Tribology International 32 (1999) 131136 [Link].

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Microstructure and tribological behaviour of nitrocarburizingquenching duplex treated steel

a,b,*

, S.R. Ge a, Q.J. Xue

School of Mechatronic Engineering, China University of Mining and Technology, Xuzhou 221008, Jiangsu, Peoples Republic of China b Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, Peoples Republic of China Received 24 September 1997; received in revised form 30 March 1999; accepted 22 April 1999

Abstract This paper explores salt bath nitrocarburizing and nitrocarburizing-quenching duplex treatment technologies. For comparison, a quenching-tempering treatment was also conducted. By means of metallographic examination, microhardness tests and X-ray diffraction analysis, the microstructures, phase structures, surface hardnesses and hardness proles of 1045 steel treated by several techniques were investigated. The ball-on-block and ring-on-block apparatuses were employed to investigate the friction coefcient and wear-resistance respectively. The surface roughness was also measured by a prolometer. The experimental results indicate that a higher sub-surface hardness and a superior hardness prole are obtained by nitrocarburizing-quenching duplex process. This in turn improves the wear-resistance and fatigue strength, although the surface hardness is somewhat lower compared with that obtained by nitrocarburizing. It also demonstrates that the -phase formed on the steel surface has signicant effects on reducing friction and improving wear-resistance. X-ray diffraction analysis shows that the phases at the nitrocarburized specimen surface are mainly -compound [Fe3(N,C)] and small amounts of Fe4N( ) and Fe23(N,C). While the phases at the nitrocarburized-quenched specimen surface are very different from those at the nitrocarburized specimen. In this case, the -compound has decomposed almost completely and the nitrogen and carbon diffuse to the -Fe at the temperature of quenching to form the supersaturated solid solution which will become martensite containing nitrogen and carbon along with retained austenite after subsequent water cooling. 1999 Published by Elsevier Science Ltd. All rights reserved.
Keywords: Nitrocarburizing; Quenching; Friction and wear; Duplex treatments

1. Introduction Recently surface modication is highly desirable to solve the problems involving friction and wear. Nitrocarburizing is a thermochemical process that diffuses nitrogen and carbon into the surface of ferrous materials, which upgrades the surface hardness of treated workpieces and yields great improvements in wear and fatigue properties [14]. Compared with conventional surface hardening processes, nitrocarburizing has many advantages such as lower treatment temperature and shorter treatment time, high degree of shape and dimensional stability, process safety and reproducibility. Because of its process characteristics and broad range

* Corresponding author.

of applications, nitrocarburizing is widely applied in the mechanical engineering industry to improve the friction, wear and fatigue properties of steel and cast-iron parts. The numerous process variants available to users today are an indication of the importance of nitrocarburizing in modern heat treatment technology. In the 1980s, new treatments or treatments including special operations (oxidation, polishing, impregnation, etc.) were developed to simultaneously improve the mechanical properties and corrosion resistance of nitrocarburized layers [57]. In addition, duplex treatments combined with nitrocarburizing have been reported [811], especially the combination of gas nitriding or gaseous nitrocarburizing with quenching. However, the liquid (salt bath) nitrocarburizing-quenching duplex treatment is rarely reported. This paper explores the uses of salt bath nitrocarburizingquenching duplex treatments as surface modication processes to increase the sliding wear performance of 1045 steel.

0301-679X/99/$ - see front matter. 1999 Published by Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 1 - 6 7 9 X ( 9 9 ) 0 0 0 2 4 - 9

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2. Experimental details 2.1. Materials and techniques The substrate material used in this study was 1045 steel with the following composition (wt%): 0.47C, 0.24Si, 0.65Mn. The test specimens were thoroughly hardened and tempered to a hardness of about 2023 HRC and ground to nal dimensions. Nitrocarburizing was performed in a 3 kW salt bath furnace. A small hole (3 mm in diameter) was drilled in each specimen so that it could be hung at the end of an iron wire to facilitate loading into the furnace. As usual, when treated in a salt bath, the specimens are rst preheated in air to about 350C for 1 hour. During the salt bath nitrocarburizing process, a reaction takes place between the salt melt and the specimens treated so that nitrogen and carbon are absorbed and diffuse into the surface of the specimens. The specimens requiring quenching are protected by anti-oxidative coatings to avoid oxidation and decarbonization when heated. Before the friction and wear tests, all the specimens were cleaned ultrasonically. The treatment parameters and detailed processing sequences for several treatments are indicated in Table 1 and Fig. 1 respectively. 2.2. Apparatuses and test procedures The friction coefcient test was conducted on a dynamic precision friction measurement apparatus (Kagadu Co. Ltd., Japan) with a ball-on-block conguration and a testing load of 3 N. The ball specimen was made of 52100 bearing steel with a hardness about 850 HV. It moved reciprocally at a speed of 1.6710 3 m/s 100 times with a sliding amplitude of 8 mm and a stationary block. The sliding wear test was conducted on a MRH-3 ring-on-block apparatus under both lubricated and unlubricated conditions. The ring was made of 52100 bearing steel with a diameter of 49.3 mm and a hardness about 5963 HRC. Under lubricated condition, the testing load was 600 N, the speed 500 rpm and the time 30 minutes. The wear volume was measured every 5 minutes and the specimen was continuously lubricated by liquid parafn at a constant drip rate of 2025 drops
Table 1 Treatment techniques Specimen no. N1 N2 N3 Treatment parameters 850C 200C 570C 570C 840C 200C (0.5 (2.0 (1.5 (1.5 (0.5 (2.0 h) h) h) h) h) h) quenched (water cooled) + tempered nitrocarburized + air cooled nitrocarburized + air cooled quenched (water cooled) + tempered

per minute. Under unlubricated condition, the testing load was 100 N, the speed 200 rpm and the time 10 minutes. The wear volume was measured every 2 minutes. The wear prole was measured by a prolometer and the wear volume was calculated by the following equation:

1 bl r 2

r2

b 2

(1)

where v is wear volume, b and l are the width and the length of wear scar respectively and r is the radius of ring. All the experimental data are averages from three tests. 3. Results and discussion 3.1. Metallography Optical microscopy was performed with a Neophot-1 microscope (Carl Zeiss, Jena). To avoid curvature of the surface of the cross-sections near the specimen edges owing to grinding and mechanical polishing, segments of the nitrocarburized and nitrocarburized-quenched specimens were provided with a nickel sheet protection mechanically. Cross-sections of the specimens were etched in a 4% solution of nitric acid in ethanol. 3.1.1. Microstructures Fig. 2 illustrates the typical microstructures of crosssections of specimens. Metallographic examination of nitrocarburized specimens indicates clearly that the outer compound layer exists as a slightly etched zone followed by the diffusion zone thereunder. The ferrite and cementite in the core remain unchanged [see Fig. 2(a)]. However, microscopic study reveals that the surface of the nitrocarburized-quenched specimen is very different from that observed on the nitrocarburized specimen. It is clear that great changes have taken place in the microstructures of the surface and core. The compound layer produced by nitrocarburizing has decomposed almost completely and the outer layer comprises now the martensite containing nitrogen and carbon along with retained austenite, the original diffusion zone changes into ne acicular martensite and retained austenite and the core is mixed martensite. Obviously, grain renement is observed [see Fig. 2(b)]. 3.1.2. Microstructure changes of nitrocarburizing quenching duplex treatment Nitrocarburizingquenching duplex treatment is a new kind of heat treatment technique, in which nitrogen and

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Fig. 1.

Processing sequences of three treatments.

of both nitrocarburizing in the surface and quenching in the core, which ensures that specimens achieve a higher surface hardness and a superior hardness prole while maintaining better mechanical properties. 3.2. Diffractometry and phase identication X-ray diffraction analysis by use of Cu-K radiation was undertaken with D/Max-3B diffractometry to examine the phase on specimen surfaces after various treatments. The tube voltage and current were 30 kV and 20 mA respectively. 3.2.1. Phase identication The X-ray diffraction proles are presented in Fig. 3. The test results show that the nitrocarburized specimen surfaces are composed chiey of -compound [Fe3(N,C)] and small amounts of Fe4N( ) and Fe23(N,C) [see Fig. 3(a)]. Because the Fe4N( ) and Fe23(N,C) are mainly distributed in the inner part of the compound layer, only one diffraction peak appears for each phase and its strength is weak. While in the diffraction prole of nitrocarburized-quenched specimen, only the (101) peak of the -phase remains and its strength is much lower. Peaks from other crystal planes disappear. At the same time, diffraction peaks of -Fe grow [see Fig. 3(b)]. This proves that the -compound has decomposed almost completely at the temperature of quenching and the nitrogen and carbon diffuse into the -Fe, thus forming a supersaturated solid solution. After subsequent water

Fig. 2. Optical micrograph of cross-sections of variously treated specimens (400).

carbon diffuse into the surface of ferrous metals to form a compound layer mainly composed of carbonitride and a diffusion zone. When the nitrocarburized specimen is heated to the austenite region thereafter, the compound layer begins to decompose and the nitrogen and carbon penetrate into the austenite. After cooling in water, martensite containing nitrogen and carbon is achieved, and it is much ner than that formed by normal quenching of unnitrocarburized 1045 steel. Meanwhile, because of further diffusion of nitrogen and carbon into the matrix, the concentration gradient becomes gentle. The nitrocarburizingquenching treatment possesses characteristics

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Fig. 3.

X-ray diffraction proles after various treatments.

cooling, this supersaturated solid solution becomes martensite containing nitrogen and carbon. 3.2.2. Phase change process of nitrocaburizing quenching duplex treatment As mentioned above, the surface layer of nitrocarburized specimen is composed of a compound layer and a diffusion zone. When the nitrocarburized specimen is heated to the eutectoid temperature (about 590C), austenite begins to form between the compound layer and the diffusion zone and its thickness increases with rising temperature. When the temperature reaches about 650C, the -compound starts to decompose; a small portion of the nitrogen atoms diffuse into the inner part of the steel and a major portion of the nitrogen atoms combine into N2, thus forming the porosity. At a temperature of about 750C the -compound has decomposed almost completely. 3.3. Hardness of case hardened layer Hardness distributions from the surface layers into the bulk materials were investigated at a load of 100 grams by use of a micro-Vickers hardness tester. Comparative surface hardnesses and hardness proles are presented in Fig. 4. In cross-sections of the nitrocarburizedquenched

specimen, the hardness gradually increased, reached a maximum value in the sub-surface layer about 0.04 mm from the surface and then decreased with a gentle slope. Nevertheless, in the nitrocarburized specimen, the hardness decreased from a maximum value at the surface layers to inner portion of the specimen. That is to say, the surface hardness of the nitrocarburizedquenched specimen is comparatively low. The lower surface hardness of the nitrocarburizedquenched specimen is related to the decrease of nitrogen and carbon contents and the increase of retained austenite on the one hand and to the porosity produced near the specimen surface owing to decomposition of the compound layer on the other hand during the quenching process. As is well known, porosity in nitrocarburized specimens decreases the hardness. Moreover, the sub-surface hardness and hardness prole of the nitrocarburizedquenched specimen are obviously higher than in the nitrocarburized specimen. This is due to the decomposition of the -compound and the further diffusion of nitrogen and carbon into the matrix, thus forming a supersaturated solid solution which will change into acicular martensite containing nitrogen and carbon after a subsequent quenching treatment. Some researchers [12] have reported that the fatigue failure mode of case hardened specimens is the forming of cracks in the sub-surface followed by surface spalling. The sub-surface of the quenchednitrocarburized specimen possesses higher hardness and stress analysis indicates that the sub-surface is in the region of greatest compression, which is benecial for preventing the formation of cracks, increasing contact fatigue strength and prolonging the service life of components. 3.4. Surface roughness Good polishability is essential for high quality manufacturing of machine parts. As mentioned above, salt bath nitrocarburizing usually builds up a compound layer approximately 1020 m thick on the surface of ferrous components. This layer consists chiey of -phase iron carbonitride beneath which is a nitrogen and carbon rich diffusion zone. It is an established fact that an increase

Fig. 4.

Hardness proles after various treatments.

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in roughness is to be expected during nitrocarburizing, independent of the process used. Based on this viewpoint, the inuence of several treatments on the surface roughness has been investigated. The results are indicated in Fig. 5. In our tests, the ground specimens had surface roughness of Ra=0.41 m. After three treatments, surface roughness increased to Ra=0.68 m, 0.80 m and 0.85 m for quenchingtempering, nitrocarburizing and nitrocarburizingquenching respectively. But with respect to the service conditions of machine parts, these changes in surface roughness were within the usual range. Wahl [5] reported that improving the level of surface nish prior to nitrocarburizing does not signicantly affect the roughness level after treatment, which indicates that the surface roughness after nitrocarburizing treatment is more dependent on the surface topography of the compound layer than on the initial surface nish. 3.5. Friction coefcient Friction tests on a series of blocks subject to several treatments were carried out under lubricated and unlubricated conditions. The test results are presented in Fig. 6. It can be seen that under both conditions, blocks nitrocarburized and nitrocarburizedquenched were found to have lower friction coefcient compared with quenched tempered specimens. This indicates that the -phase produced on the specimen has a signicant effect on reducing friction. As is well known, the friction coefcient is one of the most important characteristics of tribology. Adhesive wear theory suggests that the friction coefcient can be expressed by the equation m=tf /sy when there exists a lm on the specimen surfaces. That is to say, the friction coefcient is proportional to the shear strength of the interface tf and inversely to the compression strength of the metal matrix. Therefore, the smaller the tf and the larger the sy, the smaller the friction coefcient. It is generally believed that thermochemical treatments

Fig. 6.

Friction coefcient after various treatments.

strengthen the metal matrix by the diffusion zone thus increasing the sy on the one hand and reducing the tf on the other hand because of the intermetallic structure of the surface compound layer. The combination of these two factors could decrease the friction coefcient signicantly. In addition, it is found that under lubricated and unlubricated conditions, the friction coefcients of nitrocarburized and nitrocarburizedquenched specimens have no apparent difference. This means that lubrication has no signicant effect on reducing the friction coefcients of nitrocarburized and nitrocarburizedquenched specimens. 3.6. Wear-resistance The experimental results for lubricated and unlubricated wear tests are indicated in Figs. 7 and 8. It is found that nitrocarburizing can improve the wear-resistance signicantly under lubricated and unlubricated conditions due to the intermetallic structure, higher hardness and the lower friction coefcient of the compound layer.

Fig. 5.

Surface roughness after various treatments.

Fig. 7.

Wear volumes of various treatments under lubrication.

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burizedquenched specimen surface has decomposed almost completely and the outer layer is composed of martensite containing nitrogen and carbon along with retained austenite while that (the compound layer) of the nitrocarburized specimen is mainly composed of -compound and a small amount of Fe4N and Fe23N. 3. A higher sub-surface hardness and a superior hardness prole are obtained by nitrocarburizingquenching duplex processes which improve wear-resistance and fatigue strength.

References
Fig. 8. Wear volumes of various treatments under unlubrication. [1] Wahl G. Component properties after salt bath nitrocarburizing by Tufftride process. Heat Treatment of Metals 1995;3:6573. [2] Dawes C. Nitrocarburizing and its inuence on design in the automotive sector. Heat Treatment of Metals 1991;18(1):1930. [3] Qiang YE, Ge SR, Xue QJ. Microstructure and tribological properties of two-step nitrocarburized steel 45. Wear 1998;218:2326. [4] Qiang YH, Ge SR, Xue QJ. Sliding wear properties of salt bath austenitic nitrocarburized steel 1045. (in Chinese). Materials Protection 1998;31(3):259. [5] Wahl G, Etchells IV. QPQ surface heat treatment for corrosion resistance. Heat Treatment 1984;84:29.17. The Metals Society, London. [6] Wahl G. Modied process parameter in nitrocarburizing improve component properties and give greater economy. Materials Science Forum 1992;102104:285300. [7] Dawes C, Tranter DF. Nitrotec surface treatment. Heat Treatment 1984;84:28.18. The Metals Society, London. [8] Davies DP. Duplex hardness: advanced surface treatment technique combining nitriding and carburising. Heat Treatment of Metals 1991;18(4):97103. [9] Guo HX. Nitrocarburizing duplex strengthening (in Chinese). Heat Treatment of Metals 1995;3:35. [10] Wang BS, Feng MW. Nitrocarburizingquenching duplex treatment of steel 9SiCr (in Chinese). Heat Treatment of Metals 1996;8:389. [11] Jiang XH, Huaug YF. Applications of nitrocarburizingquenching duplex treatment (in Chinese). Heat Treatment of Metals 1995;9:267. [12] Braze JF. Rolling contact fatigue and sliding wear performance of ferritic nitrocarburized M-50 steel. Tribology Transactions 1992;35:8997.

Excellent sliding and running properties are well-established advantages of nitrocarburized components. While after nitrocarburizedquenched treatment, the wear resistance is improved even further because of the duplex strengthening of nitrocarburizing and quenching. A striking feature of nitrocarburizedquenched specimens is the higher sub-surface hardness and hardness prole of the diffusion zone. This is a major factor to promote wear resistance.

4. Conclusion On the basis of the results obtained in the course of the study on several nitrocarburizing technologies for 1045 steel, the main conclusions can be deduced as follows: 1. The results of this work conrm that the -phase produced on the specimen after nitrocarburizing has a signicant effect on reducing friction and improving the wear-resistance. 2. The phase structure of nitrocarburizedquenched specimens is different from that of ferritic nitrocarburized specimens. The compound layer on the nitrocar-