By: 28 November 2016
The story of silicon nitride

Amedica Corporation makes and develops silicon nitride ceramics. This summary was prepared to share their knowledge and passion of an incredibly versatile material that has myriad applications in medicine.

What is silicon nitride (Si3N4)?

Silicon nitride is a ceramic. It is an inorganic and non-metallic compound of silicon and nitrogen, two elements that are vital to life [1–4]. Discovered in 1857, silicon nitride remained a curiosity until commercial use began in the 1950s [5].

Manufacturing costs were reduced in the 1970s–80s, and silicon nitride quickly found a home in many industries [6]. In the 1990s, naturally occurring silicon nitride was discovered in meteorite stardust, suggesting intergalactic origins from the beginning of time [7].

silicon nitride

 

Properties

To make silicon nitride, refined material powders are mixed into a slurry, from which desired shapes are crafted, and finished in high-temperature pressure furnaces. These steps are similar to making pottery; the word ‘ceramic’ comes from the Greek root kéramos, which refers to pottery [8].

Silicon nitride is a tough and strong material that resists abrasion, corrosion and most chemicals. It has the highest fracture resistance of any advanced ceramic [9]. These properties have led to many applications throughout industry.

Amedica 5

 

Industrial uses

Human life is touched almost daily by silicon nitride. It is used in high-end bearings for gas and diesel engines, wind turbines, motorsports equipment, bicycles, rollerblades, skateboards, computer disk drives, machine tools, dental hand-pieces and flap-actuators in aircrafts [10]. If corrosion, rapid wear and electric or magnetic fields limit the use of metals, silicon nitride is used instead [7,11,12]. Silicon nitride is even used in the bearings of underwater ocean tidal flow meters, where it withstands severe seawater corrosion conditions [13].

Due to its extreme strength, hardness and resistance to chemical and thermal factors [11,12,14–16], silicon nitride is commonly used in high-speed cutting tools, and to break up rocks during oil fracking [17]. Its heat resistance has led to uses in the valve trains of gas [18] and diesel engines [11], rotors and stators in gas-turbines [19,20], automotive turbochargers [21] and rocket nozzles and thrusters [22]. Few materials can survive these extreme conditions.

 

Outer space

Silicon nitride has powered human dreams into space. It is in the cryogenic pump bearings of NASA space shuttles [23], the thrusters of the Japanese space probe Akatsuki [24], and provides a lifespan of over 10 million years of space travel to tungsten-etched memory chips for spacecraft [25].

 

Amedica 6

 

Medical implants

Amedica Corporation makes spinal implants of medical-grade silicon nitride. These implants can be dense, porous, or even a combination that mimics the cortical-cancellous nature of living bone [26,27]. Silicon nitride is extremely biocompatible and bioactive, has bacterial resistance and shows superb bone affinity [28]. With more than 25,000 spine implantations and an eight-year track record, the material has yet to fail [29].

[contd. on page 32]

Silicon nitride can also be polished to provide an exceptionally smooth and wear-resistant surface for articulating applications, such as bearings for hip and knee replacements [30–32]. It is truly the ideal biomaterial, that not only meets, but exceeds all human implant requirements, such as:

material phase stability [33];

wear resistance [33,34];

strength and fracture toughness [9];

hydrophilicity [35];

favourable imaging [36]; and

bacterial resistance [37,69,72].

Amedica 2

 

Evolution of biomaterials

In days past, wood, leather, pig bladders, glass and ivory were used to repair broken hips, and treat hip arthritis [38]. Today, metals, bone grafts and polymers are used to rebuild human bodies, and help maintain function into old age.

All biomaterials degrade in the wet, warm, saline environment of the human body – metals fret and corrode [39], plastics oxidise [40] and allograft bone never fully heals [41], all of which lead to long-term failures. For example, toxic wear from all-metal hip bearings is a well-known problem [42]; and fretting, crevice and electrochemical corrosion in total hips is an emerging failure mode [43].

Silicon nitride can address these concerns. Not only is its wear extremely low [44], but the minimal wear particles are soluble and resorb in the body [45]. Silicon nitride is also chemically resistant, hard, stiff and has a high dielectric constant, all of which discourage fretting and corrosion [46].

Plastic (polyethylene) bearings in artificial hip and knee joints oxidise over time, leading to strategies such as cross-linking [47] and vitamin E doping [48] to slow down this process. Silicon nitride’s unique surface chemistry actually absorbs oxygen from polyethylene [44,49], thus limiting polyethylene oxidation in hip and knee replacements.

Bone grafts present significant limitations by way of harvesting morbidity, lack of bioactivity, and concerns about disease transmission [41]. Even synthetic bone fillers are made mostly from a material called hydroxyapatite, which has an affinity for bone but is still very brittle [50–52]. Silicon nitride bone scaffolds and bone-fusion devices [53] provide superior and reliable mechanical strength, that can be engineered to result in bone healing similar to hydroxyapatite [54].

On X-ray images, plastic implants are invisible, whereas metals appear solid, obscuring visibility of bone anatomy behind the implant. CAT scans and MRI scans suffer distortion from metal implants, leading to sub-optimal imaging. In contrast, silicon nitride is easily seen on X-rays; it does not block imaging of bone anatomy behind the implant, and its dielectric and non-magnetic nature eliminates distortion in CAT and MRI scans [36].

In summary, silicon nitride has the right combination of strength, toughness, wear, biocompatibility, bioactivity, bone integration, structural stability, corrosion resistance and easier imaging, all of which are desirable in medical implants [55].

 

Existing medical ceramics

Ceramics such as alumina (Al2O3) and zirconia (ZrO2) have been used in hip and knee replacements because of lower wear rates than metal surfaces [56–58]. Alumina is brittle and can break suddenly [59]; zirconia is stronger, but can transform after implantation, leading to erratic outcomes [60]. Zirconia was withdrawn in 2002, in the wake of failures from uncontrolled material transformation [61].

Today, a mix of alumina and zirconia, called zirconia-toughened alumina (ZTA) is a popular ceramic used in hip and knee implants [62]. ZTA is an engineering compromise between the alumina and zirconia [63]; however, ZTA recovered during repeat surgery shows that it too can change its composition in the body, and reduce its surface mechanical integrity [64].

In the body, alumina and ZTA both release oxygen ions, which can degrade polyethylene bearings [49,65]. Silicon nitride is unique in that it is a non-oxide ceramic, which means not only is it stronger and tougher than alumina and ZTA [9], it also absorbs oxygen away from polyethylene [66,67]. This remarkable property could take hip and knee replacements into the third and fourth decades of service, something that is only a speculation today.

 

Scientific and clinical data

Besides advantages in strength, wear, corrosion resistance and fracture toughness [68], there is more to silicon nitride. Here are Amedica’s recent findings on this novel bioceramic.

 

Bone healing

Silicon nitride turns on osteoblasts and suppresses osteoclasts. A manufacturing change called ‘nitrogen-annealing’ results in a near-200 per cent increase in bone formation by cells exposed to silicon nitride [54]. This finding has profound implications.

From tribal bone-setting in ancient cultures, to modern fracture fixation, surgeons have yet to alter the biology of bone healing. Nitrogen-annealed silicon nitride could accelerate bone healing, fusion and implant ingrowth. Cells adhere preferentially to silicon nitride over polymer or metal [69]. Cell adhesion promotes tissue development, and enhances the bioactivity of materials. Cell adhesion to silicon nitride is a function of pH, chemical and ionic changes at the material surface.

 

Composite devices

In a clinical trial, a spine spacer made of solid and porous silicon nitride fused the cervical spine without added cells or bone fillers [70]. Composite devices based on porous silicon nitride herald a new class of reconstructive implants [27,71].

Amedica 3

 

Infection prevention

Bacterial infection of any biomaterial implants is a serious risk. Solutions have included material coatings, surface texturing, antibiotic treatments and other enhancements to confer bacterial resistance. Silicon nitride offers an easy solution; not only is it is inherently resistant to bacteria and biofilm formation [37,69], recent studies have proven direct bactericidal effect against oral bacteria [72].

As with cell adhesion, the antibacterial behaviour of silicon nitride relates to its complex surface phenomena – invoking chemistry, surface pH, texture and electrical charge properties [35]. The surface modulation of silicon nitride to optimise the desired properties of implants is a potent advantage of the material [35].

Amedica 4

 

 

The future

The world is becoming better informed, more active and more demanding, and people are living longer than ever before. Scientists agree that silicon nitride will lead the future of material innovations. It comes closest to addressing the challenges of biomedical implant safety, high-performance and lifetime durability [73].

With proven success in industry and medical applications, and new research showing yet more beneficial attributes, silicon nitride continues to prove itself. With increased awareness, this advanced biomaterial technology will be found increasingly across reconstructive surgery and many other medical fields.

 

References

//probably just for the web if not enough space//

  1. R. Jugdaohsingh, Silicon and bone health, J Nutr Heal. Aging, 11(2), 99–110 (2007).
  2. L.M. Jurkic, I. Cepanec, S.K. Pavelic, and K. Pavelic, Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: new perspectives for therapy, Nutr. Metab. (Lond) 10(1), 2 (2013).
  3. D.M. Reffitt, and others, Orthosilicic acid stimulates collagen type 1 synthesis and osteoblastic differentiation in human osteoblast-like cells in vitro, Bone, 32(2), 127–135 (2003).
  4. M. Schneider, The importance of ammonia in mammalian cell culture, J. Biotechnol., 46(3), 161–185 (1996).
  5. R.C. Sangster and D.J. Fisher, Part C. Si3N4 products, uses and markets; pp. 137–246 in Form. Silicon Nitride from 19th to 21st Century, 2nd ed. Geneva, Switzerland, 2015.
  6. A.J. Fyzik and D.R. Beamant, Microstructure and properties of self-reinforced silicon nitride, J. Am. Ceram. Soc., 76(11), 2737–2744 (1993).
  7. F.L. Riley, Silicon nitride and related materials, J. Am. Ceram. Soc., 83(2), 245–265 (2000).
  8. W.A. Oldfather, A note on the etymology of the word ‘ceramic,’ J. Am. Ceram. Soc., 3(7), 537–542 (1920).
  9. B.S. Bal and M.N. Rahaman, orthopedic applications of silicon nitride ceramics, Acta Biomater., 8(8), 2889–2898 (2012).
  10. L. Wang, R.W. Snidle, and L. Gu, Rolling contact silicon nitride bearing technology: a review of recent research, Wear, 246 159–173 (2000).
  11. R.N. Katz, Applications of silicon nitride based ceramics in the U.S., MRS Proc., 287 197 (1992).
  12. R. Nathan Katz, Overview of ceramic materials, design, and application; in Mech. Eng. Handb. John Wiley & Sons, Inc., 2014.
  13. N. Liu, J. Wang, B. Chen, and F. Yan, Tribochemical aspects of silicon nitride ceramic sliding against stainless steel under the lubrication of seawater, Tribol. Int., 61 205–213 (2013).
  14. K.H. Jack, Sialon tool materials, Met. Technol., 9(1), 297–301 (1982).
  15. S.T. Buljan and V.K. Sarin, The future of silicon nitride cutting tools, Carbide Tool J., 14 4–7 (1985).
  16. G. Byrne, D. Dornfeld, and B. Denkena, Advancing cutting technology, CIRP Ann. – Manuf. Technol., 52(2), 483–507 (2003).
  17. A.R. Jennings Jr. and L.R. Stowe, Hydraulic fracturing utilizing a refractory proppant, US Pat. 4,892,147, 1–4 (1990).
  18. B.J. McEntire, R.W. Wills, and R.E. Southam, The development and testing of ceramic components in piston engines, final report, prepared for the U.S. Department of Energy under Contract with Oak Ridge National Laboratories, Contract No. DE-AC05-840R21400. Oak Ridge, TN 37831-6285, 1994.
  19. W.D. Carruthers, P.F. Becher, M.K. Ferber, and J. Pollinger, Advances in the development of silicon nitride and other ceramics; pp. 1–10 in Proc. ASME Turbo Expo 2002. Amsterdam, The Netherlands, 2002.
  20. B.J. McEntire, R.R. Hengst, W.T. Collins, A.P. Taglialavore, and R.L. Yeckley, Ceramic component processing development for advanced gas turbine engines, J. Eng. Gas Turbines Power, 115(1), 1–8 (1993).
  21. T. Shimizu, Kand others, Silicon nitride turbocharger rotor for high performance automotive engines, SAE Tech. Pap., No. 900656 (1990).
  22. A.J. Eckel, Silicon nitride rocket thrusters test fired successfully, NASA Res. News, https://web.archive.org/web/20090404161958/http:// (2009).
  23. S. Roy, Space Shuttle main engine enhancements, Marshall Sp. Flight Cent. Fact Sheet, http://www.nasa.gov/centers/marshall/news/backgrou (2000).
  24. N. Kawai, and others, Fracture behavior of silicon nitride ceramics subjected to hypervelocity impact, Int. J. Impact Eng., 38(7), 542–545 (2011).
  25. J. De Vries, D. Schellenberg, and L. Abelmann, Towards gigayear storage using a silicon-nitride/tungsten based medium, Cornell Univ. arXiv1310.2961v1(cs.ET] 9,(October 2013), 1–19 (2013).
  26. K. Bodišová, and others, Porous silicon nitride ceramics designed for bone substitute applications, Ceram. Int., 39(7), 8355–8362 (2013).
  27. K.S. Ely, A.C. Khandkar, R. Lakshminarayanan, and A.A. Hofmann, Hip prosthesis with monoblock ceramic acetabular cup, US Pat. 8,133,284, (2012).
  28. T.J. Webster, A.A. Patel, M.N. Rahaman, and B.S. Bal, Anti-infective and osteointegration properties of silicon nitride, poly (ether ether ketone), and titanium implants, Acta Biomater., 8(12), 4447–4454 (2012).
  29. Personal communication from William Jordan, director of regulatory affairs and quality assurance, Amedica Corporation, Salt Lake City, UT 84119, (2014).
  30. Y.S. Zhou, and others, Study on the possibility of silicon nitride—silicon nitride as a material for hip prostheses, Mater. Sci. Eng. C, 5 125–129 (1997).
  31. M. Mazzocchi, and others, On the possibility of silicon nitride as a ceramic for structural orthopaedic implants. part ii: chemical stability and wear resistance in body environment, J. Mater. Sci. Mater. Med., 19 2889–2901 (2008).
  32. M. Mazzocchi and A. Bellosi, On the possibility of silicon nitride as a ceramic for structural orthopaedic implants. part i: processing, microstructure, mechanical properties, cytotoxicity, J. Mater. Sci. Mater. Med., 19 2881–2887 (2008).
  33. B.S. Bal, and others, Testing of silicon nitride ceramic bearings for total hip arthroplasty, J. Biomed. Mater. Res. Part B Appl. Biomater., 87(2), 447–454 (2008).
  34. BJ McEntire, BS Bal, A Lakshminarayanan, and R Bock, Silicon nitride bearings for total joint arthroplasty, Bone Jt. J, 98-B(SUPP 1), 34 (2016).
  35. RM Bock, and others, Surface modulation of silicon nitride ceramics for orthopaedic applications, Acta Biomater., 26 318–330 (2015).
  36. M Anderson, J Bernero, and D Brodke, Medical imaging characteristics of silicon nitride ceramic a new material for spinal arthroplasty implants; p. 547 in 8th Annu. Spine Arthroplast. Soc. Glob. Symp. Motion Preserv. Technol. Miami, FL, 2008.
  37. DJ Gorth, and others, Decreased bacteria activity on Si3N4 surfaces compared with PEEK or titanium, Int. J. Nanomedicine, 7 4829–4840 (2012).
  38. DR Steinberg and ME Steinberg, The early history of arthroplasty in the United States, Clin. Orthop. Relat. Res., 374 55–89 (2000).
  39. D Sun, JA Wharton, and RJW Wood, The effects of proteins and ph on tribo-corrosion performance of cast CoCrMo: a combined electrochemical and tribological study, Tribol. Surfaces Interfaces, 2(3), 150–160 (2008).
  40. SL Rowell, CR Reyes, H Malchau, and OK Muratoglu, In vivo oxidative stability changes of highly cross-linked polyethylene bearings: an ex vivo investigation, J. Arthroplasty, 30 1828–1834 (2015).
  41. AS Brydone, D Meek, and S Maclaine, Bone grafting, orthopaedic biomaterials, and the clinical need for bone engineering, Proc. Inst. Mech. Eng. Part H J. Eng. Med., 224(12), 1329–1343 (2010).
  42. JS Melvin, T Karthikeyan, R Cope, and TK Fehring, Early failures in total hip arthroplasty – a changing paradigm, J. Arthroplasty, 29(6), 1285–1288 (2014).
  43. HJ Cooper, and others, Adverse local tissue reaction arising from corrosion at the femoral neck-body junction in a dual-taper stem with a cobalt-chromium modular neck., J. Bone Joint Surg. Am., 95(10), 865–72 (2013).
  44. RC Dante and CK Kajdas, A review and a fundamental theory of silicon nitride tribochemistry, Wear, 288 27–38 (2012).
  45. J Olofsson, T Grehk, and T Berlind, evaluation of silicon nitride as a wear resistant and resorbable alternative for total hip joint replacement, Biomatter, 2(2), 94–102 (2012).
  46. M Pettersson, and others, Fretting corrosion of silicon nitride against cobalt chromium and titanium medical alloys; p. Poster 0951 in Proc. Orthop. Res. Soc. 2015.
  47. G Lewis, Properties of crosslinked ultra-high-molecular-weight polyethylene, Biomaterials, 22(4), 371–401 (2001).
  48. A Turner, and others, The antioxidant and non-antioxidant contributions of vitamin E in vitamin E blended ultra-high molecular weight polyethylene for total knee replacement, J. Mech. Behav. Biomed. Mater., 31 21–30 (2014).

49 G. Pezzotti, Bioceramics for hip joints: the physical chemistry viewpoint, Materials (Basel)., 7 4367–4410 (2014).

  1. L Sun, CC Berndt, KA Gross, and A Kucuk, Material Fundamentals and clinical performance of plasma-sprayed hydroxyapatite coatings: a review, J. Biomed. Mater. Res. Appl. Biomater., 58 570–592 (2001).
  2. AA Chaudhry, and others, High-strength nanograined and translucent hydroxyapatite monoliths via continuous hydrothermal synthesis and optimized spark plasma sintering, Acta Biomater., 7(2), 791–799 (2011).
  3. H Yoshikawa and A Myoui, Bone tissue engineering with porous hydroxyapatite ceramics, J. Artif. Organs, 8(3), 131–136 (2005).
  4. MC Anderson and R Olsen, Bone Ingrowth into Porous Silicon Nitride, J. Biomed. Mater. Res., 92A 1598–1605 (2010).
  5. G Pezzotti, and others, Silicon nitride: a synthetic mineral for vertebrate biology, Sci. Rep., (in press) (2016).
  6. BS Bal and M Rahaman, The rationale for silicon nitride bearings in orthopaedic applications; pp. 421–432 in Adv. Ceram. – Electr. Magn. Ceram. Bioceram. Ceram. Environ. INTEC Open Access Publisher, 2011.
  7. R Tsukamoto, S Chen, H Shoji, and IC Clarke, improved wear performance with crosslinked UHMWPE and zirconia implants in knee simulation; p. 1686 in Proc. 51st Annu. Meet. Orthop. Res. Soc. Orthopaedic Research Society, Washington, DC USA, 2005.
  8. S Williams, and others, Wear and deformation of ceramic-on-polyethylene total hip replacements with joint laxity and swing phase microseparation, Proc. Inst. Mech. Eng. H., 217(2), 147–53 (2003).
  9. Y Takahashi, and others, Wear degradation of long-term in vivo exposed alumina-on-alumina hip joints: linking nanometer-scale phenomena to macroscopic joint design, J. Mater. Sci. Mater. Med., 23(2), 591–603 (2012).
  10. J Garino, MN Rahaman, and BS Bal, The reliability of modern alumina bearings in total hip arthroplasty, Semin. Arthroplasty, 17(3-4), 113–119 (2006).
  11. J Chevalier, S Grandjean, M Kuntz, and G Pezzotti, On the kinetics and impact of tetragonal to monoclinic transformation in an alumina/zirconia composite for arthroplasty applications, Biomaterials, 30(29), 5279–82 (2009).
  12. Recall of zirconia ceramic femoral heads for hip implants, Bull. Am. Ceram. Soc., 80(12), 14 (2001).
  13. P Merkert, Next generation ceramic bearings; pp. 123–125 in Bioceram. Jt. Arthroplast. Steinkopff, 2003.
  14. M Kuntz, N Shneider, and R Heros, Controlled zirconia phase transformation in BIOLOX®delta – a feature of safety; pp. 79–84 in Bioceram. Altern. Bear. Jt. Arthroplast. Steinkopff, New York, 2005.
  15. BJ McEntire, and others, Surface toughness of silicon nitride bioceramics: ii, comparison with commercial oxide materials, J. Mech. Behav. Biomed. Mater., 54 346–359 (2016).
  16. G Pezzotti, K Yamada, S Sakakura, and RP Pitto, Raman Spectroscopic analysis of advanced ceramic composite for hip prosthesis, J. Am. Ceram. Soc., 91(4), 1199–1206 (2008).
  17. G Pezzotti, and others, On the molecular interaction between ceramic femoral heads and polyethylene liners in artificial hip joints: I. Phenomenology, TBD,(In Press), 1–8 (2016).
  18. G Pezzotti, and others, On the molecular interaction between ceramic femoral heads and polyethylene liners in artificial hip joints: ii. molecular scale phenomena, TBD,(In Press), 1–10 (2016).
  19. BJ McEntire, BS Bal, MN Rahaman, J Chevalier, and G Pezzotti, Ceramics and ceramic coatings in orthopaedics, J. Eur. Ceram. Soc., 35(16), 4327–4369 (2015).
  20. TJ Webster, GA Skidmore, and R Lakshminarayanan, Increased bone attachment to silicon nitride (Si3N4) materials used in interbody fusion cages (IBF) compared to polyetheretherketone (PEEK) and titanium (Ti) materials – an in vivo study; pp. 1–5 in Proc. 2012 Annu. Meet. Orthopeaedic Soc. 2012.
  21. MP Arts, JFC Wolfs, and TP Corbin, The CASCADE trial: effectiveness of ceramic versus PEEK cages for anterior cervical discectomy with interbody fusion; Protocol of a Blinded Randomized Controlled Trial, BMC Musculoskelet. Disord., 14(1), 244 (2013).
  22. RM Taylor, JP Bernero, AA Patel, DS Brodke, and AC Khandkar, Silicon nitride – a new material for spinal implants, J. Bone Jt. Surg., 92-Br(Supp I] 133 (2010).
  23. G Pezzotti, and others, silicon nitride bioceramics induce chemically driven lysis in porphyromonas gingivalis, Langmuir, (2016).
  24. Z Krstic, V Krstic, Silicon nitride: the engineering material of the future J Mater Sci 47, 535–552 (2012)

 

For more details about Amedica, please visit www.amedica.com