本研究使用非平衡磁控濺鍍法披覆含鈦類鑽碳在 AISI 316L 不銹鋼以及經由離子氮化熱處理後的 316L 不銹鋼。實驗中有五種不同的底材，分別為 316L(316)、離子氮化後的316L(N316)以及在前者披覆含鈦類鑽碳(D316、DN316)，最後一種為離子氮化再經拋光處理後，披覆含鈦類鑽碳在上面(DN316s)。分析所有底材之微結構、機械性質，並以往復式磨耗試驗機(SRV) 在0.64% NaCl溶液中進行磨耗試驗，使用316L球、Ti6Al4V球與Si3N4球三種上試件與鍍層對磨，研究其磨潤特性與磨耗機構；以電化學分析評估各種底材抗腐蝕能力；培養Raw264.7小鼠單核巨噬細胞於所有底材上，探討這些材料的生物相容性。
結果顯示含鈦類鑽碳能夠提升磨潤性質，擁有較佳的抗腐蝕能力以及良好的生物相容性。其中以經離子氮化再經拋光處理後，披覆含鈦類鑽碳之底材(DN316s)，擁有最好的抗磨潤以及抗腐蝕能力。

SUMMARY

Low temperature plasma nitriding to 316 L stainless steels is attracted special attention. AISI 316L austenitic stainless steel was pre-treated by plasma nitrided at low temperature. The deposition of the DLC coatings on the unnitrided, plasma nitrided and polished after nitriding substrates by Closed Field Unbalanced Magnetron Sputtering(CFUMBS). To simulate human body environment, wear experiments were performed by using Schwingung Reibungund Verschliss(SRV) wear tester in 0.64% NaCl solution. The specimens are prepared to wear test for 24 min under loading of 30N against 316L, Si3N4 and Ti6Al4V balls. In this study, the corrosion test is measured by polarization curves and the Purified mouse leukaemic monocyte macrophage cells(Raw264.7) is seeded on the specimens for 24h, 72h and 20h in biocompatibility test. The combination of Ti-C:H and low temperature nitriding dramatically improves the friction property of 316 L stainless steels. Accordingly, it has been concluded that the duplex treatment of nitriding and Ti-C:H film coating is effective to improve anti-corrosion and increase biocompatibility after electrochemical test and biocompatibility test

Key words: CFUMBS, Ti-C:H, wear, corrosion, biocompatibility

1.Introduction
AISI 316L stainless steel has been widely used for biomedical implants, such as pegs, bone plate and orthopedic. Although, they could suffer pitting and crevice corrosion in specific environments and their low hardness and wear resistance could limit the number of possible applications. As AISI 316L stainless steel were nitrided or caburized at low temperature, a highly corrosion resistance layer was formed. The layer is interesting because it is provided with high hardness and good wear resistance without degradation of its corrosion resistance. If the treat temperature was higher than 400°C, AISI 316L would form grain boundary chromium depletion(GBCD). This phenomenon also could call sensitization. GBCD caused AISI 316L corrode easily. The other way, it also could use shot peened method for AISI 316L to increase hardness and decrease wear rate; nevertheless, it could make crevice corrosion easily.
In recent years, diamond-like carbon (DLC) films have attracted considerable attention because of their excellent mechanical, biocompatibility, tribological and chemical inertness properties. The combination of these unique properties leads to widespread applications of DLC films in diverse areas, such as wear-resistant coating for metallic, ceramic and optical materials, corrosion protection, drill, tools. Especially excellent tribological properties makes them good selects to wear resist layers, and many studies have showed DLC as a protective coating for the surface of implants. Dong-Hwan Kim showed that the wear volume of ruby ball was much lower on DLC-coated Ti6Al4V than on the bare metal itself. J.H. Sui showed that DLC-coated on NiTi alloys had better blood compatibility and corrosion resistance than the NiTi alloys. Mei Wang cultured mouse osteoblasts on DLC-coated silicon wafer. And the result showed that DLC coating had good biocompatibility. Mahfujur Rahman showed the DLC-coated on nitrided 316L had better wear properties. Although DLC coating was famous study, but a few study of DLC coating combined wear test, electrochemical and biocompatibility.
In this study, AISI 316L stainless steel was pre-treated by nitrided at low temperature. After nitriding, the Ti-C:H film was coated on the nitride and non-treat substrate by the CFUBMS. All of the treated and untreated specimens were applied to investigate the tribology, anti-corrosion and biocompatibility properties.
2.Experimental procedure
2-1 Substrate specimens
Prior to the study, the AISI 316L samples (specimen code:316L) were polished using silicon carbide emery papers of 180, 320, 600, 1200 and 2000 grit. Final polishing was done using 5μm and 1μm Al2O3 powder in order to produce scratch-free mirror-finish surface. Then, pre-treated specimens were thoroughly degreased, ultrasonically cleaned with alcohol, rinsed with deionized water, and then dried by hot air. The AISI 316L had a diameter of 22mm7.9mm for wear test and 16mm1mm for the cell cultures and electrochemical test. Besides, it had hardness of 276HV0.025 and surface roughness Ra of 0.01μm.
2-2 Plasma Nitriding
Based on our previous study, the result of the Raw264.7 cell growth on the nitrided 316L at 723K incubation. The temperature of plasma nitriding were at (723K), chromium nitride (CrN) were formed which caused anti-corrosion and biocompatibility decrease, the reason is the grain boundary chromium depletion at high temperature treatment cause the more susceptible to corrosion at Fe atom in the AISI 316L. So, the cells are motived by the precipitates of Fe ions. Therefore, in this study, the nitrided process was carried out at lower temperature. The substrate was then heated to the required level (623K) and plasma nitriding was carried out at a pressure around 1 mbr in a gas mixture N2/H2=1/5 for 20 minutes by heating rate 10°C/min. After that the specimens were nitrided for 23h at 663K by using a gas mixture N2/H2=1/5 under the pressure of 0.5 mbr (0.375 Torr). Finally, the specimens is used nitrogen cooling for 10min to room temperature with cooling rate 36°C/min. The mean hardness and roughness of treated specimens (specimen code:N316) were respectively 573HV0.025 and Ra of 0.07μm. After nitriding, the some specimens (specimen code:N316s) were polished using 5µm and 1µm Al2O3 powder in order to smooth surface. The nitriding phase composition, texture and crystalline structure were determined by an X-ray diffractometer (Rigaku MiniFlex II), with Cu Kα radiation.
The roughness increase in general after nitriding treatment. The hardness value given for the DN316 is likely flawed by the influence of the substrate as the Ti-C:H layer is relatively thin. As the hardness of substrate increases, the hardness of the Ti-C:H coating increases. It also shows the nanoindentation test the maximum indentation of depth with Ti-C:H coating. The three types coatings of depth are less than one tenth of the coating thickness. According to paper, as the maximum indentation of depth less than one tenth thickness of coating, the coating hardness was not effect by substrate property. But in this study, the same Ti-C:H films possess difference values of hardness, it should be the Ti-C:H films are too thin (1μm), resulting in the substrate hardness affect the coating hardness.
2-3 Deposition details
The deposition of the Ti-C:H coatings on the unnitrided and plasma nitrided substrates by the DC unbalanced magnetron sputtering method. According previously study, the Ti content in the Ti-C:H 3.5 at% had excellent wear performance. Therefore, in this study the doped Ti element is controlled about 3.5 at.% in Ti-C:H coating. Prior to the deposition process, the specimens were cleaned for 20 minutes in Ar plasma using a DC voltage with a magnitude of 340 V and a pulse frequency of 150 kHz. We coated the pure Ti interlayer to increase the adhesion before coated major coating Ti-C:H. In this experiment, Ti-C:H coating deposited on nitrided, non-treated 316L. There are three types of the coated specimen to analysis：Ti-C:H coated on the 316L substrates (specimen code:D316), nitrided 316L(specimen code:DN316) and polished after nitriding 316L(specimen code:DN316s).
2-4 Hardness tests
In this study, surface nanoindentation measurements were carried out using a load of 5mN with The LBI Nanoindenter(UNAT-M,Germany). And microhardness of the cross-sectional measurements were carried out using a load of 25g each 0.5µm for 20 second with Vicker’s hardness tester(Matsuzawa MXT-70,Japan).
2-5 Ramam analysis
Raman spectroscopy is an effective technique to characterize the C－C bond structure of the DLC film. Generally, the Raman peak of DLC is composed of two broad peaks, namely the D peak (disorder peak) and G peak (graphite peak). According to literature, the high frequency band (G band centred around 1560 cm-1) in DLC Raman spectra has been assigned to the graphite-like sp2-bonded
and the low frequency bond (D band centred around 1350 cm-1) has been assigned to the sp3-bonded phase. That is to say, the locations of the G peak are proportional to the sp2 content in DLC film. It is believed that the content of sp3 bonds or the value of sp3/sp2 determines the main performance of DLC film. The smaller the intensity ratio of ID/IG, the higher the content of sp3 bonds in diamond-like carbon, and the DLC is more similar to the diamond.
2-6 Scratch tester
A scratch tester was used to carry out the scratch adhesion tests. The machine was equipped with frictional force measurement. The nominal maximum load was 100 N for 1 cm by diameter 300nm of diamond vertebra.
2-7 Wear tests
The tribological properties were performed using a reciprocating wear test machine (SRV, Germany). The configuration of the SRV test machine consisted of a fixed lower specimen supporter and a replaceable upper specimen holder. The upper specimen is a ball, while the lower specimen is a uncoating and coating disk in the test. The balls (ϕ 10 mm) used as upper specimens (counterbodies) in the SRV tester were 316L, Ti6Al4V and Si3N4. The uncoated lower specimens were 316L stainless steel, nitrided and coated DLC films disks. The tests were performed at room temperature and atmospheric pressure with 0.64% NaCl solution. In addition, a constant 30 N normal load, 1 mm stroke, 50 Hz frequencyand 24 min test duration were employed. H. Yoshida sorted out during various human activities, such as brisk walking, walking up and down stairs, between general artificial hip cup load status is 3.28MPa. W. W. Park, who use the pin-on-disk wear test simulation of artificial hip joints, calculated 2.45N load is about 9.27MPa. Therefore, this study parameters set in terms of wear far more than ordinary artificial hip joint load, can show the reliability of experimental results. The maximum depth and wear rate of wear scars on the lower test contacted disk was measured respectively test three times on each specimen by using a White Light Interferometers, and we determined coatings wear performance with average value.
2-8 Electrochemical
Corrosion electric potential (Ecorr.) obtained from the polarization curve is an experimental potentiostatic anodic polarization method used to evaluate chemical corrosion resistance of materials. The un-coated, nitrided and DLC coated on un-coated and nitrided specimens were placed in a 5600 Electrochemical Workstation apparatus using corrosive media of 0.64vol.% NaCl aqueous solution. The anodic polarization was started from 0.5V to 3V with respect to a standard saturated calomel electrode (SCE), and scanning area of 1 cm2 at scanning speed of 0.01 V s-1. The corrosion experiments were performed at room temperature.
2-9 Biocompatibility
The cell culture experiments were applied for biological measurements. The each specimens were sterilized with 95% ethanol, inserted into 24-well polystyrene cell culture plates and seeded with RAW264.7, suspended in Dulbecco’s modified Eagle’s Minimum Essential Medium (DMEM) with 10% fetal bovine serum (Sebak GmbH), and gentamicin (40 lg/mL). Each well contained 10,000 cells (i.e., 4974 cells/cm2) and 2 mL of the medium. After culturing for 24, 72 and 120 h, the cells were rinsed with Phosphate buffered saline (PBS). Cell viability tests were performed by MTT assay (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenil tetrazolium bromide) as follows. For MTT assay, all samples were transferred to a fresh plate, 500 μl of MTT reagent was added to each well and incubated for 2 h at 37 °C. The MTT was reduced to an insoluble formazan precipitate by mitochondrial succinic dehydrogenase of viable cells. The absorbance of the content of each well was measured at Λ=570 nm with a 96-well microplate reader on a ELISA reader (Enzyme-linked Immuno-sorbent Assay, BioTekFLx800). In the end, the cells were dried by using 95% alcohol and observed by SEM.

3. Results and discussion
3-1 Nitrided result analysis
In the case of AISI 316L samples, γ-Fe peaks(43.5°,50.7°,74.5°) are visible. It also showed the CrO3 peaks(21.5°,24.9°) that was the anti-corrosion reason of AISI 316L. At low temperature expanded austenite (S-phase, Fe4N) is formed during plasma nitriding at 663K. The S-phase(40.3°,46.6°,68.4°) was highly corrosion resistant because of the absence of Cr segregation and was extremely hard because of the nature of its expanded lattice. As described in 2.2 section, If the temperature of plasma nitriding were higher than 663K, chromium nitride (CrN 37.5°,43.6°) were formed which caused anti-corrosion and biocompatibility decrease.
3-2 Ti-DLC coating analysis
It showed that the deposition thickness of 1µm for DLC coating, 180nm for Ti middle layer and 4µm for nitrided layer.
The GDS of the DN316 specimens showed carbon concentration decrease with depth increase and showed the nitrogen concentration was 20% at 0.3 to 2.3µm, approximately. After that, nitrogen concentration decrease with depth increase to 5.3µm.
HV microhardness measurements were carried out on the cross-sections of the treated samples. It display HV microhardness of AISI 316L (316L), nitrided(N316) and DLC coating on nitride(DN316) cross-sectional samples. It showed that the highest hardness of DN316 and then N316 specimens appear on the surface. An increase in the cross-sectional depth decrease the hardness of material.
The Raman spectra of the DLC films revealed that the D peak and G peak located at 1366 cm−1 and 1550 cm−1,respectively. And the ID/IG are 0.75. The ID/IG ratio is calculated by intensity ratio of D peak and G peak. These spectra are typical of amorphous a-C:H carbon. According to amorphization trajectory, the DLC specimens had almost 10% sp3 amprphous composition.
The typical scratch from each coating type were taken from the point of the wear track where the coating failed. The exact load range and the measurement scale are shown as well. It can clearly be seen from these pictures that the D316 and the DN316 coatings are much more lower than the DN316s coatings. The critical load of three kind specimens is 19.6N(D316), 18.5N(DN316) and 30.9N(DN316s). DN316s had higher critical load and rated 1.6 times with D316 and DN316 specimens.
3.3. Wear tests
It shows the dependence of wear depth and friction coefficient of all the test specimen sliding against different counterbodies. It shows all of the wear depths and coefficient of friction after sliding against AISI 316L ball. The coefficient of friction significantly reduced after coating DLC films. the DN316s possessed the lowest friction coefficient (0.09), it has reduced friction coefficient 7.9 times comparing wth 316L specimen. It also shows the coating of D316 and DN316 specimen are broken because the wear depths exceed the coating thickness, the DN316s also possessed the lowest wear depth. Compare it with 316L, it improved the 5.6 times. It displayed the specimens sliding against Si3N4 ball, all of the coating specimens (D316, DN316 and DN316s) possessed low wear depth(1.3µm, 1.0µm, 0.9µm, respectively) and friction coefficient(0.06, 0.07, 0.06, respectively), but the uncoated and nitrided specimens (respectively 316L and N316) also possessed high wear depth and friction coefficient. The same, DN316s reduced the 14.9 times of wear depth and 13.2 times of friction coefficient as comparing with 316L. It is obvious that the specimen of coated DLC films can decrease the friction coefficient and wear depth effectively, It shows using counterbody Ti6Al4V ball, all of the specimens have the large wear depth and friction coefficient. Overall, the DN316s possessed the smallest friction coefficient, wear depth and wear rate as sliding against Si3N4, 316 L and Ti6Al4V ball, respectively, it can decrease the wear rate respectively 156.1, 16.2, 29.4 times as compared with untreated 316L sample. B. Hashemi showed that the wear rate of AISI 316L after 570°C nitriding treatment improved 7.3 times against a 5 mm diameter SAE 52100 pin (ball) with 10N loading by rotating pin-on-disc wear testing machine with a speed of 2 cm/s. The all of specimens had maximum wear depth/wear rate and friction coefficient as sliding against Ti6Al4V ball. The suggestion reasons described as follow. Ti6Al4V had the smallest value and the most large contact area against Ti6Al4V ball, because the decrease in Young's Modulus increases the deformability of material. The other inference is the thermal conductivity of Ti6Al4V is one fifth of iron. So, the heat during wear sliding is difficult to transmit and loss. After that, the Ti6Al4V formed Titania particles during wear process and the hardness of the Titania is greater than Ti6Al4V. Because the Titania mixed in wear particles, the wear depth and wear rate of all specimens are the highest values as sliding against Ti6Al4V ball. Si3N4 ball had the highest Young's Modulus and hardness(2000HV0.025) in three types upper specimens. So, the wear depth and wear rate of 316 and N316 sliding against Si3N4 ball is more larger than the against 316 ball. But the wear depth and wear rate of D316, DN316 and DN316s sliding against Si3N4 ball is more lower than the against 316L ball.
3-4 corrosion properties
The corrosion properties were investigated by studying the anodic polarization behaviour as shown in the polarization curves depicted in Fig. 11. After the corrosion tests were completed for both the coated, nitrided and virgin materials of AISI 316L, the corrosion current density (Icorr) and corrosion potentials(Ecorr) were estimated by the turning point between the anodic curve and anode curve. The estimated values are provided in Table 5. The free corrosion potential and corrosion current density of the 316L sample were -0.1667V and 1.265E-7 A/cm2, respectively. However, the parameters of the N316 were -0.156 V and 1.12E-7 A/cm2. There was a significant improvement in corrosion resistance after the treatments evidenced by a shift of the whole polarization curve towards the region of lower free corrosion current density and higher free corrosion potential. This results can confirm that forming the S-phase can increase anti-corrosion. The polarization curves in Fig. 11 show that the corrosion potential for DLC coated specimens is better anti-corrosion than nitrided and 316L substrates. The sample surfaces after corrosion tests were observed using SEM as shown in Fig. 12. Fig. 12 shows the surface morphology of the coated and uncoated samples after the potentiodynamic corrosion test. Fig. 12(a) shows the 316L surface after corrosion test is corroded seriously and deep pits. Fig. 12(b) shows the N316 surface after corrosion test is ferric oxide precipitate on the white position and no pitting is observed. Fig. 12(c) shows the D316 surface after corrosion test has a few small and shallow corrosion pits on the surface. Fig. 12(d) shows the DN316 surface after corrosion test has large and few ferric oxide precipitate on the white position. Fig. 12(e) shows the DN316s surface after corrosion test has also ferric oxide precipitate as Fig. 12(b). Comparing Fig. 12(d) and Fig. 12(e), the ferric oxide precipitate on the white position of the DN316s are significant reduction. The results showed that the DLC316s film exhibited the best corrosion resistance.
3-5 biocompatibility
It shows that the Raw264.7 cells growth well and the coverage area of cells increased with time. And in day5, the cells incubated on 316L and DLC specimens looked packed around the surface, but the N316 had not cover the entire surface.
The cell number increases with time moreover DLC-N316s had the greatest number of cells. After coating DLC films, the roughnes increase slight, so the contact angle of DLC specimens is larger than N316 and 316L. The contact angle of N316 is larger than 316L because the roughness increases after nitriding. The contact angle decrease in general with increase hydrophilicity. The cell attachment and spreading appear to be related to the surface wettability. Cells on the hydrophobic surfaces attach more slowly and weakly and spread less, but on the other hand, the hydrophilic samples induce better cell adhesion and proliferation. Because the human cells are more able to adapt on the hydrophilic environment. Although, the contact angle of Ti-C:H coating are large than 316L and N316, the Ti-C:H films amount of cells are more than 316L and N316. Therefore, the Ti-C:H coating improve the amount of cells to enhance the contact angle reduction caused problems.
4. Conclusions
Ti-C:H is deposited on nitride and untreated AISI 316L by CFUMBS method using a mixture of CH4 and Ar . According the SEM cross-sectional and GDS, the depth of DLC coating and nitrided films are 1µm and 4µm, respectively. Overall, the adhesion wear of upper specimens/ Ti6Al4V wear pair had maximum wear depth and wear rate on all specimens. The optimum coating for tribological properties against a Ti6Al4V or a AISI 316L steel or a Si3N4 ceramic ball is DN316s. Especially, the optimum wear pair is DN316s against Si3N4 ceramic ball. The DN316s specimens possessed the highest hardness, excellent adhesion and tribological performance.
Corrosion experimental results have confirmed that the corrosion resistance of the AISI 316L are markedly improved due to the nitriding treatment and the deposition of DLC films. After plasma nitriding an AISI 316L austenitic stainless steels it was observed that the nitrided layer of specimens nitrided at 390 °C shows predominantly expanded austenite(S-phase). Forming the S-phase on AISI 316L will increase anti-corrosion because of absence of Cr segregation. Plasma nitriding treatment can improve the pitting corrosion of AISI 316L. Anti-corrosion properties of the DLC films deposited on AISI 316L, 316L were investigated using potentiodynamic polarization experiments. The DLC films improves the ability of corrosion protection of DLC film on AISI 316.
In the biocompatibility, no obviously increased cell death or immediate toxicity was found in all films. Comparing the cell viability and contact angle, the quantity of cells increases as the contact angle decreases. DLC316s had the best biocompatibility because of the deposition of DLC coating and the least contact angle.

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