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A STUDY OF ACTIVE SCREEN PLASMA NITRIDING

C. X. Li, T. Bell, and H. Dong


A ctive screen plasma nitriding ( ASPN) is an emerging surface engineering technology that oVers many advantages over the conventional dc plasma nitriding ( DCPN) . In this work, samples of a low alloy steel 722M 24 were A S plasma nitrided with various gas compositions and using diVerent active screen setups. Normal dc plasma nitriding was also performed under similar conditions for comparison. T he nitrided samples were characterised with a variety of analytical techniques, including optical microscopy and SEM for morphological and structural ex amination, X R D for phase identi cation, and microhardness testing for surface hardness and hardness pro le measurements. It has been shown that A SPN can achieve a similar INTRODUCTION Plasma nitriding using glow discharge technology has been widely accepted in industry over the past thirty years. This relatively new nitriding process is carried out in a vacuum, where high voltage electrical potential is applied to the workpiece (cathode) and the furnace wall (anode) to form plasma, through which the active nitriding species are transferred to the sample surface.1 It is well known that plasma nitriding oVers many advantages over traditional gas nitriding and bath nitriding, particularly, in terms of reduced gas consumption, reduced energy consumption, and the complete removal of any environmental hazard.2 Nonetheless, the rapid development and the uptake of the dc plasma nitriding technology into industrial surface engineering have recently been slowed down.3 In the conventional dc system, the components to be treated are subject to a high cathodic potential, so that plasma forms directly on the component surface to provide the active nitriding species and to heat the components. While this is eYcient for heating and treating relatively simple shapes or small loads, the normal dc technique has inherent shortcomings, which cannot meet the demands in many situations. DiYculties in maintaining a uniform chamber temperature, particularly in full workloads of components with varied dimensions, damage caused to parts by arcing, the edging eVect and the hollow cathode eVect in dc plasma nitriding have been contributory factors in this.3 , 4 To overcome these common problems associated with conventional dc plasma nitriding, many eVorts have been made in the past few years. One of the recent steps forward in this was the invention of the active screen (AS) plasma nitriding technology.5 In such a novel nitriding process, the entire workload is surrounded by a large metal screen or cage, on which, a high voltage cathodic potential is applied (so that the term active screen is used). The worktable and the parts to be treated are placed in a oating potential or subjected to a relative lower bias voltage, e.g. 100 to 200 V. Therefore, it is on the active screen, rather than on the component surface, that
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nitriding eVect as the normal DCPN but without the common problems associated with dc nitriding such as the arcing surface damage, the edging eVect, and the hollow cathode eVect. T he mechanism of nitrogen mass transfer in A S plasma nitriding has been investigated, and a modi ed sputtering deposition model has been used to ex plain the A S plasma nitriding ex perimental results. SE /427 T he authors are in the School of M etallurgy and Materials, T he University of Birmingham, Birmingham B15 2T T , UK ( c.x .li@bham.ac.uk). M anuscript received 17 December 2001; accepted 19 A pril 2002.
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the plasma is formed. The plasma heats up the active screen, and radiation from the screen provides the heat that brings components to the required temperature for treatment. The plasma formed on the screen also contains a mixture of ions, electrons, and other active nitriding species, which are then encouraged to ow through the screen and over the workload by a specially designed gas ow. As such, very complex shaped components can be treated, producing uniform modi ed layers on all parts of diVerent geometry and size in a heavily loaded chamber. Since plasma is not formed on the component surface, the arcing damage and the edge eVect are eliminated.3 In the present work, samples of a low alloy steel 722M24 were plasma nitrided using the active screen plasma nitriding technique. Experiments were carried out in a normal dc nitriding unit with the addition of a prototype active screen setup. The aims of the work were to compare the plasma nitriding response of the low alloy steel with two diVerent nitriding processes of ASPN and DCPN, and to investigate the mechanism of nitrogen mass transfer involved in the AS plasma nitriding. EXPERIMENTAL Materials The material used in this study was a hardened, tempered low alloy steel 722M24 with an average substrate hardness of 310 HV01. The chemical composition of the steel was Fe026C344Cr054Mo 048Mn (wt-%). Samples were cut from 25 mm diameter bar to discs of 8 mm thickness. Two at surfaces of the discs were wet ground with SiC papers from 240 grit down to 1200 grit. The samples were cleaned in soapy water and then acetone before nitriding. Nitriding experiment Nitriding was carried out in a dc plasma nitriding unit (40 kW Klo ckner), which comprises a sealed chamber, a vacuum system, a dc power supply system, a gas supply system, and a temperature measurement and control system. The nitriding
DOI 10.1179/026708401225005250

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not subject to any applied electrical potential, and consequently, there was no plasma formed directly on the sample surface. The distance between the sample ( at) surface and the top lid was 12 mm. The nearest distance from the mesh cylinder to the sample edge was about 28 mm. Heating was achieved by radiation from the active screen, including the cylinder mesh and the top lid. Temperature was measured on a dummy sample, which was also isolated and placed on the table in a symmetrical position to the samples to be treated. AS nitriding procedures were the same as normal dc nitriding. All the experiments were performed at 500C for 5 h with a chamber pressure of 500 Pa. Three gas compositions were used: 25%N2 + 75%H2 , 25%N2 + 75%Ar, and 100%N2 . The heating rate was controlled to 500 K h 1 .
1: sample; 2: dummy sample for temperature control; 3: isolated sample table; 4: mesh cylinder, cathode; 5: top lid, cathode; 6: furnace wall, anode

Schematic diagram showing active screen plasma nitriding setup

process and nitriding parameters were controlled by a microprocessor incorporated in the unit. For dc nitriding, the samples to be treated were directly placed on the cathodic working table as normal. The furnace wall was connected to the dc source as the anode. Temperatures were measured by a thermocouple inserted into a hole of 3 mm diameter in a dummy sample. The process began with evacuating the chamber, back lling with treatment gases, heating the samples up to the treatment temperature using glow discharge on the sample, maintaining the temperature for a set time, and nally cooling down to room temperature in the furnace. Active screen (AS) plasma nitriding was carried out in the same dc nitriding furnace but a mesh cylinder of 120 mm diameter and 130 mm height was used to serve as part of the active screen. The cylinder was made of 07 mm thick perforated steel sheet, which had uniformly distributed round holes of 8 mm diameter. The centre to centre distance between each neighbouring hole was 92 mm, accordingly, the open area fraction of the mesh was 68%. As shown in a schematic diagram in Fig. 1, the cylinder was placed on the dc nitriding worktable and connected to the cathodic potential. It had a removable top lid made of low carbon steel plate of 1 mm thick. In a later stage of the test, the top lid was changed to one of the following materials and setup: (i) same mesh sheet as the cylinder (ii) without a lid (iii) copper plate lid (iv) titanium plate lid. The cylinder and the lid were well cleaned by chemical etching in diluted HCl solution, mechanical grinding with 1200 SiC paper, and ultrasonic cleaning in soapy water and then in acetone. Before the nitriding experiment, the active screen (cylinder and the lid) was sputter cleaned and pre-nitrided inside the nitriding chamber to eliminate the residual contaminate on the surface and to prevent arcing. A sample table of 100 mm diameter was placed inside the active screen but isolated from the cathode potential. As a result, the samples on this table were

Characterisation of plasma nitrided samples Various techniques have been used to characterise the structures and properties of the plasma nitrided steel. Microstructure analysis was carried out using both optical microscopy (OM ) and scanning electron microscopy (SEM). Nitrogen depth pro les were measured with a Leco GDS-750 QDP glow discharge spectrometer. Phase constituents on the nitrided surface were analysed with an Xpert Philips X-ray di Vractometer using Cu K a radiation. Surface microhardness (HV) and microhardness depth pro les were measured with a Mitutoyo MVK-H microhardness tester at a load of 01 kg. RESULTS AS plasma nitriding response Samples of 722M24 steel were plasma nitrided at 500C for 5 h in 500 Pa 25%N2 + 75%H2 gases using AS nitriding and normal dc nitriding techniques. A mesh cylinder and a steel plate top lid, as described previously, were used as the active screen in AS nitriding. After treatment, the appearance of the samples was examined visually. It was found that the dc nitrided sample had the well established nonuniform surface appearance associated with dc nitriding, i.e. a ring with a diVerent colour from the central area existed along the edge of the at sample surface. The width of the discoloured ring was about 1 to 2 mm on the disc of 25 mm diameter. This nonuniform appearance has been a common problem for normal dc plasma nitriding and has been explained in terms of the non-uniform sputtering on the sample surface.6 In comparison, the AS nitrided sample had a uniform matt grey surface through the entire sample surface. No edging discoloration was found. Microstructures of nitrided samples were examined on cross-sectioned and etched samples under optical and scanning electron microscopes. Despite the di Verence in working principles, the ASPN and DCPN nitriding processes produced identical case structures: a compound layer on the surface and a nitrogen diVusion layer underneath. This is shown in the optical microstructures shown in Fig. 2, and a SEM microstructure in Fig. 3. The compound layer in the AS nitrided sample is slightly thicker than that in dc nitrided sample but it is equally dense and could not be etched by the diluted nital solution. The di Vusion zone revealed the morphology of the typical lath martensite structure surrounded by the grain boundary nitride and dispersed with ne nitrides.
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4 N itrogen distribution in near surface of A S and dc plasma nitrided 722M 24 steel

Optical microstructures of dc and A S plasma nitrided 722M 24 steel: 500 C for 5 h in 25%N +75%H 2 2

Indeed, very little microstructural variation was observed between the AS and dc nitrided samples. Nitrogen concentrations in the nitrided surface were measured with a glow discharge spectrometer (Leco GDS 750). Figure 4 shows that AS nitriding produced a similar nitrogen depth pro le as dc nitriding. Both are characterised by an initial high nitrogen region near the surface and gradually reduced nitrogen regions underneath. However, a signi cant diVerence exists in that the nitrogen content in the AS nitrided surface is higher than that in the dc nitrided surface up to a depth of about 6 mm. It is known that the high nitrogen concentration is related to the presence of iron nitrides of c -Fe4 N

and/or e-Fe2 3 N in the compound layer. The lower nitride c -Fe4 N has a theoretical nitrogen content of 59 wt-% and the higher nitride e-Fe2 3 N has a nitrogen content of 77111 wt-%. In principle, the thickness of, and the phase constituents in the compound layer can be estimated from the nitrogen pro les. In Fig. 4, the slightly deeper high nitrogen pro le in the ASPN sample suggests that AS nitriding produced a slightly thicker compound layer. This is in agreement with the microscopy observations as shown in Fig. 2. The higher nitrogen content in the AS nitrided compound layer suggests it may contain more e phase, which has been con rmed by XRD results as shown below. X-ray diVraction analysis was performed on the nitrided surface with a Philips X-ray diVractometer using Cu K a radiation (l = 0154 nm). The scanning angle (2h ) was varied from 30 to 100 and the scanning rate was 002 deg s 1 . The XRD patterns shown in Fig. 5 indicate that both ASPN and DCPN treated sample surfaces consist of a mixed structure of c -Fe4 N and e-Fe2 3 N. However, the relative peak intensities of the two phases are diVerent in two samples. The comparison becomes easier by just

SEM microstructure of AS nitrided sample: 500C for 5 h in 25%N + 75%H 2 2


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5 X R D patterns of a dc and b A S plasma nitrided 722M 24 sample surface

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H ardness pro les of a dc and b A S nitrided samples

8 E Vect of gas composition on surface hardness of A S and dc nitrided samples

considering the relative intensities of the rst strong peak for each phase, i.e. e (101) and c (200). Figure 5a shows the peak of e(101) is slightly lower than that of c (200) in the DCPN sample, and their relative intensity, as expressed by I e(1 0 1 ) / I c ( 2 0 0 ) , is 097. This indicates that slightly more or at least a comparable amount of c phase is present in the compound layer of dc nitrided sample. In comparison, Fig. 5b shows that the peak of c (200) was reduced to a much lower level in the AS nitrided surface; the relative intensity of I e(1 0 1 ) / I c (2 0 0 ) increased to 597, suggesting that the fraction of e phase in the AS nitrided compound layer is much higher. It appears that the AS plasma nitriding process facilitated the formation of e phase in this test. Regardless of the above diVerences in nitrogen concentration and phase constituents, the hardness values measured on the sample surfaces were identical. The average surface hardness of ten tests (for each sample) was 1025 HV01 for ASPN and 1038 HV01 for DCPN treated samples. Figure 6 shows that the hardness pro les and the case depth produced by two nitriding processes practically have little diVerence. EV ect of nitriding gases To study the eVect of nitriding gas on the AS nitriding response, two gas mixtures, 25%N2 + 75%Ar and 100%N2 , were used for nitriding to replace the normal gases of 25%N2 + 75% H2 . The active screen setup and all the other processing conditions, e.g. chamber pressure (500 Pa), nitriding temperature (500C), nitriding time (5 h), and processing pro-

cedures were kept the same. Glow discharge spectrometry (GDS) analysis showed that AS nitriding using N 2 + Ar produced a nitrogen pro le similar to that with a normal gas of N2 + H2 (Fig. 7). XRD results showed that the compound layer was also dominated with e phase, the relative intensity of e(101) and c (200), i.e. I e(1 0 1 ) / I c (2 0 0 ) , was 716. Microstructural observations showed that the compound layer thickness was little changed by using N2 + Ar. Hardness measured on the sample surface is slightly lower than AS nitriding with N2 + H2 (Fig. 8), but the hardness measured in the diVusion zone is almost the same (Fig. 9). It can be seen that AS nitriding using N2 + Ar can achieve a similar hardening eVect as using N2 + H2 . However, when pure nitrogen was used, nitrogen di Vused only to a very shallow depth below the surface, and the nitrogen content was also much lower (Fig. 7). No compound layer could be observed on the surface under a microscope. The surface hardness (HV01) of the AS nitrided sample was nearly the same as the untreated steel (Fig. 8). No hardening eVect was found below the surface either. Therefore, AS nitriding using pure nitrogen did not produce any noticeable hardening in this test. EVect of active screen setup The eVect of active screen setup on AS nitriding response was investigated by using diV erent top lid materials and diVerent lid setups, including with mesh lid, without lid, with copper plate lid, and with titanium plate lid. The mesh cylinder and the sample arrangement were kept the same, and the nitriding processing parameters were 500 Pa chamber pressure,

E Vect of gas composition on nitrogen distribution in plasma nitrided surface

9 E Vect of gas composition on hardness pro le of A S nitrided samples


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Surface hardness of samples nitrided with various active screen ( top lid) setups: A SP iron plate lid; A SM iron mesh; A SO-bl without top lid ( dark area) ; A SO-wh without top lid ( white area) ; A ST i T i top lid; A SCu Cu top lid

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N itrogen distribution in samples A S nitrided with iron plate (A SP) and without top lid (A SO )

25%N2 + 75%H2 gas, 500C, and 5 h. The results are summarised below. Nitriding with mesh lid The top steel plate was changed to a mesh lid, which was made from the same perforated steel sheet as the mesh cylinder. Characterisation results showed that using mesh lid (ASM) can produce a similar nitriding eVect as that with a steel plate (ASP), this included a similar average surface hardness on the surface (Fig. 10) and a similar hardness pro le in the nitrided case (Fig. 11). The compound layer on the surface was also dominated with e phase, the relative intensity of I e(1 0 1 ) / I c (2 0 0 ) was 325, which was lower than 597 for ASPN in 25N2 + 75H2 and 716 for ASPN in 25N2 + 75Ar samples. Nitriding without top lid When the upper lid was removed, AS nitriding produced a non-uniform surface, which could be seen visually. Toward the edge and near the mesh cylinder, the sample surface was dark grey, which had a similar matt grey appearance as that found on samples nitrided with a steel mesh (ASM) or a steel plate (ASP) top lid. The dark grey colour gradually faded away with an increase in the distance from the mesh cylinder, and towards the centre the samples surface more or less retained the original metallic sheen, where the original grinding marks could be clearly seen. For convenience, the area with dark (or black)

colour is indicated by ASO-bl, and the area with metallic sheen (white) by ASO-wh. Although the surface hardness (HV01) did not vary much within the two distinct areas (Fig. 10), the nitrogen concentrations were indeed much lower and shallower (Fig. 12). Corresponding to the non-uniform appearance and the non-uniform nitrogen distribution, the hardening in the diVusion zone was also non-uniform. Figure 11 shows that the black area (ASO-bl ) had a similar hardness pro le compared to samples nitrided using steel plate (ASP) or mesh (ASM). In contrast, the white area (ASO-wh) had a lower and shallower hardness pro le, indicating a lower nitrogen diVusion case depth. Nitriding with T i or Cu lid When a titanium plate was used as the top lid in AS nitriding (ASTi), the nitrided sample surface became golden mixed with purple in colour, presumably owing to the formation of titanium nitride. The GDS result in Fig. 13a shows that the nitrided surface of less than 1 mm contains Ti and N. Because the layer was too thin, the XRD could not detect any Ti or TiN, but only showed the peaks of the substrate a-Fe. Surface hardness measurements at 01 kg load showed a very small hardening eVect (Fig. 10). However, no hardening was found below the surface (Fig. 11). When a copper plate was used as the top lid, the AS nitrided sample (ASCu) surface was covered with a layer of copper which can be easily identi ed by the reddish brown colour. The copper layer was about 12 mm thick as shown by the GDS results in Fig. 13b. No hardening eVect was found either on the sample surface (Fig. 10) or beneath it (Fig. 11). DISCUSSION Nitrogen transfer from atmosphere to sample surface As with any other type of nitriding, AS plasma nitriding is also expected to be a multistage process, which involves the nitrogen transfer from the plasma atmosphere to the solid surface, and then from the solid surface into the substrate. The mechanism of nitrogen atom production and transfer from the media to the component surface is one of the principal di Verences between plasma nitriding and gas or bath nitriding, and the diVerence between AS nitriding and dc nitriding if there is any. Several models have been proposed in the past to explain the mass transfer mechanism in dc plasma nitriding. These include the

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H ardness pro les of samples nitrided with various active screen setups
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Chemical composition in samples A S nitrided with a T i plate (A ST i) and b Cu plate (A SCu) as top lid in active screen

models of sputtering and recondensation, 7 nitrogen ion implantation, 8 low energetic Nm H+ n bombardment, 9 nitrogen adsorption, 1 0 and neutral and ion adsorption. 1 1 However, some of these models can be easily excluded from AS plasma nitriding process as discussed below. The nitrogenhydrogen ion bombardment theory suggests that nitrogenhydrogen molecular ions, e.g. NH+ and NH+ 2 , play decisive roles for nitrogen mass transfer in plasma nitriding.9 The molecular ions of nitrogenhydrogen will dissociate upon hitting the cathode, supplying the active nitrogen which penetrates the surface barrier. However, the fact that nitriding can be performed with a N2 + Ar gas mixture with the AS technique in this test, and dc technique in other work8 suggests that hydrogen, and in turn NH+ and NH+ 2 , are not necessary for plasma nitriding. The implantation theory proposes that plasma nitriding is either achieved by the penetration of the high energy nitrogen atoms, 8 or by nitrogen ion (N+ ) implantation.1 2 However, it is known that with industrial ion implantation, the energy of ions can be as high as 100 keV, yet, the penetration depth of ions, e.g. N+ , is limited only to the top most surface layer within a depth of less than 0102 mm.1 3 In dc plasma nitriding, the energy of nitrogen ions is normally less than 05 keV with a potential of about 500 V between the cathode and the anode. While in AS nitriding, the sample is in a oating potential, and the nitrogen ions or atoms away from the cathodic active screen would have far less energy than those in either ion implantation or normal dc nitriding. Therefore, high energy atom penetration or ion implantation could not play a major role in nitrogen transportation in AS plasma nitriding.

It is also doubtful that the adsorption of nitrogen to the sample surface could be a major factor in nitrogen mass transfer. This is because in nitriding with pure nitrogen, the sample was immersed in the plasma which can contain nitrogen ions of N+ , N+ 2 and nitrogen neutrals of N, N2 ,1 4 however, the nitriding eVect was minimal for both AS nitriding and in dc nitriding as shown in Figs. 8 and 9. Hudiss experiment with rf plasma9 proved that a sample immersed in an rf plasma of di Verent compositions of N2 H2 Ar gases would not nitride if there was no current between the cathode and the anode. The discussions above lead the present authors to consider that the sputtering and recondensation model, as established in dc plasma nitriding, also could be the most likely mechanism for nitrogen mass transfer in AS plasma nitriding. The original model requires sputtering of iron from the cathodic components into the cathode potential drop region where FeN is formed, which is then backscattered and deposited on the cathode, and in turn decomposes to release nitrogen in the a-Fe lattice to form the case.7 In the present study, it was found that the sputtering and deposition in AS nitriding were not only signi cant, but also closely related to the nitriding eVect. The most apparent evidence of sputtering and deposition was when copper was used as part of the active screen. In this case, a copper layer was formed on the steel sample surface, which could be visually seen and detected by GDS and XRD analysis. When titanium plate was used as part of the active screen, a titanium deposition product was found to cover the sample surface. Unfortunately, the deposition of copper and titanium products did not bring much nitrogen to the sample surface, and there was no noticeable case hardening. The deposition phenomenon was not so distinct when a steel plate or a steel mesh was used as the screen. However, under high resolution SEM (Hitachi 4000, FEG-SEM), the morphology of the deposition can indeed be revealed. Figure 14 shows the FEGSEM images of dc and AS plasma nitrided sample surfaces. It can be seen that the dc nitrided sample consists of particles of irregular size and distribution, presumably, caused by the continuous sputtering of the cathodic sample surface during nitriding. In contrast, the AS nitrided surface consists of multiple particles with well de ned boundaries. The size of the particles is in submicrometre scale, and most of them have a hexagonal surface. Figure 15 shows the particles at even higher magni cation. The detailed composition of each particle was not analysed in this test, but the XRD measurement performed on the sample surface proved that they are iron nitrides consisting mainly of e phase. The existence, the morphology, and the distribution of these particles were found to depend on the AS nitriding conditions. In nitriding with argon, a similar particlelike surface as Fig. 14b was produced although the average size of the particles appeared to be slightly bigger. In nitriding with pure nitrogen, seldom could any particles be found, with the sample surface remaining the original grinding marks. While in nitriding without a top lid (ASO), a non-uniform deposition was found in accordance with the visually observed non-uniform appearance. Toward the edge and near the mesh cylinder (dark area), the particles
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Non-uniformly distributed iron nitride particles on A S nitrided surface: 500 C, 25%N + 75H for 5 h, without 2 2 top lid 30 000

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M orphologies of a dc and b A S nitrided sample surface: 500C in 25%N + 75H for 5 h; steel plate as top lid in 2 2 active screen 10 000

were similar to Fig. 14b. While in the central area (white area), the deposition is of poorer quantity and is non-uniform, as shown in Fig. 16. It seems the growth of the surface layer was achieved by the pileup of particles with each of them occupying a lower energy position. These iron nitride particles could be formed by the growth of iron nitride on the sample surface, but most likely, it was the product of sputtering and deposition. It should be mentioned that, in the original sputtering and deposition model,7 sputtering is achieved by the accelerating species imparting energy and detaching iron atoms from the cathodic sample surface, which subsequently react with active nitrogen in the plasma to form iron nitride that is then backscattered onto the cathodic sample surface. In this test, the sputtering occurred on the cathodic active screen instead of the isolated sample surface. In addition, the steel screen was pre-nitrided before the test so that a compound layer of iron nitride had

already been formed on the screen surface before the nitriding test. It is therefore assumed that sputtering of the (polycrystalline) iron nitride occurred, probably by multi-bombardment, detaching material from the active screen in the form of not only atoms of Fe and N but also as particles of iron nitrides. Part of the detached material will be backscattered to the cathodic active screen as in dc nitriding, and part will be transported to the sample surface, where, on the way, further reaction with active nitrogen could occur, introducing more nitrogen to the sample surface. Nitrogen transfer from sample surface to substrate As a result of nitrogen mass transfer from the plasma atmosphere to the sample surface, e.g. by iron nitride deposition, a compound layer will form and a nitrogen gradient is built up on the surface. Nitrogen would then be released from the iron nitride in the compound layer and transferred into the substrate by a diVusion controlled process similar to that in dc nitriding. The nal nitrogen diVusion case depth is determined by the nitrogen gradient, nitriding temperature, and nitriding time. At a xed time and temperature, the case depth will only be determined by the nitrogen gradient. However, the case depth is not proportionally increasing with the nitrogen content and compound layer thickness on the surface. It has been shown that in the dc nitriding, once the nitrogen potential is higher than the threshold for the compound layer formation, the nitrogen case depth will not be in uenced by further increasing the nitrogen potential, although the thickness and the nitrogen content of the compound layer are further increased by using higher nitrogen potential.1 5 The formation of a compound layer establishes a constant nitrogen concentration at the compound /matrix interface, thus creating a similar nitrogen gradient, and thereby producing an identical hardness pro le. Similarly, in AS nitriding, once the iron nitride compound layer is formed on the sample surface, the case depth will then be aVected only by the nitriding temperature and time. On the other hand, if there is no iron nitride compound layer formed on the surface and the nitrogen concentration on the sample surface is lower, the nitrogen diVusion case depth will be adversely aVected.

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Iron nitride particles on A S nitrided surface at higher magni cation 50 000


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Interpretations of AS plasma nitriding results Based on the above discussions, the AS nitriding experiment results obtained in this test can be explained. For example, dc nitriding and AS nitriding in this test can produce a compound layer on the sample surface. Although the phase composition and the nitrogen content in the compound layer was diVerent, the nitrogen concentration at the interface of the compound layer and substrate can be the same. Therefore, dc nitriding and AS nitriding can produce similar nitrogen di Vusion case depth and hardness pro les. However, in dc nitriding, the sputtering and condensation occurred on the same sample surface. At the beginning, the sputtering product might be iron, but after the formation of a compound layer, sputtering of the iron nitride rather than iron alone would occur. This will sputter away part of the nitrogen that has already transported to the sample surface. While in AS nitriding, there was no sputtering away of iron nitride from the sample surface but only from the active screen, therefore, the ASPN sample surface has a higher nitrogen content and more e phase. When Ar was used to replace hydrogen, similar iron nitride deposition occurs on the sample surface, therefore, the case depth is also similar. However, when pure nitrogen was used, there was no iron nitride deposits found on the sample surface. Probably, the energy of the ion in pure nitrogen plasma in this test was too low to cause enough sputtering. Although the sample was immersed in the plasma, there was little nitrogen mass transfer to the sample surface, and thus, the nitriding eVect was minimal. CONCLUSIONS In summary, active screen plasma nitriding can achieve a similar hardening eVect as dc plasma nitriding, but without the common problems associated with dc plasma nitriding such as arcing surface damage, the hollow cathode eVect, and the edging eVect. The nitrogen mass transfer in AS plasma

nitriding is achieved by the sputtering of cathodic active screen and the deposition of iron nitride on the sample surface. Nitrogen is released from the iron nitride in the compound layer and transferred into the substrate by a diVusion controlled process. Without iron nitride deposition, the nitriding case depth is minimal, and with non-uniform iron nitride deposition, there would be a non-uniform nitriding case depth. ACKOWLEDGEMENTS The authors wish to acknowledge J. Georges for his kind permission to use his patented AS nitriding technique for this study. The nancial support by the European Community Brite/Euram Programme under project of BPRP-CT-97-0564 is also acknowledged. REFERENCES
1. j. m. obrien: Plasma nitriding, ASM Handbook, Vol. 4, Heat treating, 420424; 1994, Materials Park, OH, ASM International. 2. t. bell and p. a. dearnley: Surf . Eng ., 1994, 10, 123128. 3. j. georges: TC plasma nitriding, Proc. 12th IFHTSE Cong., Melbourne, Australia, 2000, International Federation of Heat Treating and Surface Engineering, Vol. 3, 229235. 4. w. k. liliental, l. maldzinski, t. n. tarfa, and g. j. tymowski: Frequently encountered nitriding problems, with special emphasis on hot work tools, Proc 12th IFHTSE Cong., Melbourne, Australia, 2000, International Federation of Heat Treating and Surface Engineering, Vol. 3, 219227. 5. j. georges: United States Patent, No. 5,989,363, No. 23, 1999. 6. a. wells and i. le r. strydom: Surf . Eng ., 1986, 2, 263267. 7. b. edenhofer: Heat T reat . Met ., 1974, (1 ), 23 28; (2 ), 59 67. 8. b. xu and y. zhang: Surf . Eng ., 1987, 3, 226232. 9. m. hudis: J. Appl . Phys ., 1973, 44, (4), 14891496. 10. g. g. tibbetts: J. Appl . Phys ., 1974, 45, (11), 50725073. 11. a. szabo and h. wilhelmi: Ha rt.-T ech . Mitt ., 1984, 39, (4), 148154. 12. b. b. arzamazov and t. a. panayoti: Ionic composition of the cathode area at ion nitriding, Proc. 11th IFHTSE Cong., Florence, Italy, October 1998, International Federation of Heat Treatment and Surface Engineering, Vol. 1, 311319. 13. j. k. hirvonen and b. d. sartwell: Ion implantation, ASM Handbook, Vol. 5, Surface engineering, 605610; 1994, Materials Park, OH, ASM International. 14. m. m. shahin: J . Chem. Phys ., 1965, 43, (5), 17981805. 15. y. sun and t. bell: Mater . Sci . Eng . A , 1991, A140, 419434.

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