Do DLC-like features in Raman spectra of tribofilms really mean they are DLC formed by friction?

doi:10.21203/rs.3.rs-2114549/v1

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Do DLC-like features in Raman spectra of tribofilms really mean they are DLC formed by friction?

https://doi.org/10.21203/rs.3.rs-2114549/v1

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Many previous studies of tribofilms have interpreted D- and G-bands in Raman spectra as evidence that diamond-like carbon (DLC) was formed during sliding. DLC and other amorphous-carbon films are produced by high-energy processes or high-temperature pyrolysis. Since neither of these conditions commonly occurs in a sliding interface, it seems unlikely that such materials could be produced during simple frictional sliding. To understand this apparent contradiction, we systematically analyzed tribofilms produced from vapor and liquid lubrication experiments using Raman spectroscopy with varied laser power and wavelength. The results provide evidence that DLC-like features in Raman spectra of tribofilms formed from organic molecules originate, not by tribochemical synthesis in situ during the tribo-testing as suggested previously, but rather from post-synthesis photochemical degradation of carbonaceous organic matter during the Raman analysis.

Organic molecules can undergo various chemical reactions at sliding interfaces [1]. Such reactions can be driven thermally via frictional heat or mechanochemically via shear-induced activation. The latter are specifically called tribochemical reactions [2]. Various reactions can occur upon shear of molecules at tribological interfaces; these include degradation or fragmentation (dissociation) whose products will desorb or diffuse into the surrounding medium and/or formation of tribofilms that remain on the surface and provide beneficial lubrication effects [3–10]. Tribofilms, present inside the sliding track or piled up around the contact region, are often analyzed with Raman spectroscopy [11–29]. This technique is used because it provides vibrational spectroscopic information of ‘small amounts’ of samples. When the excitation beam is focused onto a small area through an optical microscope (as in confocal Raman spectroscopy), a sample within a 1 ~ 10 μm² area can be analyzed with good detection efficiency of the scattered Raman signal [30]. Thus, Raman spectroscopy works well for the analysis of tribofilms that are accumulated in a small area.

Many Raman spectra of tribofilms reported in the literature show two characteristic vibrational bands of diamond-like carbon (DLC) [11–29] at ~ 1360 cm^− 1 and ~ 1570 cm^− 1, which are called D- and G-bands, respectively [31, 32]. Note that this feature is typical of almost all amorphous carbon (a-C) materials, including cokes produced by thermal degradation of organics [31–37]. The wiΔThs and relative intensities of these two peaks vary depending on the chemical composition and structure of the DLC [34, 38–41]. DLC is known to be a good solid lubricant material with excellent lubrication efficiency and superior wear resistance [42–47]; the observation of DLC-like spectral features in Raman analyses of tribofilms has been used as evidence of the formation of DLC during tribochemical reactions (in some literature, tribocatalytic reactions). The typical conclusion drawn from such results is that DLC formation is responsible for the good lubrication performance of a given tribochemical system. Examples of previous studies in which DLC-like Raman spectral features were observed from tribofilms formed by tribochemical reactions are suμmarized in Table 1.

Table 1

Reports of DLC-like spectral features in Raman analyses of tribofilms in sliding tracks. Materials, applied load, sliding speed as well as the wavelength (λ_EX) and power of the Raman excitation laser used in the cited literature are given. We have estimated, whenever possible, the temperature rise due to frictional heat (ΔT_sliding) and laser irradiation (ΔT_Raman) using the information reported in each paper. Details of the temperature calculations are in the Supporting Information.
System studied	Applied load (N)	Sliding speed (cm/s)	ΔT_sliding (^oC)	λ_EX (nm)*	Laser power (W)	Obj. lens (NA or mag×)	ΔT_Raman (^oC)	ref
Steel-on-steel with hexa-fluoropropene oxide lubricant	3	5	155	514.5	10	50×	186	[11]
Metal-on-metal sliding with protein in contact	-	-	-	514.5	10	-	-	[12]
Polyether ether ketone on steel	2	10	17	-	-	-	-	[13]
Steel/steel sliding contact in MoΔTC / mineral base oil	40	30	79	488/ 785	0.1–10	0.75	39	[14]
metal-on-metal (MoM) sliding with protein in contact	8–64	-	-	514.5	10	-	-	[15]
MoN_x-Cu-coated steel ball on disk in PAO oil	20	-	-	325	-	-	-	[16]
Steel ball on steel substrate in PAO4 + CPCa	10	20	10	514.5	-	-	-	[17]
Different metal surfaces lubricated with polysulfide (EP additive)	10	1	-	532	-	50×	-	[18]
Sapphire spheres slide on nanocrystalline Pt-Au film in ambient hydrocarbon	1	0.1	0.11	532	1.5	0.5	43	[19]
Steel/steel contact lubricated by base oil	20	13	77	514	-	-	-	[20]
Steel ball on steel substrate in PAO4 + CPCa	10	20	9.8	473	-	-	-	[21, 22]
Steel/steel contact lubricated by CPCa /CBCa in base oil	10	5	0.7	-	-	-	-	[23]
Steel ball slid on steel disc in PAO4/lubricant additives	10	10	7.2	532	-	-	-	[24]
Si₃N₄ ball slid on substrate with CN_x coatings	0.4	20–27	3.1	-	-	-	-	[25]
Conical tip slid on ceramic matrix composite	0.006–0.02	0.0008–0.008	10^− 4	488	1	-	-	[26]
Steel/steel contact lubricated by isooctane and hexadecane	1.96	12	11	532	-	20×	-	[27]
Steel/steel contact lubricated by cyclic hydrocarbon vapors	0.5	0.3	0.35	532	2.05	0.9	67	[28]
Different steel surfaces lubricated by formation of wear-protective tribofilms	2–6	10	-	473	1.25	0.95	35	[29]
* Photon energy in eV of λ_EX is 325nm = 3.81 eV [UV]; 473 nm = 2.62 eV; 514 nm = 2.41 eV; 532 nm = 2.33 eV; 633 nm = 1.96 eV; 785 nm = 1.58 eV [near-IR]

The observation of DLC-like Raman features from tribofilms produced from organic molecules (lubricants or lubricant additives) is interesting, but it raises an important question. DLC films are typically produced by high-energy processes such as physical vapor deposition (PVD) via magnetic sputtering or plasma-enhanced chemical vapor deposition (PECVD) [42, 44, 48]. Various types of a-C can be produced via pyrolysis of organic precursors, but it requires quite high temperatures (> 700–800 ^oC) and often oxygen-lean conditions [36, 49–52]. Frictional heat generated during the sliding process in most tribo-testing conditions reported in the literature (see Table 1) is not high enough to induce carbonization of organic products or residues. This leads to the question: How could such materials requiring high-energy or high-temperature synthesis processes be produced during simple frictional sliding?

In previous studies using x-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and infrared (IR) spectroscopy, it was shown that tribofilms formed from allyl alcohol, a-pinene, n-decane, cyclohexene, monoester, benzene and hexadecane, etc. are polymeric or oligomeric species, although their exact chemical structures are not known [3, 7–10, 53–56]. Various reaction pathways that are not thermally accessible can be activated during the shear process [2]. Organic species constituting tribofilms may be unstable and can easily degrade under the irradiation of the high-power laser used for Raman analysis. Photochemical reactions can readily occur, without substantial substrate heating (see Table 1), if light absorption induces electronic excitation from the ground state to an antibonding orbital of a molecule [33, 57]. Even when the single photon energy is smaller than the energy needed for electronic transition to the dissociative antibonding orbital, multi-photon excitation can occur when the laser beam is focused into a small area [58].

In this study, we present experimental evidence indicating that the DLC-like features in Raman spectra of tribofilms may originate from post-synthesis photochemical degradation of carbonaceous organic matters during the Raman analysis, not by tribochemical synthesis in situ during the tribo-testing. Therefore, any presentation of tribochemical synthesis of DLC-like tribofilms by friction, even on catalytically active surfaces, solely based on the Raman analysis result of tribofilms, should first rule out the possibility of photochemical degradation.

Vapor phase lubrication (VPL) conditions were first used to produce tribofilms on two different substrates, AISI 440C stainless steel (SS; McMaster-Carr) and 4 mm thick soda lime silicate (SLS; PPG) glass. The SS plate was polished with sandpaper and alumina slurry to the root-mean-square surface roughness (R_q) of ~ 20 nm. VPL provides a unique opportunity to collect low-vapor-pressure products without losing them to the surrounding because there is no liquid solvent present [59]. The precursor was methylcyclopentane and its partial pressure was about 3745 Pa at 20°C (30% with respect to the saturation vapor pressure) [28]. An AISI 440C stainless steel ball (diameter = 3 cm; R_q ≈ 4 nm [9]) was loaded at 0.5 N against the SS plate. At this load, the maximum Hertzian contact pressure was estimated to be 450 MPa. A borosilicate glass ball (Pyrex; diameter = 3 mm;) was used as the counter-body to the glass plate at a normal load at the maximum Hertzian contact pressure of 320 MPa. For both material systems, the sliding speed was 3 mm/s and the length of sliding tracks was 2.3 mm. With these experimental conditions, the flash temperature due to frictional heat was calculated to be 0.4℃ on the SS plate [60] (see supporting information). The produced tribofilms were analyzed with Raman spectroscopy using a Horiba LabRam HR Evolution Vis-NIR system. The excitation wavelengths were 532 nm, 633 nm, and 785 nm, and the excitation laser was focused with an objective lens 50× (NA = 0.5) or 100× (NA = 0.9). The data acquisition time was 10 seconds. The thickness of the tribofilms was analyzed with atomic force microscopy (AFM; Bruker Digital Instrument Multimode). Bruker TESPA-V2 probes were used to image the sliding tracks in tapping mode. For the selected tribofilms, force-distance curves were recorded and the data were fitted with the Johnson-Kendall-Roberts (JKR) model to estimate the elastic modulus [7, 8].

Oil-lubricated conditions, which are more relevant to industrial conditions, were also tested. A multi-functional tribometer (RTEC MFT-5000) with a reciprocating module was used to produce the tribofilm deposit on the ball. The flat AISI 52100 steel samples were heat-treated to obtain Vickers hardness of 311 ± 22 HV. The heat treatment procedure consisted of solution treatment at 900°C for 1 hour, followed by quenching in water at room temperature and then aging at 550°C for 1 hour. The flat samples were then polished using the standard metallographic technique to an average R_q of ~ 22nm. An AISI 52100 steel ball (52100 ball) with a diameter of 9.5 mm and R_q of ~ 5.6 nm was used. Tribological tests were conducted at 25°C and about 24% relative humidity under a normal load of 2 N, a reciprocating frequency of 5 Hz, and a stroke length of 10 mm, using PAO-4 as the lubricant. This normal load corresponded to a maximum Hertzian contact pressure of 611 MPa. After 1 hour of tribo-testing, a dark-colored deposit accumulated on the ball, which was then rinsed with hexane to remove the residual lubricant. Raman spectra were collected using a Horiba LabRam HR Evolution confocal Raman microscope with the excitation laser wavelength of 473 nm and a 100× objective lens (NA = 0.95) to select the region of interest for the analysis. The laser power used for data collection was varied between 1–10% of the 25 mW full power. The data acquisition time was 90 sec.

A further study the tribofilms generated in oil-lubricated conditions was conducted at a faster speed and run for longer time using a different lubricant, dodecane, subjected to boundary lubrication conditions. This experiment was performed with a flat D2 steel sample and a 52100 ball. Both substrate and ball have a Vickers hardness about 800 HV. The flat D2 substrate was used for this experiment instead of 52100 because a larger production of tribofilm was observed with the D2 steel than 52100 when lubricated with dodecane [29]. The test was conducted for 5 hours at normal load of 5 N and sliding speed of 1 m/s, with the contact being fully flooded in dodecane. After the experiment, the tribofilm accumulated at the leading edge of the wear scar on the 52100 ball was examined by Raman spectroscopy after a short hexane rinse to remove residual dodecane, and after soaking for 24 hours in dichloromethane (DCM), followed by a five-minute sonication in hexane to remove the remaining hydrocarbons. Raman spectroscopy was conducted with a Horiba LabRam HR Evolution confocal Raman microscope with the laser excitation wavelength of 473 nm, laser power of 1.25 mW and 100× objective lens (NA = 0.95). The data acquisition time was 90 s.

As a control experiment, two reference samples were analyzed with Raman spectroscopy (Horiba LabRam HR Evolution Vis-NIR). One was organic granulated cane sugar (Great Value, Walmart) purchased at a local grocery store, and the other was an air-dried inner bark of a poplar tree (~ 30 years old, dead) collected from a house yard at State College, PA.

Figure 1 shows the Raman spectra of the tribofilms produced on SS during VPL of methylcyclopentane [28]. For irradiation with low power (0.41mW) at 532 nm (= 2.33 eV photon energy, Fig. 1a), the tribofilm showed a large fluorescence background and negligible D- and G-bands. The fluorescence background means that the tribofilm absorbs the 532 nm irradiation and is excited electronically [61]. Electronic excitation in the visible wavelength is often observed for polyaromatic hydrocarbons [62]. It is possible that such aromatic components were produced and present in the tribofilm. When the 532 nm excitation laser power was increased to 2.05 mW, the “DLC-like” D- and G-bands appeared over the fluorescence background. At the same time, a burn mark could be seen in the illuminated spot (middle panel in Fig. 1a). When the laser power was reduced back to 0.41 mW, the D- and G-band features remained. This result implied that the D- and G-bands were induced by the high intensity laser via photochemical degradation. Note that, since the 2.05 mW laser beam was focused onto ~ 1 μm² area with a 100× objective lens, the actual power density was on the order of 10⁵ W/cm². Heat diffusion calculations show that the maximum temperature rise was only 47 K at this laser power level [29].

To further support the hypothesis of photochemical degradation, we collected Raman spectra using longer wavelength excitations for tribofilms produced the same way as those analyzed above (Fig. 1b-c). When the photon energy was lowered from 532 nm (2.33 eV) to 633nm (1.96 eV) and 785 nm (1.58 eV), the critical power needed to observe the appearance of the D- and G-bands was much higher. The difference in the baseline slope was because the fluorescence emission wavelength, as well as detector sensitivity, vary with excitation wavelength. There were no discernable D- and G-band features in the initial low-power spectra, and their appearance was accompanied by a burn mark on the sample surface. Once observed after irradiation at a high power, the D- and G-band features with reduced intensities remained in the Raman spectra collected with a lower power at the same location. These results supported the hypothesis that the observed D- and G-band features from the tribofilm were due to photochemical degradation of tribopolymers, not direct formation of DLC or a-C from tribochemical reactions during sliding.

Many tribofilms reported in the literature had iridescent colors in optical microscope images [8, 59, 63–67]. Such colors can also be seen in the optical images in Fig. 1. They are produced via interference of light rays reflected from the top and bottom of thin films [68–71]. If the tribofilm surface was rough, they would look black in the optical image due to light scattering. Thus, seeing iridescent colors means that the top surface of the tribofilm is quite smooth. From this, we conjecture that the tribofilm was more like a viscous liquid during the synthesis process, flowing locally to form a smooth surface to minimize surface free energy. This suggests that the tribofilm consists of oligomeric or polymeric matter. In fact, when the tribofilm was indented with an AFM tip, it exhibited compressive deformation, from which the elastic modulus was estimated to be ~ 1 GPa (see the Supporting Information). This value is about two orders of magnitude lower than the modulus of tribopolymers after photochemical degradation estimated from the full-width-half-maximum of the G-band in the Raman spectrum (\({G}_{FWHM}\)) collected with 532 nm excitation shown in Fig. 1a (see the Supporting Information) using the same empirical correlations of \({G}_{FWHM}\) with the elastic modulus of amorphous carbon [34, 41]. This comparison again supports the suggestion that, although a tribofilm may exhibit the D- and G-band features in the Raman analysis, the result should not necessarily be interpreted as a DLC film produced tribochemically during the friction test.

One may question if the metallic substrate could catalyze the formation of DLC. In the case of SS, the surface is covered with chromium oxide. Although specific activation is required, chromium oxide has the catalytic ability to polymerize olefins [72, 73]. Although such catalytically active sites may facilitate tribofilm formation and photochemical conversion of the film to DLC under laser beam irradiation, their presence is not critically needed. To test this hypothesis, we conducted the same VPL testing on 4 mm thick SLS glass (as an inert reference sample) and analyzed with Raman spectroscopy. The tribofilm formation yield on the SLS surface was about one tenth that on the SS surface. The threshold laser power needed to observe the D- and G-band features in the Raman spectrum was found to be higher for the tribofilm on SLS (Fig. 2) than for the tribofilm on SS (Fig. 1a). The most likely reason is that SLS is transparent at 532 nm, while SS is reflective. In other words, the tribofilm on the SLS surface would experience less photon exposure than the SS surface at the same irradiation condition.

The tribofilms formed in liquid lubrication conditions measured at the sufficiently high laser power showed the same photochemical degradation behavior as seen in the VPL experiments. Figure 3a shows the variation of Raman spectra obtained at a fixed spot on the tribofilm with respect to the laser power. Raman measurements were conducted at 1.25 mW, followed by 2.5 mW, and then by 1.25 mW again. At the initial 1.25 mW irradiation, the D- and G-band intensities were around 3 and 5, respectively, after removal of the background. Upon subjecting the same spot to 2.5 mW, their intensities rose to ~ 20 and ~ 42, respectively, closely resembling the characteristic D- and G-bands of DLC-like materials. When repeated at 1.25 mW laser power again, the same spot yielded D- and G-band intensities of ~ 7 and ~ 10, respectively. Figure 3b shows the same exercise done on a different spot with laser power starting at 0.25 mW, followed by 1.25 mW, and then back to 0.25 mW again. The fact that similar signatures were obtained at 0.25 mW laser power before and after the exposure to 1.25 mW laser power indicates that the degree of photochemical degradation was relatively small at this low power condition. Note, however, that the Raman band positions obtained at 0.25 and 1.25 mW (Fig. 3b) are slightly shifted from those obtained at 2.5 mW (Fig. 3a), suggesting that the chemical nature of the original tribofilm is different from that induced by high-power laser irradiation. In summary, these results demonstrate that sufficiently high-power laser radiation can induce photochemical degradation of the tribofilm formed in PAO-4.

The high-speed (1 m/s) ball-on-disk tribotest was conducted to determine if a DLC tribofilm could be formed tribochemically under more severe experimental conditions. In this case, the average flash temperature was about 150°C above ambient [60] (see the supporting information). The tribofilm formed after such tribotests shows two broad peaks around 1300 cm^− 1 and 1580 cm^− 1 (Fig. 4), which are similar to the Raman D and G band signatures of DLC respectively. However, after soaking the tribofilm in DCM for 24 hours, followed by a short sonication in hexane, these bands disappear. The dissolution of the tribofilm in DCM suggests that the tribofilm is not DLC. Instead, the tribofilm might be another carbon-containing oligomer that happens to have the Raman spectral features similar to those of DLC [21]. Many carbonaceous materials have Raman peaks near the D- and G- band peak positions [21, 74–76], and a change in the D- and G- band peak intensities was also observed between oxidized and non-oxidized samples of carbonaceous material [77]. Therefore, the appearance of D- and G- bands cannot be the sole indicator that DLC has been produced tribochemically.

The photochemical degradation caused by the high-intensity laser beam during a Raman analysis suggests that tribochemically produced organic species are unstable. When thin films of polystyrene (PS) were deposited on pristine SS and SLS surfaces and the Raman spectrum was collected with the 532 nm excitation at 10.3 mW, the vibrational spectral features of PS did not change at all, indicating that PS did not degrade (Fig. 5). Note that the baseline of the PS Raman spectrum is quite flat, indicating that there is no electronic excitation. In the UV-VIS absorption spectrum, PS shows a peak around 270 nm (which corresponds to 4.6 eV) [78, 79]. Thus, its photochemical activity is negligible at 532 nm irradiation. In comparison, the tribofilms studied here absorb the 532 nm laser beam and fluoresce (Figs. 1, 2). Such electronic excitation and subsequent relaxation processes are likely to be accompanied by photochemical degradation reactions [57] that occur more readily at shorter-wavelength laser excitation [33].

Note that the excitation laser beam used for the Raman analysis can degrade even stable compounds if the laser power is sufficiently high. To demonstrate this, we did a series of control experiments with a granule of cane sugar and of the inner bark of a poplar tree. Figure 6 shows the Raman spectra of cane sugar and tree bark collected at the high laser power. When cane sugar was irradiated with 17 mW of 532 nm excitation laser (Fig. 6a), the collected Raman spectrum was in good agreement with that found in the literature and did not change over time [80]. When the laser power was increased to 34 mW, the sharp molecular vibration features disappeared gradually, and a broad fluorescent background grew over time. Eventually, weak but clearly noticeable D- and G-band features appeared on top of the fluorescent background. After subtracting the background of the raw spectra, apparent D- and G- bands were observed. Similar to the tribofilm case, this appearance was accompanied with a burn mark (beam damage) on the sample surface. In this case, it is possible that the degradation process was thermochemical. With a 100 × (NA = 0.9) objective lens, the irradiation of laser beam of 532 nm and 34 mW can cause the maximum temperature rise of the sugar surface to ~ 1300 K, assuming the thermal conductivity of sugar is 0.15 W/m-K [81, 82] and the absorption cross section is 0.01 [83] (see supporting information).

In the case of the poplar bark (Fig. 6b), only a broad fluorescence background signal was detected at 3.4 mW irradiation. This must be due to the autofluorescence of lignin components in the bark [84, 85]. At 34 mW, a clear burn mark was observed, and the DLC-like D- and G-bands appeared in the Raman spectrum. Because pyrolysis of tree bark is known to produce active carbon materials [86, 87], a similar degradation process is expected under the high-intensity laser irradiation, producing the “DLC-like” D- and G-band features in the collected spectrum. Therefore, it is possible that thermochemical degradation reactions can also take place when conducting Raman experiment at high laser power.

It is noted that, in Table 1, many studies reporting the DLC-like Raman spectra used excitation wavelengths shorter than the ones used in this study. If the photon energy is higher, then the possibility of photochemical degradation during the Raman analysis is even higher [33]. Many papers reported Raman spectra after background removal to show the D- and G-bands clearly (as shown in Fig. 3) [88–93]. However, it should be noted that the fluorescence background in a Raman spectrum gives very important structural information. The fluorescence background at a low-power excitation indicates that the tribofilm absorbs the probe beam and undergoes electronic excitation from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) [94]. This may mean that the tribochemical reaction products contain polyaromatic compounds [95, 96]. These species can readily be converted to a-C via photochemical degradation during the Raman analysis if the excitation laser energy or power is sufficiently high (Figs. 1–4 and 6).

The origin of DLC-like features in the Raman spectra of tribofilms produced by tribochemical reactions was explored. Three direct pieces of evidence were presented to indicate that DLC was not formed in situ by shearing several material pairs in the presence of a carbon-based liquid- or vaper-phase lubricant.

When the Raman spectrum of a tribofilm was collected with a low laser power, there were no obvious D- and G- peaks other than a fluorescence background, indicating that the tribofilm might contained polyaromatic compounds. As the laser power increased, clear D- and G- bands appeared, along with a burning mark, suggesting that D- and G- bands were the result of photochemical degradation of the tribofilm. Once the photochemical degradation occurred, the Raman spectrum of the same tribofilm measured again with a low laser power still show the D- and G- band features, although at lower intensities The occurrence of a photochemical reaction of the tribofilm depends on Raman excitation wavelength.

The elastic modulus of the tribofilms, measured using nanoindentation, was two orders of magnitudes lower than that of traditional DLC, indicating the mechanical properties of the tribofilm and DLC were different. Further, the fact that the Raman spectrum of the tribofilm changed significantly before and after soaking in the organic solvent suggested that the tribofilm is chemically distinct from DLC.

The Raman laser can degrade the structurally stable carbonaceous materials, resulting in the same burning marks and the DLC-like Raman features if the laser power is high enough to induce photochemical or thermochemical reactions.

Thus, the claim of tribochemical formation of DLC from tribotest solely based on Raman analysis needs to be revisited. Without independent spectroscopic or mechanical evidence, future studies should not interpret Raman data as evidence that DLC is synthesized via tribochemical or tribocatalytic processes from organic precursors.

Acknowledgements.

The authors thank PPG Industries, Inc for providing the soda lime silicate glass substrate. This work was supported by National Science Foundation (Grant No. 1912199, 2038494, and 2038499). Northwestern funding sources: National Science Foundation (Grant No. CMMI-1662606) and Army Research Laboratory Vehicle Technology Directorate (VTD) under Cooperative Agreement Number W911NF-20-2-0292.

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Do DLC-like features in Raman spectra of tribofilms really mean they are DLC formed by friction?

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