Advances in Materials Science and Engineering
Volume 2017 (2017), Article ID 2703986, 7 pages
https://doi.org/10.1155/2017/2703986

Research Article

Experimental Investigation of Isothermal Section of the B-Cr-Fe Phase Diagram at 1353 K

Viera Homolová and Lucia Čiripová

Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 040 01 Košice, Slovakia

Correspondence should be addressed to Viera Homolová; vhomolova@saske.sk

Received 28 February 2017; Accepted 20 April 2017; Published 11 May 2017

Academic Editor: Pavel Lejcek

Copyright © 2017 Viera Homolová and Lucia Čiripová. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

The isothermal section of the B-Cr-Fe ternary system was studied experimentally at 1353 K. X-ray diffraction and scanning electron microscopy equipped with EDX analyzer were used for determination of phase equilibria and composition of the coexisting phases in the B-Cr-Fe model alloys after long-term annealing (1500–2205 h). Two iron borides FeB and Fe₂B, six chromium borides Cr₂B, Cr₅B₃, CrB, Cr₃B₄, CrB₂, and CrB₄ and also iron and chromium solid solutions (α(Fe,Cr), α(Cr,Fe), γ(Fe,Cr)) and β-rhombohedral B were observed in the alloys. High solubilities of the third element in binary borides and no ternary phase were found. Based on the experimental results, isothermal section of the B-Cr-Fe system at 1353 K was determined.

1. Introduction

The knowledge about phase equilibria of the B-Cr-Fe system is important in several fields of materials research. The system is subsystem of various complex alloys, for example, modified ferritic steels for energy industry [1–3], steels for production abrasive, and corrosion-resistant components [4]. Information about the system is also important for study of boride coatings on various alloys and metals, including iron [5, 6].

Borides of transition metals, including chromium borides, have unique combination of thermal, mechanical, magnetic, and electrophysical properties and are being widely used in atomic power and chemical industry [7, 8].

The B-Cr-Fe system has been experimentally studied by only a few authors. Gorbunov and Bodurjan [9] investigated system at 1373 K after annealing for 320 h and Chepiga and Kuzma [10] at 973 and 1173 K after annealing for 400 and 750 h, respectively. In the works [9, 10], some questionable phases were found. CrB₆ boride, found by Gorbunov and Bodurjan [9] and also by Chepiga and Kuzma [10], is not boride, but it is oxyboride as it was later clarified [11]. Besides the phase, Gorbunov and Bodurjan [9] found Cr₄B and Cr₂B₅ phases. The phase that was predicted as Cr₂B₅ was not observed by any other investigators neither in ternary B-Cr-Fe [10] nor in binary B-Cr system [12]. Regarding the Cr₄B phase, it was shown that the phase is orthorhombic Cr₂B phase [13]. The phase constitution of the system at 1373 K was investigated also by Gianoglio et al. [14], but, however, only in region up to 50 at% boron.

The present work is focused on experimental study of phase equilibria of the B-Cr-Fe system at 1353 K in the entire composition range after long time annealing within 1500–2205 h that guarantee to achieve equilibrium state.

2. Experimental Procedure

High purity powders of Fe (99.98%), B (99.9%), and Cr (99.99%) were used as input material for the production of twenty B-Cr-Fe alloys. Powders were mixed, pressed into cylindrical pellets at a pressure of 700 MPa, and subsequently melted. The melting was carried out in an argon arc furnace on water cooled copper plate in argon atmosphere of 99.999% purity. The solidified alloys (15 g) were remelted several times in order to achieve good homogeneity. The final chemical compositions of the produced alloys were determined by atomic absorption spectroscopy; see Table 1. The alloys were then sealed into evacuated silica glass tubes with titanium turnings and annealed at 1353 K within 1500–2205 h. After the annealing, the samples were quenched into cold water.

Table 1: Chemical compositions of model alloys, conditions of annealing, and phases identified in the alloys after annealing.

Composition [at.%]
Annealing
Identified phases

17Fe-65B-18Cr
1353 K/1848 h
CrB₂, CrB₄, FeB

33Fe-62B-5Cr
1353 K/1848 h
B, FeB, CrB₄

8Fe-56B-36Cr
1353 K/1848 h
Cr₃B₄, CrB

50Fe-40B-10Cr
1353 K/1848 h
Fe₂B, FeB

32Fe-40B-28Cr
1353 K/1848 h
CrB, FeB, Cr₂B

15Fe-40B-45Cr
1353 K/1848 h
CrB, Cr₂B, Cr₅B₃

15Fe-25B-60Cr
1353 K/1848 h
Cr₂B, α(Cr,Fe)

8Fe-10B-82Cr
1353 K/1848 h
Cr₂B, α(Cr,Fe)

5Fe-52B-43Cr
1353 K/1848 h
CrB, Cr₃B₄

48Fe-10B-42Cr
1353 K/1848 h
Cr₂B, α(Fe,Cr)

70Fe-10B-20Cr
1353 K/1848 h
Cr₂B, α(Fe,Cr)

8Fe-62B-30Cr
1353 K/1848 h
CrB₂, Cr₃B₄

10Fe-25B-65Cr
1353 K/1848 h
Cr₂B, α(Cr,Fe)

3Fe-35B-62Cr
1353 K/1848 h
Cr₂B, Cr₅B₃

10Fe-38B-52Cr
1353 K/1848 h
CrB, Cr₂B, Cr₅B₃

37Fe-45B-18Cr
1353 K/2205 h
Fe₂B, FeB, Cr₂B

23Fe-45B-32Cr
1353 K/1500 h
Cr₂B, CrB, FeB

29Fe-51B-20Cr
1353 K/1688 h
Cr₃B₄, CrB, FeB

20Fe-52B-28Cr
1353 K/1688 h
Cr₃B₄, CrB, FeB

45Fe-30B-25Cr
1353 K/2205 h
Cr₂B, Fe₂B, γ(Fe,Cr)

The annealed material was studied by X-ray diffraction (Philips X’Pert Pro) and scanning electron microscopy (JEOL JSM-7000F) equipped with “Thermal FEG” and INCA EDX analyzer. The analyzer enables quantitative analysis for elements above and including atomic number 5 (boron). Backscattered electron image mode of scanning electron microscopy was used to study the alloy microstructure.

3. Results and Discussion

All phases identified by experimental method in alloys are given in Table 1. Two iron borides FeB and Fe₂B, six chromium borides Cr₂B, Cr₅B₃, CrB, Cr₃B₄, CrB₂, and CrB₄, and also iron and chromium solid solutions (α(Fe,Cr), α(Cr,Fe), γ(Fe,Cr)) and β-rhombohedral B were found in alloys. The borides in the system form at high temperatures. Most of them form from the liquid during production process of the alloys. Following long-term isothermal annealing leads to achievement of equilibrium chemical compositions of the phases. Crystallographic phase data of observed borides are given in Table 2. The CrB₄ boride was found in 17Fe-65B-18Cr and 33Fe-62B-5Cr alloys. This phase, known from binary B-Cr system [12], has not been observed in ternary B-Cr-Fe system till now [9, 10]. The Cr₂B₅ boride that was found by Gorbunov and Bodurjan at 1373 K after annealing for 320 h was not found. No ternary phase was found in the B-Cr-Fe system. It is in accordance with the mentioned literature [9, 10, 14].

Table 2: Crystal structure data of borides.

Phase
Pearson symbol
Space group
Reference

FeB
oP8
Pbmn
[15]

Fe₂B
tI12
I4/mcm
[15]

CrB₄
oI10
Immm
[12]

CrB₂
hP3
P6/mmm
[12]

Cr₃B₄
oI14
Immm
[12]

CrB
oC8
Cmcm
[12]

Cr₅B₃
tI32
I4/mcm
[12]

Cr₂B
oF40
Fddd
[12]

Figure 1 shows SEM microstructure of the selected alloys. EDX-spectra of the borides in alloys are illustrated on Figure 2. X-ray diffraction patterns of the selected alloys are shown on Figure 3.

(a)

(b)

(c)

(d)

(e)

Figure 1: Microstructure of investigated B-Cr-Fe alloys after annealing at 1353 K for 1848 h: 50Fe-40B-10Cr (a); 15Fe-25B-60Cr (b); 8Fe-10B-82Cr (c); 33Fe-62B-5Cr (d); 8Fe-62B-30Cr (e).

(a)

(b)

(c)

(d)

(e)

(f)

(g)

Figure 2: EDX spectrum of the CrB₄ in 33Fe-62B-5Cr alloy (a); CrB₂ in 17Fe-65B-18Cr alloy (b); Cr₃B₄ in 8Fe-62B-30Cr alloy (c); CrB boride in 15Fe-40B-45Cr alloy (d); FeB boride in 50Fe-40B-10Cr alloy (e); Cr₂B boride in 15Fe-40B-45Cr alloy (f); Fe₂B boride in 50Fe-40B-10Cr alloy (g).

(a)

(b)

(c)

(d)

(e)

(f)

Figure 3: X-ray spectrum of the investigated B-Cr-Fe alloys after annealing at 1353 K: 20Fe-52B-28Cr alloy (a); 50Fe-40B-10Cr alloy (b); 10Fe-38B-52Cr alloy (c); 3Fe-35B-62Cr alloy (d); 15Fe-25B-60Cr alloy (e); 45Fe-30B-25Cr alloy (f).

Four three-phase equilibria FeB+CrB₄+B (Figure 1(d)), FeB+CrB₄+CrB₂, FeB+CrB₂+Cr₃B₄, and FeB+Cr₃B₄+CrB (Figure 3(a)) were found in the part of phase diagram with boron content up 50 at.% (Figure 4). There are some differences between phase equilibria presented in this paper and equilibria at 1373 K from work [9], as shown in Table 3. The differences in this part of the phase diagram are connected with the CrB₆ and Cr₂B₅ phases [9]. However, the CrB₆ phase, as was mentioned in introduction, is not right determined. The existence of Cr₂B₅ boride was not confirmed by present experimental results.

Table 3: Three-phase fields in experimentally determined B-Cr-Fe phase diagram at 1373 K according to the literature [9, 14].

[9]
[14]

FeB B CrB₆

FeB CrB₆ Cr₂B₅

FeB Cr₂B₅ CrB₂

FeB CrB₂ Cr₃B₄

FeB CrB Cr₃B₄

FeB Fe₂B Cr₂B
FeB Fe₂B Cr₂B

FeB Cr₂B CrB
FeB Cr₂B CrB

Cr₂B Cr₅B₃ CrB
Cr₂B Cr₅B₃ CrB

Fe₂B α(Fe,Cr) γ(Fe,Cr)
Fe₂B α(Fe,Cr) γ(Fe,Cr)

Fe₂B α(Fe,Cr) Cr₂B
Fe₂B α(Fe,Cr) Cr₂B

Cr₂B Cr₄B α(Cr,Fe)

Figure 4: The experimentally determined isothermal section of the B-Cr-Fe phase diagram at 1353 K. Compositions of model alloys are marked by .

A part of the isothermal section of the phase diagram with boron range 33–50 at.% contains three three-phase equilibria CrB+Cr₅B₃+Cr₂B (Figure 3(c)), FeB+Cr₂B+Fe₂B, and FeB+CrB+Cr₂B (Figure 4). The same three-phase equilibria were found also at 1373 K in the works [9, 14].

Two three-phase equilibria Fe₂B+Cr₂B+γ(Fe,Cr) (Figure 3(f)) and Cr₂B+γ(Fe,Cr)+α(Fe,Cr) are in the iron rich corner of the phase diagram at the temperature 1353 K (Figure 4). About 9 at.% of chromium was found in the γ(Fe,Cr)-phase in 45Fe-30B-25Cr alloy with phase equilibria Fe₂B+Cr₂B+γ(Fe,Cr). Both Gorbunov and Bodurjan [9] and Gianoglio et al. [14] found Fe₂B+Cr₂B+α(Fe,Cr) and Fe₂B+γ(Fe,Cr)+α(Fe,Cr) equilibria at 1373 K (Table 3), however, with different amount of chromium in the α(Fe,Cr)-phase in Fe₂B+Cr₂B+α(Fe,Cr) equilibrium, about 35 at% of Cr according to [9] and 18 at% according to [14]. The differences between observed phase fields of the part of isothermal section in the present work at 1353 K and in works [9, 14] at 1373 K indicate that the equilibrium phase fields are changed at temperature from temperature range 1353–1373 K.

All found borides dissolve third element. It is illustrated by EDX-spectra on Figure 2. Cr₂B phase has the highest solubility of the third element among all borides in the system. The boride dissolves up to 39 at.% of Fe. The solubility is high also in CrB, FeB, and Fe₂B phases. It was found that Fe₂B contains up to 15 at.% of chromium and FeB dissolves up to 16 at.% of Cr. The CrB phase dissolves up to 15 at.% of Fe. Besides them, high solubility of iron is observed also in Cr₃B₄ boride, Figure 2(c), that contains up to 15 at.% of Fe. Various amounts of dissolved iron were measured also in other chromium borides. In particular, Cr₅B₃ contains up to 6 at.% of Fe, CrB₂ dissolves up to 2 at.% of Fe, Figure 2(b), and CrB₄ contains up to 7 at.% of Fe, Figure 2(a).

All the mentioned experimental results, that is, equilibrium phase compositions and composition of phases, were used to determine the isothermal section of B-Cr-Fe phase diagram at 1353 K that is shown in Figure 4.

4. Conclusions

In the work, phase equilibria of the B-Cr-Fe model alloys at 1353 K were studied experimentally. The achieved results can be summarized as follows:

(i)Two iron borides FeB and Fe₂B, six chromium borides Cr₂B, Cr₅B₃, CrB, Cr₃B₄, CrB₂, and CrB₄, and also iron and chromium solid solutions (α(Fe,Cr), α(Cr,Fe), γ(Fe,Cr)) and β-rhombohedral B are equilibrium phases in the system at 1353 K.(ii)8 three-phase equilibria were found in the phase diagram at the temperature.(iii)Solubilities of the third element in all binary borides were determined. High solubilities were found in Cr₂B, CrB, Cr₃B₄, FeB, and Fe₂B phases.(iv)No ternary phase was found.

Based on the experimental results, isothermal section of the B-Cr-Fe system at 1353 K was established.

Conflicts of Interest

The authors declare that there are no conflicts of interest regarding the publication of this paper.

Acknowledgments

The present work was supported by Slovak Grant Agency (VEGA) under Grant no. 2/0153/15. Thanks are also due to Dr. P. Repovský for help at production of alloys.

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