Novel solid-lubricant materials for multifunctional applications

10 May 2016
Surojit Gupta, M. F. Riyad, Sujan Ghosh, and Ross Dunnigan
The addition of thermodynamically stable nanolaminates to thermosets and thermoplastics improves the performance of polymer matrix composites.

Polymers and their composites possess excellent friction and wear characteristics, corrosion resistance, and mechanical properties that make them potential replacements for metals in many applications.1–6 Self-lubricating composites are particularly attractive because of their simple design, easy operability, and low cost, among other things. Moreover, the use of additives such as kaolin,2 molybdenum disulfide,3, 7 multiwalled carbon nanotubes,5,8,9 calcium stearate,6 wollastonite,10 short fibers,11 boron trioxide,12 serpentine,13 and silica14 has been shown to further enhance the mechanical and tribological performance of polymers. In previous studies7–14 it has been hypothesized that the addition of hard, machinable, conductive, and lubricious particles, such as Ti3SiC2 (MAX phase) will significantly alter the mechanical and tribological behavior of polymer matrix composites (PMCs). Briefly, Mn+1AXn (MAX) phases (more than 60 phases) are thermodynamically stable nanolaminates where n is 1, 2, or 3, M is an early transition metal element such as titanium (Ti), A is an A-group element such as silicon (Si), and X is carbon (C) or nitrogen. MAX phases are layered hexagonal, with two formula units per cell. These solids are highly damage tolerant, thermal shock resistant, and readily machinable.15–19

In a series of studies, we have reported that the addition of Ti3SiC2 particulates, in both thermosets23 and thermoplastics20–22 enhances the mechanical performance and solid-lubrication behavior of PMCs. We have coined the term MAXPOL—composites of MAX phases and polymers—to designate this new generation of composites. Our detailed methods for fabrication and the characterization procedure are available elsewhere.19, 23 We have found that MAXPOL composites show solid-lubrication behavior during self-mating,20, 21 and here we review some of the important results from our recent studies.

Scanning electron microscopy (SEM) images of Ti3SiC2-UHMWPE (ultra-high-molecular-weight polyethylene) composites are shown in Figure 1.20 We find that the Ti3SiC2 particulates are well dispersed in the UHMWPE matrix when the concentration of Ti3SiC2 particulates is about 5vol.%, as shown in Figure 1(b) and (c). In contrast, the Ti3SiC2 particulates segregate to form Ti3SiC2- and UHMWPE-rich interfaces around the UHMWPE matrix at higher concentrations of Ti3SiC2, as shown in Figure 1(d) to (i). At this juncture, we are not sure of the exact mechanism causing this behavior, but most probably, dewetting of Ti3SiC2 particulates by the polymer causes the Ti3SiC2 particulates to segregate in Ti3SiC2-rich polymer regions.


Secondary electron (SE) scanning electron microscopy (SEM) images of (a) pure ultra-high-molecular-weight polyethylene (UHMWPE), (b) 5vol.% Ti3SiC2(MAX phase)-UHMWPE, and (c) a backscatter electron (BSE) image of the same region. (d) and (g) are SE SEM images of 20 and 35vol.% Ti3SiC2, respectively. The same samples are shown at higher magnification in (e) and (h), and as BSE images of the same regions in (f) and (i).20

The mean friction coefficient (μmean) and wear rate (WR) of our composites, as a function of the addition of Ti3SiC2 particulates, are summarized in Figure 2. UHMWPE sliding against itself exhibts a higher μmean compared with the Ti3SiC2-UHMWPE composite sliding against itself, as shown in Figure 2(a). Teflon-Ti3SiC2 and polyetheretherketone (PEEK)-Ti3SiC2 composites showed a similar trend, which suggests that Ti3SiC2 particulates may prove an effective solid-lubricant additive in a host of polymer matrices.


Plot of (a) the mean friction coefficient (μmean) and (b) wear rate (WR), as a function of adding of Ti3SiC2to UHMWPE composites. PEEK: Polyetheretherketone. Tab: Test material.20–22

The WR results—see Figure 2(b)—are also very promising. During self-mating, both surfaces showed wear. The total WR of the UHMWPE surfaces was less than about 1.6 × 10−4mm3/N.m, whereas in 5vol.% Ti3SiC2-UHMWPE and 20vol.% Ti3SiC2-UHMWPE the WR was negligible (less than 4 × 10−7mm3/N.m). The WR then increased to about 2 × 10−6mm3/N.m in 35vol.% Ti3SiC2-UHMWPE. We could not detect wear in the 5vol.% Ti3SiC2-UHMWPE and 20vol.% Ti3SiC2-UHMWPE compositions after cycling for 10,000m. This further indicates the long-term stability of these composites during self-mating.20

A detailed investigation of the wear tracks showed that the tribology of Ti3SiC2-UHMWPE composites is driven by the formation of tribofilms.19, 23 We have previously shown that the tribological behavior of MAX phases and their composites is driven by tribofilm formation.19 The tribofilms formed during self-mating of Ti3SiC2-UHMWPE composites made thin layers over each tribosurface. Using a previously proposed classification,19 we find that the tribofilms correspond to type IIIa. A simple schematic diagram, in which lubricious tribofilms are formed at tribocontacts, is shown in Figure 3.


Schematic illustration of the formation of a type IIIa tribofilm. (a) Tribocontact formation during self-mating of MAXPOL (MAX phases plus polymers). (b) Formation of tribofilms by mild adhesive wear and triboxidation of both surfaces during tribology studies. (c) SE SEM image of type IIIa tribofilms. Ti0.76Si0.24O1.9{Cx}: Example chemical composition of a type IIIa tribofilm.19,20

In summary, we have synthesized and characterized novel MAXPOL composites. The addition of Ti3SiC2 particulates enhances both the mechanical behavior and, especially, the tribological performance of the materials. Tribofilms that formed during self-mating of Ti3SiC2-UHMWPE composites were barely visible to the naked eye and formed thin layers over each tribosurface (as observed by SEM). We therefore classified these tribofilms as type IIIa.20 Our tribological studies showed that the addition of Ti3SiC2 in the UHMWPE matrix imparts self-lubricity to the composites and aids in decreasing adhesive wear during dry sliding of polymer-on-polymer tribocouples. In particular—when used in a polymer matrix to reduce adhesive wear—Ti3SiC2 particulates can lead to the development of polymer-on-polymer wear couples, which may provide engineers with novel approaches for designing devices.24 We are currently conducting studies to investigate the wetting behavior of Ti3SiC2 and polymers. We are also exploring novel polymer systems such as PEEK, Teflon, and polylactic acid. In addition, we are developing novel techniques for 3D printing of these composites.


Authors

Surojit Gupta
University of North Dakota

Surojit Gupta is an assistant professor in the Department of Mechanical Engineering. He has given numerous presentations and has published more than 40 papers.

M. F. Riyad
University of North Dakota

M. F. Riyad is working as a graduate research associate in the Department of Mechanical and Aerospace Engineering at The Ohio State University. He received his BSc (2009) in mechanical engineering from Khulna University of Engineering and Technology, Bangladesh, and completed his MSc (2014) in mechanical engineering at the University of North Dakota.

Sujan Ghosh
University of North Dakota

Sujan Ghosh completed his BSc in mechanical engineering in 2012 and then worked in a pharmaceutical company. He joined the University of North Dakota in spring 2015 to pursue an MSc in mechanical engineering. He is currently working in the Advanced Materials Research Group with Surojit Gupta on multifunctional MAXPOL and MRM (MAX reinforced metal) composites.

Ross Dunnigan
University of North Dakota

Ross Dunnigan is currently a graduate research fellow in the Department of Mechanical Engineering. He is designing novel polymers for additive manufacturing, has given numerous presentations, and has two publications. He is expected to graduate in May 2016.


References

  1. Y. Q. Wang and J. Li, Sliding wear behavior and mechanism of ultra-high molecular weight polyethylene, Mater. Sci. Eng. A 266, pp. 155-160, 1999.

  2. G. Guofang, Y. Huayong and F. Xin, Tribological properties of kaolin filled UHMWPE composites in unlubricated sliding, Wear 256, pp. 88-94, 2004.

  3. V. Pettarin, M. J. Churruca, D. Felhös, J. Karger-Kocsis and P. M. Frontini, Changes in tribological performance of high molecular weight high density polyethylene induced by the addition of molybdenum disulphide particles, Wear 269, pp. 31-45, 2010.

  4. S. W. Zhang, State-of-the-art of polymer tribology, Tribol. Int'l 31, pp. 49-60, 1998.

  5. Y. Xue, W. Wu, O. Jacobs and B. Schädel, Tribological behaviour of UHMWPE/HDPE blends reinforced with multi-wall carbon nanotubes, Polym. Test. 25, pp. 221-229, 2006.

  6. C. V. Panin, L. A. Kornienko, T. Nguyen Suan, L. R. Ivanova and M. A. Poltaranin, The effect of adding calcium stearate on wear-resistance of ultra-high molecular weight polyethylene, Procedia Eng. 113, pp. 490-498, 2015.

  7. B. Ben Difallah, M. Kharrat, M. Dammak and G. Monteil, Improvement in the tribological performance of polycarbonate via the incorporation of molybdenum disulfide particles, Tribol. Trans. 57, pp. 806-813, 2014.

  8. S. Suñer, C. L. Bladen, N. Gowland, J. L. Tipper and N. Emami, Investigation of wear and wear particles from a UHMWPE/multi-walled carbon nanotube nanocomposite for total joint replacements, Wear 317, pp. 163-169, 2014.

  9. Y. Liu and S. K. Sinha, Wear performances and wear mechanism study of bulk UHMWPE composites with nacre and CNT fillers and PFPE overcoat, Wear 300, pp. 44-54, 2013.

  10. J. Tong, Y. Ma and M. Jiang, Effects of the wollastonite fiber modification on the sliding wear behavior of the UHMWPE composites, Wear 255, pp. 734-741, 2003.

  11. L. Chang and K. Friedrich, Enhancement effect of nanoparticles on the sliding wear of short fiber-reinforced polymer composites: a critical discussion of wear mechanisms, Tribol. Int'l 43, pp. 2355-2364, 2010.

  12. B. R. Burroughs, J.-H. Kim and T. A. Blanchet, Boric acid self-lubrication of B2O3-filled polymer composites, Tribol. Trans. 42, pp. 592-600, 1999.

  13. Z. Jia and Y. Yang, Self-lubricating properties of PTFE/serpentine nanocomposite against steel at different loads and sliding velocities, Compos. Part B: Eng. 43, pp. 2072-2078, 2012.

  14. D. Felhös, J. Karger-Kocsis and D. Xu, Tribological testing of peroxide cured HNBR with different MWCNT and silica contents under dry sliding and rolling conditions against steel, J. Appl. Polym. Sci. 108, pp. 2840-2851, 2008.

  15. M. W. Barsoum and M. Radovic, Elastic and mechanical properties of the MAX phases, Annu. Rev. Mater. Res. 41, pp. 195-227, 2011.

  16. M. W. Barsoum and T. El-Raghy, Synthesis and characterization of a remarkable ceramic: Ti3SiC2, J. Am. Ceram. Soc. 79, pp. 1953-1956, 1996.

  17. M. W. Barsoum, The MN +1AXN phases: a new class of solids; thermodynamically stable nanolaminates, Prog. Solid State Chem. 28, pp. 201-281, 2000.

  18. S. Amini, M. W. Barsoum and T. El-Raghy, Synthesis and mechanical properties of fully dense Ti2SC, J. Am. Ceram. Soc. 90, pp. 3953-3958, 2007.

  19. S. Gupta and M. W. Barsoum, On the tribology of the MAX phases and their composites during dry sliding: a review, Wear 271, pp. 1878-1894, 2011.

  20. S. Gupta and M. F. Riyad, Synthesis and tribological behavior of novel UHMWPE-Ti3SiC2 composites, Polym Compos., 2016.

  21. S. Ghosh, R. Dunnigan and S. Gupta, Synthesis and tribological behavior of novel wear resistant PEEK-Ti3SiC2 composites, J. Eng. Tribol., under revi.

  22. S. Ghosh, R. Dunnigan and S. Gupta, Novel self-lubricating Teflon-Ti3SiC2 composites, to be subm.

  23. S. Gupta, T. Hammann, R. Johnson and M. F. Riyad, Tribological behavior of novel Ti3SiC2 (natural nanolaminates)-reinforced epoxy composites during dry sliding, Tribol. Trans. 58, pp. 560-566, 2015.

  24. S. C. Scholes and A. Unsworth, The wear performance of PEEK-OPTIMA based self-mating couples, Wear 268, pp. 380-387, 2010.

DOI:  10.2417/spepro.006444