Effects of Cr and V additions on the microstructure and properties of high-vanadium wear-resistant alloy steel

Abstract

The effects of chromium and vanadium additions on the microstructure, hardness and wear resistance of high-vanadium alloy steel (containing 5–10 wt-% V and 2–10 wt-% Cr) were studied by means of optical microscopy, scanning electron microscope (SEM), X-ray diffraction (XRD), energy dispersive spectrometer (EDS), Vickers hardness and Rockwell-hardness tester & M-200 ring block wear tester. Researching results showed that the solidification structure of high-vanadium wear-resistant alloy steel was mainly consisted α-Fe (martensite), vanadium carbide (VC), M₃C and M₇C₃. Vanadium is mainly distributed over VC, and certain amount of vanadium exists in the matrix and M₇C₃ type eutectic carbide. Chromium is mainly distributed over the M₇C₃, and the matrix also contains a small quantity of chromium. It is found that the content of VC increases with the increase of vanadium content when carbon and chromium contents are constant. The change of micro- and macro-hardness was not obvious with the increase of vanadium content. The content of M₇C₃ type eutectic carbides increases gradually with the increase of chromium content when carbon and vanadium contents are constant. The micro- and macro-hardness increases with the increase of chromium content. The increase of vanadium content brings to the increase of wear resistance of alloy steel when carbon and chromium contents are constant. The change of chromium content had no obvious effect on wear resistance of high-vanadium alloy steel when carbon and vanadium contents. The increase of vanadium content brings to the increase of wear resistance of alloy steel when carbon and chromium contents are constant. The wear resistance of as-cast high-vanadium alloy steel is the best when the content of vanadium and chromium is 10 wt-% and 5 wt-% respectively.

Introduction

At present, wear-resistant metal materials are divided into three main types: high manganese steel, wear-resistant alloy steel and high chromium white cast iron. High manganese steel, which has a hundred years of history, has been widely used as the traditional wear resistant material since it was launching in the market in 1882.^1,2 It is found that high manganese steel shows excellent wear resistance, but this advantage is only when it is in the high impact, high stress and hard abrasive. Its yield strength is low. In order to improve the wear resistance of high manganese steel, the scientists proposed the measures that the chromium, molybdenum, vanadium, etc. were added in it. However, its service life was not significantly increased. Therefore, it has been gradually being replaced by other wear-resistant materials in many areas.^3,4

On the basis of silicon and manganese alloy elements, alloy wear resistant steel developed through the addition of chromium, molybdenum, nickel and other trace elements. The alloy system is from single composition manganese, silicon, chromium, boron, tungsten and vanadium series to complex composition of chromium-manganese-silicon-molybdenum-other trace elements of the multi-component complex system. Wear-resisting alloy steel shows better strength, toughness and wear resistance than high manganese steel under the middle or low impact load. The hardening capacity and hardenability of wear-resisting alloy steel are poor. The microstructure of high chromium cast iron contains more than 20% of the high hardness eutectic carbide. High chromium cast iron has excellent wear resistance. However, it is easy to be deformed and dehisced under high temperature heat treatment. The hardness of the carbide of low alloy white cast iron is low. The carbide is continuously distributed, with very big brittle.^4–6

Vanadium is abundant in China. High-vanadium alloy steel had high hardness and excellent wear resistance. However, the ordinary high-vanadium wear-resistant alloy steel can obtain high hardness only after high temperature quenching process.^7,8 Therefore, the effects of chromium and vanadium additions on the structure and properties of high-vanadium wear-resistant alloy steel was studied, expecting to obtain high-vanadium wear-resistant alloy steel with high hardness and good wear resistance. However, effects of chromium and vanadium additions on the microstructure and performance of high-vanadium wear-resistant alloy steel is also lack of systematic research. This paper mainly investigated the solidification structure of high-vanadium wear-resistant alloy steel with 5, 8, 10 wt-% vanadium and 2, 5, 10 wt-% chromium, respectively, and the effect of chromium and vanadium additions on the hardness and wear resistance of high-vanadium wear-resistant alloy steel, which will provide guidance for the industrial application of cast high-vanadium alloy steel.

Material and methods

Material preparation

High-vanadium wear-resistant alloy steel used in present study was melted in a 10 kg-capacity medium frequency vacuum induction furnace. The vacuum degree was 10⁻⁴pa. Initial charge materials were clean pig iron and steel scrap. Ferro-alloys such as Fe-51 wt-%V, Fe-62 wt-%Cr, Fe-75 wt-%Si and Fe-78 wt-%Mn were added to a slag-free molten steel so as to minimise the oxidation loss and the slag formation. The melt was subsequently super-heated to 1620°C and transferred into a pre-heated teapot ladle. After removal of any dross and slag, the melt was poured at 1500°C into the metal moulds to produce ingot of ϕ80 mm × 200 mm, followed by air cooling to room temperature.

The metallographic analysis of the specimens was all measured on the centre of ϕ80 mm cross section of the bars in the square of 15 mm × 15 mm. The samples were etched with 4% nital for optical microscopy (OM) examination.⁹ The designed chemical composition of high-vanadium alloy steel was listed in Table 1. The actual composition was listed in Table 2.

Table 1

The designed chemical compositions of high-vanadium wear-resistant alloy steel (wt-%)

No.	C	Si	Mn	Cr	V	P	S	Fe
1	3.0	0.8	0.8	2.0	5.0	< 0.05	< 0.05	Bal.
2	3.0	0.8	0.8	2.0	8.0	< 0.05	< 0.05	Bal.
3	3.0	0.8	0.8	2.0	10.0	< 0.05	< 0.05	Bal.
4	3.0	0.8	0.8	5.0	10.0	< 0.05	< 0.05	Bal.
5	3.0	0.8	0.8	10.0	10.0	< 0.05	< 0.05	Bal.

Table 2

The XRF test chemical compositions (wt-%)

No.	Si	Mn	Cr	V	Fe
1	1.18	0.89	2.46	4.70	Bal.
2	1.00	0.98	2.78	7.62	Bal.
3	1.57	0.88	2.79	8.47	Bal.
4	1.59	1.00	5.96	9.15	Bal.
5	1.39	1.00	9.25	11.01	Bal.

Experimental analysis

The microanalysis examination of the specimens was carried out by using OM, X-ray diffraction (XRD), scanning electron microscope (SEM)and two electron（SEI）image. The SEM used was an S-3400 microscope (Japan) with energy dispersive spectrometer (EDS) attached. XRD was performed on a SHIMADZU Japan XRD-7000 diffractometer with copper kα radiation coupling continuous scanning at 40 kV and 200 mA as an X-ray source. The specimen was scanned in the angular 2θ ranging from 10° to 90° with a step size of 0.2° and a collection time of 10s.

The macro-hardness measurement was done using an HR-150A-type Rockwell-hardness tester. The test load was 150 kg. The micro-hardness of the matrix in high-vanadium wear-resistant alloy was measured by means of an HV-1000 digital display micro Vivtorinox hardness tester with a load of 200gf and the time of 10s. Five indentations were made on each sample under each experimental condition to check reproducibility of the hardness data.

Wear tests were conducted in a conventional ring block abrasion testing machine (M-200) for a load of 60kgf, a wheel rotation rate of 200 rev min⁻¹, and a total of 6000 wheel revolutions. Figure 1 shows a schematic drawing of ring block abrasion testing machine. The specimen sizes were 10 mm × 10 mm × 15 mm. The grinding ring material is GCr15 and its hardness and specifications are 60–62HRC (After quenching) and ϕ40mm × 10 mm respectively.^10,11 Its main chemical compositions were 1.03wt-%C, 1.49wt-%Cr, 0.35wt-%Mn and 0.27wt-%Si. Before the experiment, the specimens were cleaned with alcohol, and the masses of the specimens were measured gravimetrically with 0.1 mg sensitivity. Then, they were assembled into the apparatus. Following a ‘running in’ period, tests were conducted. After one running in test, three tests wear performed on each specimen. The results of wear tests were the average of three tests. The wear resistance of sample is the ratio of wear time/weight loss, and its unit is min mg⁻¹. The weight loss was measured by TG328B balance (Sense is 0.1 mg, and weighing range is 200 g). The worn surface was observed by JSM6510 electron microscope with an EDS.

Results

Solidification process of high-vanadium alloy steel

Figure 2 and Figure 3 are the liquidus projection of Fe-5Cr-V-C, Fe-15Cr-V-C and Fe-5Cr-5W-5Mo-V-C and quasi binary phase diagram of (Fe-5Cr-5Mo-5W-2C)-V given in literature.^12,13 When the content of C is 3wt-%, first, primary vanadium carbides (VCs) formed during solidification process. Then, the VC precipitated gradually with the decrease of temperature, and the content of V in liquid phase decreased. The eutectic reaction （L → (γ +MC)） occurs when the vanadium content is decreased to the point of eutectic composition.^{7–8,12–16} The austenite is not a faceted crystal, but the VC is a typical faceted crystal. Both have a relatively large divorced eutectic tendency. The contents of Cr and other elements in the liquid phase increased gradually because of segregation. L→ (γ +MC+M₇C₃) was reached at the point of ternary eutectic, precipitating carbides MC and M₇C₃.

Solidification microstructure of high-vanadium alloy steel

The as-cast metallurgical structures of high-vanadium wear-resistant alloy steel for different vanadium and chromium content are shown in Fig. 4. The solidification microstructures of high-vanadium wear-resistant alloy steel consist of α-Fe and carbides. The XRD pattern of Fig. 5 shows that when the content of vanadium is less than 5wt-%, the carbides contain VC, M₃C and M₇C₃. When the content of vanadium is greater than 5wt-%, the carbides contain VC and M₇C₃. The micro-hardness of matrix is 500–800 Hv, which indicates that α-Fe in high-vanadium wear-resistant alloy steel may be martensite.¹⁷

Figure 6 presents the results of EDS analysis of high-vanadium wear-resistant alloy steel. It is found that the distribution of vanadium and chromium elements is not homogeneous in as-cast high-vanadium wear-resistant alloy steel. Vanadium is mainly distributed over the carbide, especially MC type carbide.¹⁶ There is also a small amount of vanadium in the matrix and M₇C₃ type eutectic carbides. Chromium is mainly distributed over the M₇C₃ type eutectic carbides, and there a small amount of chromium in the matrix. Figures 6b and f indicate that manganese is mainly distributed over the carbide and matrix. The main reason is that M₇C₃ type carbide is hexagonal crystal system, the lattice parameters are 13.980 Å, 13.980 Å, 4.523 Å, respectively.^18,19 Its octahedral interstice is about 2.73, and the atomic radius of manganese is only 1.79, so the manganese will dissolve into the carbide.

It is found that the formation of different types of carbides depends on the strong carbide forming elements. Vanadium is beneficial to the formation of MC carbide.^16,20–21 Figure 4 is the metallurgical structure of high-vanadium wear-resistant alloy steel. Figure 4a–c shows that the amount of VC increases gradually with the increase of vanadium content when carbon and chromium contents are constant and the morphology of VC is transformed gradually from the strip, short rod to the civilised shape and nodular, and size becomes significantly larger (from 4.5∼12μm to 9∼20μm).²² However, the amount of M₇C₃ type eutectic carbides forming at the grain boundaries decreases. When carbon and vanadium contents are constant, the M₇C₃ type eutectic carbides have been obviously refined and its amount increases gradually with the increase of chromium content.^16,23 Figure 4d shows that the morphology of VC changes rarely with the increase of chromium content. It is still the civilised shape and nodular-based on. The VC amount decreases obviously when chromium content increases further, but the amount of M₇C₃ type eutectic carbides increases obviously. The effect of chromium and vanadium addition on the morphology of matrix is not obvious.

According to the morphology of VC, the area fraction of VC was calculated by means of Photoshop, Pro Plus image and other software. The results (as shown in Fig. 7) reveal that the amount of VC increases with the increase in vanadium content when chromium and carbon contents are constant. The amount of VC gradually reduced with the increase in chromium content when vanadium and carbon contents are constant. Vanadium is a strong carbide element. Vanadium exists in the form of carbides regardless of the high or low carbon content in the alloy steel.^3,24 VC amount increases gradually with the increase of vanadium content. Because the radius of Cr and Fe is similar, Cr is able to displace the iron element in the carbides. This makes structure of the carbides change, forming the M₇C₃ type eutectic carbide.

The morphology of VC was further observed by SEM, as is shown in Fig. 8. The microstructure of the VC can be clearly seen. When carbon and vanadium contents are constant, the amount of VC increases gradually with the increase of vanadium content. The morphology of VC gradually transformed from strip and short rod to variolated, spherical and lumpy, and the size became significantly larger. However, the amount of M7C3 type eutectic carbides forming at the grain boundaries decreases.²⁵ The effect on the formation of VC is not very great with the increase in chromium content when the carbon and vanadium contents are constant. The morphology of VC is still the civilised shape and nodular-based on. But it can be seen that VC particles have been obviously refined. The amount of M₇C₃ type eutectic carbide increases with the increase in chromium content.

Effect of V and Cr on hardness of high-vanadium alloy steel

Effect of vanadium and chromium contents on the macro-hardness of high-vanadium wear-resistant alloy steel is shown in Fig. 9. It can be seen that the change of the hardness of high-vanadium wear-resistant alloy steel is not obvious with the increase in vanadium content, as shown in Fig. 9a. However, the macro-hardness of high-vanadium wear-resistant alloy steel increases gradually with the increase of chromium content when vanadium content is 10 wt-%. The macro-hardness of high-vanadium wear-resistant alloy steel reaches 67.2 HRC when vanadium and chromium contents are 10wt-% and 10wt-% respectively, as shown in Fig. 9b. The effect of vanadium and chromium contents on the micro-hardness of high-vanadium wear-resistant alloy steel is shown in Fig. 10. It can be seen that the change of micro-hardness and macro-hardness are basically the same.

Effect of V and Cr on wear resistance of high-vanadium alloy steel

The effect of vanadium and chromium content on the abrasion resistance was shown in Figs. 11–13. It can be seen that the wear loss was gradually reduced with the increase of vanadium content. Wear resistance (namely ratio of wear time and wear loss) changed from 0.83 min mg⁻¹ to 1.84 min mg⁻¹ and increased 2.23 times, as shown in Fig. 11. When the vanadium content was 10wt-%, the wear loss decreased first and then had an increasing trend. The wear resistance of alloy steel raised first and then had a downward trend. But the change was not obvious, as shown in Fig. 12. Figure 13 shows that the abrasion resistance of high-vanadium alloy steel increased with the increase of vanadium and chromium contents. It is optimal when the vanadium and chromium contents are 10wt-% and 5wt-% respectively.

Discussion

Relation among hardness and chromium and vanadium content

Many studies^16,26–28 show that except the type and morphology of hard phase, the type of matrix has an important influence on the hardness of the high-vanadium wear-resistant alloy steel. Furthermore, the matrix hardness and hard phase quantity also have an important influence on the hardness of high-vanadium wear resistant alloy. It also pointed out that there were other phases in addition to the presence of the eutectic in the high-vanadium wear-resistant alloy steel. The hardness of the specimen (No. 1) with 3wt-%C and 5wt-%V is much larger than the No. 2. According to the principle of carbon balance, the ratio of carbon content and the amount of carbon balance in the No. 1 is larger than the No. 2. Compared with the No. 1, the quantity of strong carbide forming elements is higher in No. 2, and carbon occupied by carbide is higher. So the content of carbon in the martensite matrix will be greatly reduced, which leads to the hardness of the sample No. 2 is lower than No. 1. The macro-hardness increases with the increase of chromium content when vanadium content is 10wt-%. The main reasons are the following: First of all, vanadium as a strong carbide element combined with carbon to form VC. The quantity of M₇C₃ type eutectic carbides increases significantly with the increase of chromium content. Second, chromium in the alloy steel entered into the matrix, and formed α-(Fe, Cr) solid solution in the cooling process, which improves the hardness of the matrix through a solid solution effect. The higher the chromium content, the solid solution strengthening effect is more obvious. Meanwhile, the morphology of the VC is obviously refined because of the addition of chromium. The fine grain strengthening can also improve the hardness.

Analysis on worn surface of cast high-vanadium alloy steel

Figure 14 shows the worn surface morphology of high-vanadium wear-resistant alloy steel. The main wear types of high-vanadium wear-resistant alloy steel are micro-cutting and carbide breaking. The worn surface of No. 1 specimen contains a layer of sheet metal and the upcoming loss of lamellar debris, as shown in Fig. 14a. However, the worn surface of No. 2 specimen appeared deep and wide furrows and pits (seen Fig. 14b). The main reason is that the hardness of No. 2 matrix is lower than of No. 1, and the matrix is not strong enough to support hard phase. This causes the hard phase falling off and forming a pit. Furthermore, this also makes wear surface forming deep furrows. No. 3 specimen appears the furrow which is different between depth and width with a small amount of hard phase particles (seen Fig. 14c). The worn surface of No. 4 specimen appears a few shallow furrows and a large number of prominent black materials (seen Fig. 14d). The worn surface of No. 5 specimen appeared relatively shallow furrows and granular debris (seen Fig. 14e). Figure 9 shows the hardness gradually increased with the increase in chromium content, which played a good supporting role for hard phase. The hard phase is firmly combined with the matrix and cannot scale off easily.

Relationship among composition, microstructure, hardness and wear resistance of as-cast high-vanadium alloy steel

The wear resistance of the as-cast high-vanadium wear-resistant alloy steel is closely related to vanadium and chromium contents and the amount, shape, distribution and hardness of VC and M₇C₃ type eutectic carbides.²⁹ Many researches show that the wear resistance of metal materials is mainly determined by the hardness when the hardness is below HRC57, and the wear resistance is mainly determined by the quantity, shape, distribution of VC and matrix structure when the hardness is over HRC57.³⁰ Due to the addition of chromium, it may also be influenced by the coaction of the VC and M₇C₃ eutectic carbide. From the above analysis we can know that as chromium and carbon content are constant, the change of the hardness is not obvious with the increasing in vanadium content. However, Fig. 8 shows the size of hard phase VC became large gradually. By means of Photoshop, we have measured that the size of the VC in No. 2 and No. 3 is about 4.5∼12μm and 9∼20μm, respectively. Figure 8 shows the quantity of VC increased gradually, while the quantity of M₇C₃ type eutectic carbides gradually reduced. The enhanced phase VC is superior to the enhanced phase M₇C₃ in the hardness and morphology, and which is dispersed in the matrix, and significantly improves wear resistance.³¹ Therefore, the wear resistance of alloy steel is gradually increased with the increase of vanadium content. In the case of vanadium and carbon content unchanged, the wear resistance of alloy steel first rise and then fall with the increase in chromium content. The wear resistance of No. 4 sample is the best. Because its hardness is HRC57, and hardness is moderate. It is effective to fix and support carbide in the process of wear, and outstanding high hardness carbide can effectively resist the wear. With the increase in chromium content, the VC was significantly refined, the stress concentration is small, and the carbide is not easy to break.³² So the wear resistance is the best.

The wear resistance decreases when the chromium content increases further. The reason is that when the hardness is HRC67 (greater than HRC57), the wear resistance is mainly determined by the number, morphology and distribution of VC and M₇C₃ type eutectic carbide. The M₇C₃ type eutectic carbides increases gradually and the quantity of VC decreases gradually with the increase in the chromium content. M₇C₃ type eutectic carbides with rod-shaped and strip shape is more likely to produce fragmentation compared with a round lump VC when the stress state is the same. Furrows can also be seen on the worn surface of high-vanadium wear-resistant alloy steel. Because the hardness of shedding VC and M₇C₃ type eutectic carbide is much higher than the matrix, VC and M₇C₃ type eutectic carbide enter into the surface of the sample under greater pressure, and plough the material under shear stress.

Conclusions

The carbides in the low chromium high-vanadium wear-resistant alloy steel are mainly VC, and vanadium element is mainly distributed over the VC. The content of vanadium in the matrix and M₇C₃ type eutectic carbides is little.

When carbon and chromium contents are constant, the quantity of VC (VC) in high-vanadium alloy steel increases and the quantity of M₇C₃ type eutectic carbides decreases obviously with the increase of vanadium content. The morphology of VC changes from strip and short rod to variolated, spherical and lumpy-based.

VC particles have been obviously refined and the amount of M₇C₃ type eutectic carbide increases with the increase of chromium content. The increase of chromium content leads to an obvious increase in the hardness of the steel.

The wear resistance of high-vanadium alloy steel increases with the increase of vanadium content when chromium and carbon content are constant. The change of wear resistance of high-vanadium wear-resistant alloy steel is not obvious with the increase of chromium content. The wear resistance is the best when the contents of vanadium and chromium are 10 wt-% and 5 wt-% respectively.

Footnotes

Acknowledgement

The authors appreciate the financial support for this work from the Natural Science Foundation of China under Grants No 51475005.

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