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Materials science communication

High-temperature behavior of the boride layer of 45# carbon steel

P.X. Yan , X.M. Zhang, J.W. Xu, Z.G. Wu, Q.M. Song
Department of Physics, Lanzhou University, Lanzhou 730000, PR China Received 6 September 2000; received in revised form 7 November 2000; accepted 5 December 2000

Abstract The high-temperature behavior of boronized layer of 45# carbon steel has been studied in detail by using high-temperature X-ray diffractometer (HTXRD), difference temperature analysis (DTA) technique, high-temperature microscope, high-temperature hardness tester. Research results show that (1) the hardness of the boride layer decrease with temperature, (2) there is no oxidation of boride layer on the measuring range of the temperature, and (3) the threshold temperature of the phase transformation of the boride layer from FeB to Fe2 B is about 860 C. 2001 Published by Elsevier Science B.V.
Keywords: Boronizing; High-temperature X-ray diffractometer; Difference temperature analysis; Hardness

1. Introduction Boronizing is one of the chemical heat treatment techniques that used in various metal surface engineering [15]. It is a diffusion process whereby a single phase Fe2 B or a double inter-metallic phase (Fe2 B, FeB) is obtained by diffusing boron atoms into the surface of metallic materials. The boronized metal surface is of high hardness, good wear resistance, excellent corrosion resistance and ideal oxidation resistance. However, the main disadvantage of boronizing is the embrittlement of boronized layers. One of the methods to overcome this shortcoming is forming single phase Fe2 B on the metal surface through choosing boroning processes. The low-grade boron Fe2 B phase with low embrittlement is especially desirable for industrial application. There are several boronizing methods that can form ideal single Fe2 B phase in boride layer [68]. Many studies have been done on the acquisition of boronized layers, boronizing mechanism, phases of boride layers and their properties at room temperature. Few research works on the high-temperature behavior of boronized layers had been carried out. Although one found that the FeB phases could transform into Fe2 B phase through heat treatment at high temperature [9], no more details and mechanism of transformation of boride layers has been reported. We even do not know what is the shape of boride at high temperature. However, it is well known that boronizing processes are usually carried out on the

high-temperature environment, so it is necessary to study the high-temperature behavior of boride layers in order to obtain the detail information about boronizing mechanism. Moreover, lots of boronized workpieces are used on the high-temperature environment, which also needs one to know the high-temperature behavior of the boride layers. In this paper, using a high-temperature microscopy, a high-temperature X-ray diffractometer (HTXRD), a difference thermal analysis (DTA) apparatus and other techniques, the behavior of the boride layer at high temperature has been investigated.

2. Experimental 45# carbon steel was chosen as sample to be boronized. The composition of the 45# steel are 98.61% Fe, 0.48% C, 0.62% Mn, 0.25% Si, 0.04% S and 0.008% P. The steel sample was cut into three kinds of specimens with size of 4 8 2.5 mm3 , 5 5 1 mm3 and 3.5 0.5 mm2 , respectively. The solid boronizing technique was used to boronize the steel specimens. The used solid boron-yielding agents consist of boron carbide, potassium boron uorate, carbofrax, activated charcoal and a few other constituents. All the boronizing processes were carried out at the temperature of 950 C for 8 h. The high-temperature microscopy analysis and high-temperature hardness test were characterized by using Union Model HM-100 ultra-high-temperature microscope. Model Rigaku D/Max-B-HTXRD was used to analyze the structure parameters of boride layers. The PCT-2

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0254-0584/01/$ see front matter 2001 Published by Elsevier Science B.V. PII: S 0 2 5 4 - 0 5 8 4 ( 0 1 ) 0 0 2 7 0 - X

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P.X. Yan et al. / Materials Chemistry and Physics 71 (2001) 107110

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model DTA technique was used to measure heat effect of boronized samples.

3. Results and discussion 3.1. Measurement of high-temperature hardness By using Union Model HM-100 high-temperature hardness tester, the Vickers hardness of the boronized layer at different temperatures were measured in situ with temperature increasing at a load of 100 g. The indentation head is made of blue gem. The loading rate is 10 g s1 . The loading time is 10 s. The mean data of hardness of three points along the boride teeth was used as the hardness of boronized layers. The measuring hardness ranged from room temperature to 1100 C. Fig. 1 shows the hardness values of boride layer and 45# steel substrate varying with temperature. It is noted that hardness of both boride layer and 45# steel substrate decrease with temperature. The hardness of boride layer has a high value of Hv1858 at room temperature, which is far higher than that of 45# steel substrate. It is still contain a relative high hardness value of Hv605 at the temperature reaches up to 600 C. The hardness of the boride layer decreases to a low value of Hv350 at the temperature of 700 C. But the value is still higher than that of the substrate. The hardness of boride layer is only Hv110 at the temperature of 900 C. That means that the boride completely loses its high hardness at the temperature of 900 C. 3.2. Microscopy observation of boride layer Combination using video machine and high-temperature microscope, a series of micrographs of the boride layer at different temperatures had been observed and recorded. It persists 10 min for each point of the temperature at which the photograph of the boride layer is taken. The microstructure change of boride layer with temperature is displayed in Fig. 2. A typical structure of the boride layer at room

temperature has been showed in Fig. 2a. It is noted clearly that the zigzag teeth structure of the boride layer. The thickness of the boride layer is about 20 m. The boride layer consists of FeB and Fe2 B phases. The near-surface layer is FeB, and inside is Fe2 B with big boride teeth imbedding substrate. The microstructure of the boride layer changes very slowly with temperature. Microscope observation shows that the structure shape of boride layer below the temperature of 860 C does not exhibit an obvious change comparing with that at room temperature. Up to the temperature of 865 C, the shapes of the boride teeth begin to display a little change (as shown in Fig. 2b). This result demonstrates that the boride layer is of a very stable structure. Obvious shape change of the boride layer took place at the temperature of 1000 C (as shown in Fig. 2c). Fig. 2c shows that the boride teeth began to melt. At the temperature of 1040 C, no clear boride teeth could be seen and the boride layer is melted completely (see Fig. 2d). This results seem not to obey the FeB phase diagram, in which the melting points of FeB and Fe2 B are 1389 and 1650 C, respectively. In fact, the melting phenomena only take place on the observed surface of FeB and Fe2 B phase, but inside matrix FeB and Fe2 B phase cannot be melted. This is because that the chemical state of FeB and Fe2 B on surface are quite different with inside matrix phases. 3.3. High-temperature X-ray diffraction X-ray diffraction of the boride layer was carried out at the temperature of 30, 400, 600, 750, 860, 900 and 950 C. The boronized sample was kept at each point of the temperature for 10 min during X-ray diffraction test. The N2 gas was introduced into the sample chamber to protect the boronized sample from oxidization. The X-ray diffraction data are listed in Table 1. As shown in Table 1, no peaks of Fe2 B phase can be observed below 860 C. Why no diffraction peaks of Fe2 B phase can be found on the X-ray diffraction pattern? The reason is that the FeB phase covers outside of the boride layer whose thickness is about 40 m, and Fe2 B phase exists inside of the boride layer. The penetration depth of X-ray for metal materials is only about 20 m, and so Fe2 B phase cannot be detected. The diffraction peaks of Fe2 B phase appear above the temperature of 860 C. The peak intensities of Fe2 B phase increase with temperature. This shows that the amounts of the phase increase with temperature. Whereas, the peak intensities of FeB phase reduce obviously along with the appearance of Fe2 B phase. This means that the FeB phase could change into Fe2 B phase at temperature of about 860 C. This result is consistent with the following thermal analysis. 3.4. Thermal analysis of the boride layer

Fig. 1. Dependence of the Vickers hardness of the boride layer and steel substrate upon temperature.

Both DTA and TG are popular thermal analysis techniques to investigate the phase transformation and other thermal

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Fig. 2. Micrographs of the boride layer at different temperatures (magnication : 1000): (a) at room temperature; (b) at 865 C; (c) at 1000 C; (d) at 1040 C. Table 1 The peak intensity of X-ray diffraction of boride layer of 45# steel d () Peak intensity (arb. units) 30 C 2.76 2.56 2.38 2.19 2.12 2.01 1.90 1.83 1.81 1.63 1.60 1.47 53.0 104.2 59.4 112.9 89.3 35.7 36.7 34.2 118.1 40.1 148.0 35.7 137.6 133.5 70.8 63.45 63.4 54.6 31.4 400 C 36.7 98.6 52.5 119.8 62.8 600 C 30.0 85.1 48.2 88.7 41.9 750 C 24.4 60.0 36.6 104.2 49.4 36.1 34.9 26.2 167.3 30.9 31 28.4 118.3 187.0 19.9 37.2 860 C 900 C 950 C FeB Fe2 B FeB FeB Fe2 B FeB + Fe2 B FeB Fe2 B FeB Fe2 B FeB FeB Phase

133.6 199.2 48.6

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higher height shows a fast phase transformation from FeB to Fe2 B. 4. Summary The hardness of the boride layer of 45# steel will decrease with temperature. The hardness of boride layer has a high value of Hv1858 at room temperature, which is far higher than that of 45# steel substrate. It is still contain a relative high hardness value of Hv605 at the temperature of 600 C. The hardness of boride layer decrease to a low value of Hv350 at the temperature of 700 C, but is still higher than that of the substrate. There is no oxidation before 730 C, and only a slight oxidation between 730 and 930 C for the boride layer. The transformation temperature from FeB phase to Fe2 B phase is about 860 C. No obvious change of morphology of the boride layer below temperature of 860 C can be observed. At 1000 C, the boride teeth on the observed surface began to melt. Acknowledgements This program is partly supported by the research funding of Education Ministry of China. References
[1] J.R. Ni, L.L. Ge, Heat Treatment Met. China 1 (2000) 30. [2] Y.F. Liu, H.Q. Li, H.D. Li, Y.P. Wu, Heat Treatment Met. China 9 (1999) 28. [3] A.N. Safonov, Met. Sci. Heat Treat. 40 (1998) 6. [4] G. Palombarini, M. Carbucicchio, J. Mater. Sci. Lett. 3 (1984) 791. [5] P.X. Yan, Y.C. Su, Mater. Chem. Phys. 39 (1995) 308. [6] R. Chatterjee-Fisher, O. Schaaber, Proceedings of the 16th International Conference on Heat Treatment, Stratford upon Avon, UK, The Metals Society, London, 1976, pp. 2730. [7] P.X. Yan, Thin Solid Films 214 (1992) 44. [8] M. Deger, M. Riehle, W. Schatt, Neue Hutte 17 (1972) 341. [9] A.C.V. Mafuschka, Boronizing, Heyden, Philadelphia, PA, 1980.

Fig. 3. DTATGT curves of the boride layer of 45# carbon steel.

behavior of metal materials. By detecting the difference of temperature between the measured material and reference material with the temperature, one could obtain the information about phase transformation of the materials. In this investigation, the PCT-2 model DTA apparatus was used to measure DTA and TG curves of boride layer in an air environment. Fig. 3 shows the curves of DTA, TG and temperature, respectively. No obvious weight gain of the boronized sample can be observed on the TG curve. This demonstrates that the boronized layer is of an excellent oxidation resistance at high temperature. There are two peaks on the DTA curve, which are caused by phase transformation of the boronized layer and 45# steel, respectively. The thermal absorption peak at 731 C is due to the austenite phase transformation of 45# steel. The peak of liberation of heat at the temperature of 864 C corresponds to the phase transformation from FeB to Fe2 B in the boride layer. This result coincides with the above analysis of X-ray diffraction. On the other hand, this temperature should be a threshold value for transformation to take place. The peak at 864 C with a