muestras para el análisis de la microestructura utilizando MEB, EDS y DRX. Además, se determinó la microdureza de muestras seleccionadas de la aleación ternaria Bi-Ge-Sb, la dureza se determinó utilizando ensayos Vickers.


Submitted: 21 March 2016; Accepted: 28 February 2017; Available On-line: 11 July 2017

Citation/Citar como: Premovic, M.; Minić, D.; Kolarevic, M.; Manasijevic, D.; Živković, D.; Djordjevic, A.; Milisavljevic, D. (2017) “Electrical properties of ternary Bi-Ge-Sb and Al-Cu-Sb alloys”. Rev. Metal. 53(3): e098. http://dx.doi.org/10.3989/revmetalm.098

KEYWORDS: Electrical conductivity; Hardness; Materials testing; Microstructure

PALABRAS CLAVE: Conductividad eléctrica; Dureza; Materiales de muestra; Microestructura

ORCID ID: Milena Premovic (http://orcid.org/0000-0003-0532-7048); Duško Minić (http://orcid.org/0000-0002-0432-6038); Milan Kolarevic (http://orcid.org/0000-0001-6521-5035); Dragan Manasijevic (http://orcid.org/0000-0002-7828-8994); Dragana Živković (http://orcid.org/0000-0002-2745-5676); Aleksandar Djordjevic (http://orcid.org/0000-0002-5136-7019); Dusan Milisavljevic (http://orcid.org/0000-0003-0598-2392)

Copyright: © 2017 CSIC. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY) Spain 3.0.




Antimony is an important metal in the world economy because of the applications in many industries, such as electronics industry, military industry, pharmaceutical industry, etc. (Vinhal et al., 2016). The largest producer of antimony is China with 114 Sb mines and approximately 90% of the world’s production (He et al., 2012; Sun et al., 2016). The other producers are Canada, Russia, Bolivia and South Africa.

In the electronics industry antimony is used for making semiconductor devices, such as infrared detectors and diodes (Serrano et al., 2016). Antimony compounds are used to make bullets (Johnson et al., 2005), flame-retardant materials, car brake liner lubricants, type metal (in printing presses), enamels, cable sheathing, catalysts for the production of polyethylene terephthalate (PET) and alloy additives glass and pottery (Bech et al., 2012; Cui et al., 2015; Macgregor et al., 2015). On the other hand antimony is used as a medicine in the treatment of Leishmaniasis and their potential usefulness in AIDS and cancer therapy (Pierart et al., 2015).

Beside wide application of antimony it is important to study different combination of antimony with other element. During the past decades so many combination and also different composition of binary systems based on Sb were studied (Liu et al., 2013; Gierlotka, 2014) and later ternary systems (Zobač et al., 2015; Guo et al., 2016).

These two ternary systems Al-Cu-Sb and Bi-Ge-Sb were investigated before by the same group of authors as this paper. The ternary Al-Cu-Sb system was previously investigated by Minić et al. (2013) who experimentally studied liquid surface, three vertical sections and two isothermal sections at 200 ºC and 400 ºC. Another ternary Bi-Ge-Sb system was investigated by Premovic et al. (2014). In the paper given by Premovic et al. (2014) are investigated liquid projection, invariant reactions, three vertical sections, as well as isothermal sections at 100 ºC and 500 ºC.

In this paper electrical properties and microstructure of the alloy samples from the ternary Al-Cu-Sb and Bi-Ge-Sb systems are presented. Beside mentioned properties results of SEM-EDS and XRD measurement are presented as well. Also micro hardness was determined for some alloys from ternary Bi-Ge-Sb system. This kind of paper or similar (Illescas et al., 2009; Verbeken et al., 2010) will give a better insight into properties of alloys which should contribute to further development of application area.


All investigated samples were prepared from high purity (99.999 at. %) element produced by Alfa Aesar (Germany) in an induction furnace under high-purity argon atmosphere. Given that Sb is highly volatile an additional amount of Sb (about 1 to 2 at. %) was added to compensate for the weight loss. Additional amount of antimony is highly recommended especially for high antimony systems. In general, the average loss of mass during melting of samples was about 1 at.%.

Microstructural analysis was carried out by TESCAN VEGA3 scanning electron microscope with energy dispersive spectroscopy (EDS) (Oxford Instruments X-act) and by light microscopy using (LOM) OLYMPUS GX41 inverted metallographic microscope. Samples were prepared by the classic metallographic procedure without etching. Polished samples were firstly subjected to EDS elemental mapping to check compositional homogeneity and possible segregation and then analyzed. Overall composition and compositions of coexisting phases was determined using EDS point and area analysis.

XRD patterns of the studied samples were recorded on a D2 PHASER powder diffractometer equipped with a dynamic scintillation detector and ceramic X-ray Cu tube (KFLCu-2K) in a 2θ range of 5º to 75º with a step size of 0.02º. The patterns were analyzed using Topas 4.2 software and ICDD databases PDF2 (2013).

As the next step, electrical conductivity and hardness measurements were performed. Electrical conductivity measurements were carried out using Foerster SIGMATEST 2.069 eddy current instrument. The microhardness of the phases present in the microstructure was determined using a Vickers microhardness tester Sinowon, model Vexus ZHV-1000V.


The alloy samples from ternary Bi-Ge-Sb system were investigated using several different techniques. Thirteen ternary alloy samples were observed with light optical microscopy, same samples were subjected to the measurement of the electrical conductivity. Further each phase detected in microstructure is subjected for determination of the microhardness. Additionally two ternary samples are investigated with XRD and SEM-EDS techniques.

Eight alloy samples from ternary Al-Cu-Sb system were observed with light optical microscopy and on same samples electrical conductivity were determined. For better insight into microstructures two ternary alloys are investigated with SEM-EDS and XRD techniques.

In Table 1 are presented list of phases for both ternary system with their corresponding Pearson symbols.

Table 1. Considered phases and their crystal structures for ternary Bi-Ge-Sb and Al-Cu-Sb system
Phase name Common name Pearson symbol Space group
Bi-Ge-Sb system
RHOMBO_A7 (Bi, Sb) hR2 R3m
DIAMOND_A4 α (Ge) cF8 Fd3m
Al-Cu-Sb system
RHOMBO_A7 (Sb) hR2 R3m
FCC_A1 (Al, Cu) cF4 Fm3m
ALCU-ETA AlCu mC20 Cm/2
AL2CU_TYPE Al2Cu tI12 I4/mcm
ALCU_DELTA Al2Cu3 hP42 R3m
ALCU_ZETA Al9Cu11 oI24 Imm2
BCC_A2 Cu3Al cF16 Fm3m
ALSB AlSb cF8 F43m
BCC_A2 Cu3Sb cF16 Fm3m
CUSB_ETA Cu2Sb tP6 P4/nmm
CUSB_ZETA Cu73Sb20 hP26 F3
CUSB_GAMMA Cu11Sb2 hP2 P63/mmc
CUSB_DELTA Cu9Sb2 hP* P63/mmc

Thirteen alloy samples for investigation of electrical conductivity were selected along three vertical sections Ge-BiSb, Sb-BiGe and Bi-GeSb for ternary Bi-Ge-Sb and eight alloy samples from two vertical sections Al-CuSb and Sb-AlCu for ternary Al-Cu-Sb. The obtained values of the electrical conductivity of the studied alloy samples are given in Table 2. Also in Table 2 are presented experimentally obtained values for five binary alloys and literature value for electrical conductivity of pure elements, which are taken from online database periodictable, Electrical Conductivity of the elements (Gray et al., 2013).

Table 2. Electrical conductivity of the alloy from ternary Bi-Ge-Sb and Al-Cu-Sb systems
    Electrical conductivity (MS/m)  
    Values for different measurement  
Number Composition of sample (at.%) 1 2 3 4 5 Mean value
1 Bi50Sb50 1.1865 1.1744 1.1754 1.1706 1.1736 1.1761
2 Bi40Ge20Sb40 0.3782 0.3767 0.3089 0.3154 0.379 0.35164
3 Bi30Ge40Sb30 0.3334 0.3437 0.3118 0.2739 0.316 0.31576
4 Bi20Ge60Sb20 0.266 0.2396 0.2492 0.2479 0.2656 0.25366
5 Bi10Ge80Sb10 0.1879 0.1987 0.2019 0.1829 0.1889 0.19206
  Ge100   0.002        
6 Bi50Ge50 0.3005 0.2495 0.2598 0.2698 0.2987 0.27566
7 Bi40Ge40Sb20 0.1987 0.1903 0.2013 0.189 0.2056 0.19698
8 Bi30Ge30Sb40 0.3077 0.2376 0.2532 0.3085 0.3226 0.28592
9 Bi22.5Ge22.5Sb55 0.6067 0.6103 0.6146 0.5752 0.6257 0.6065
10 Bi20Ge20Sb60 0.8105 0.821 0.8065 0.8113 0.7889 0.80764
11 Bi10Ge10Sb80 1.444 1.433 1.427 1.44 1.439 1.4366
  Sb100   2.5000        
12 Ge50Sb50 0.3487 0.3398 0.3402 0.3494 0.3509 0.3458
13 Bi20Ge40Sb40 0.3576 0.2743 0.3465 0.3833 0.3527 0.34288
14 Bi40Ge30Sb30 0.3897 0.3879 0.4298 0.3786 0.399 0.397
15 Bi60Ge20Sb20 0.4319 0.4222 0.4231 0.4207 0.4021 0.42
16 Bi80Ge10Sb10 0.5698 0.5598 0.5823 0.5598 0.5987 0.57408
  Bi100   0.77        
17 Al50Sb50 7.9833 7.8874 7.9884 7.8474 7.4354 7.8283
18 Al40Sb40Cu20 5.9883 5.0999 5.8453 5.8343 5.9182 5.7372
19 Al30Sb30Cu40 4.3758 4.3763 4.3792 4.3801 4.3778 4.3778
20 Al20Sb20Cu60 7.9883 6.9002 7.5455 7.8876 5.0877 7.0818
21 Al10Sb10Cu80 14.9875 13.9804 12.9887 14.0232 15.0011 14.1961
  Cu100   59        
22 Al50Cu50 28.8723 26.9893 27.7759 23.9874 29.8750 27.4999
23 Al40Sb20Cu40 2.9872 2.9310 2.9857 3.0974 3.1121 3.0226
24 Al30Sb40Cu30 0.4621 0.4617 0.4504 0.4593 0.4583 0.4583
25 Al20Sb60Cu20 0.7613 0.7493 0.7016 0.7291 0.7353 0.7353
26 Al10Sb80Cu10 1.1270 1.1080 1.1070 1.1270 1.1172 1.1172

In comparison of the obtained experimental results of electrical conductivity given in Table 2, it is clearly visible that ternary Al-Cu-Sb alloys have a significantly higher value of the electrical conductivity than alloy from ternary Bi-Ge-Sb system.

Based on experimentally determined values of electrical conductivity given in Table 2 and using an appropriate mathematical model, electrical conductivity of all other alloys in ternary systems have been calculated.

To define a mathematical model for electric conductivity of alloys software package Design Expert v. were used. Out of possible canonical or Scheffe models (Cornell, 1990; Kolarević, 2004; Lazić, 2004) that meet the requirements of adequacy recommended is Special Quartic model, Eq. (1):

The Analysis of variance (ANOVA) implies that the model is significant. However, the diagnosis of the statistical properties of the assumed model found that the distribution of residuals is not normal and that it is necessary to transform the mathematical model in order to meet the conditions of normality. The Box-Cox diagnostics (Box and Draper, 2006; Myers et al., 2009) recommends a ”Square Root“ transformation for the variance stabilization.

The Model summary statistics for ”Square Root“ model transformation are suggested Special Quartic Mixture Model. Again using the Analysis of variance (ANOVA) sugested model was checked. Value such as F factor, p-value and R-squared are statistical value which are important in way of searching a best model. According to the statistic calculation the highest value of the R-squared, F factor and low value of p-value factor (p value should be lower then 0.0001) justified the model. Obtained value for F and R for the Special Quartic Mixture Model for ternary Al-Cu-Sb system are F=86.26 and R-Squared=0.931. Which are in comparison with F and R value for other models significantly higher and chosen model is justified. Same check was done for ternary Bi-Ge-Sb and obtained value for F=526.34 and R-Squared=0.9827 which also justified chosen Special Quartic Mixture Model.

For both ternary systems Al-Cu-Sb and Bi-Ge-Sb same mathematichal model were used and same procedure was applied.

The final equation of the predictive model for Bi-Ge-Sb system is given as Eq. (2):

The final equation of the predictive model for Al-Cu-Sb system is given as Eq. (3):

Based on defined models electrical conductivity were predicted for all other alloys in the ternary systems and iso-lines for electrical conductivity of alloys defined by Eq. (2) and Eq. (3) are shown in Fig. 1 (a and b) respectively.

Figure 1. Iso-lines of electrical conductivity for the ternary: a) Bi-Ge-Sb (left), and b) Al-Cu-Sb (right) systems.


Some of the obtained light optical micrographs are presented in Fig. 2. All alloy samples from ternary Bi-Ge-Sb system have same three (Bi)+(Sb)+(Ge) phases in structure.

Figure 2. Microstructures for the selected alloys samples.


From micrographs presented on Fig. 2, is clearly visible that all samples are from three phase region. For better insight into microstructure two additionally samples per ternary system are investigated with SEM-EDS and XRD techniques. Obtained results are presented in Table 3. Microstructure of other samples which are not presented on Fig. 2, are presented in Table 4. All microstructures of samples from ternary Al-Cu-Sb are given in Fig. 2.

Table 3. Experimentally determined phase compositions and lattice parameters of the ternary Bi-Ge-Sb and Al-Cu-Sb systems
S Overall composition (at.%) Experiment. determined phases Compositions of phases (at.%) Lattice parameters (Å)
Bi Ge Al Cu Sb a=b c
A 12.03 Bi
74.58 Ge
13.39 Sb
B 9.21 Al
11.03 Cu
79.76 Sb
C 27.15 Bi
45.01 Ge
27.84 Sb
D 23.73 Al
55.52 Cu
20.75 Sb
Table 4. Measured Vickers microhardness of the phases in the ternary Bi-Ge-Sb system

Experimentally results of XRD are compared with literature data. Literature value for lattice parameters of solid solution (Bi) are a=b=4.546 Å and c=11.862 Å defined by Cucka and Barrett (1962). Lattice parameter for solid solution (Sb) are compared with data given by Barrett et al. (1963), a=b=3.301 Å and c=11.232 Å. Obtained result for (Bi) and (Sb) solid solution are in reasonable agreement with literature, small deviation is visible because of solubility Sb in Bi and conversely. Data for (Ge) are used from Swanson and Tatge (1953) were determined lattice parameter are a=b=c=5.658 Å. Three detected intermetallic phases AlSb, Al4Cu9 and Cu2Sb from Al-Cu-Sb system are in good agreement with data given by Woolley and Smith (1958), Westman (1965), and Pearson (1985) respectively. In Fig. 3 are presented two SEM microstructure for samples A and B (see Table 3). On both micrographs are visible three phases region. Sample A rich with (Ge) formed structure with three solid solution (Bi) light phases, (Sb) grey and (Ge) darkest phase. On micrographs from LOM (see Fig. 2) is hard to notice difference between (Sb) and (Bi) phases and on SEM micrographs phases are clearly visible. Sample B belongs to three phases region (Sb)+AlSb+Cu2Sb.

Figure 3. SEM micrographs for samples: a) A-Bi12.03Ge74.58Sb13.39 (left), and b) B-Al9.21Sb79.76Cu11.03 (right).


Alloy samples from ternary Bi-Ge-Sb are further investigated with micro-Vickers hardness test and results of test are shown in Table 4. Each phase was tested several times (from ten up to twenty) at different position and mean value of hardness are given in Table 4 with micrographs after testing.

Experimentally obtained hardness for solid solution (Ge) is in the range of values from 844.78 MN.m-2 to 860.22 MN.m-2. In microstructures is very difficult to distinguish solid solution (Bi) from solid solution (Sb) and hardness of this two phases is determined as a harness of (Bi)+(Sb) solid solution with value in the range from 64.992 MN.m-2 to 110.244 MN.m-2. This big difference in hardness is possible to justify by quantity of Bi and Sb in alloy. Alloys rich with Sb have a higher value of hardness than alloys rich with Bi.


This paper presents experimental results of microstructure, electrical properties and mechanical properties of alloy from two ternary systems.
Ternary Bi-Ge-Sb system has been investigated with a large number of sample using different experimental techniques. In microstructure of all samples were detect three solid solution (Bi), (Ge) and (Sb). All samples from three different vertical section belong to three phases region (Bi)+(Ge)+(Sb). Using SEM-EDS technic has been determined composition of the samples and phases presented in microstructure. Using XRD techniques lattice parameters were determined and confirmed phases detect with SEM-EDS. Micro-Vickers hardness test used for determination of the phase hardness detected in microstructure in the ternary Bi-Ge-Sb alloy samples. Each detected phase were tested several times at different position and determined mean value from all measurement for solid solution (Ge) is 852.8267 MN.m-2 and for solid solution (Bi)+(Sb) is 85.06631 MN.m-2.
Ternary Al-Cu-Sb system was investigated with same experimental techniques as a ternary Bi-Ge-Sb system except determination of phase hardness. Using SEM-EDS and XRD techniques two alloy samples were investigated and in their structure were determined three phases region in sample B, AlSb+Sb+Cu2Sb and AlSb+Cu2Sb+Al4Cu9 in sample D. Other prepared samples from two vertical sections are observed with light optical microscopy. In obtained micrographs are clearly visible that all samples belong to the three phase region.
Electrical conductivity for alloys from both ternary systems and electrical conductivity for binary alloy (BiGe, GeSb, BiSb, AlSb and AlCu) have been measured. Obtained results show that ternary alloy Bi10Ge10Sb80 have highest value for electrical conductivity from other ternary alloy in ternary Bi-Ge-Sb system. On the other hand results of the conductivity for alloy samples from ternary Al-Cu-Sb system were in a wide range of value from 0.4583 MS/m up to 14.1961 MS/m. The highest value of the electrical conductivity was obtained for ternary alloy Al10Sb10Cu80. Besides experimental work using appropriated mathematical model has been calculated electrical conductivity for all other possible ternary alloy and results are presented as a iso-lines of electrical conductivity.


This work was supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia, under Project No. ON172037 and TR37020.


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