Silicon nitride (Si₃N₄)

History of Silicon Nitride

Silicon nitride (Si₃N₄) is a non-metallic compound composed of silicon and nitrogen, first discovered in 1857. The first synthetic silicon nitride was developed by Deville and Wohler in 1859. Since its discovery, silicon nitride had remained an academic curiosity for almost a century, until the 1950s when commercial interests started to increase and the material was developed in various refractory applications. Notable strides in manufacturing processes during the 1970s through the 1980s reduced the production cost of the compound, and silicon nitride quickly established a foothold in many industrial applications, particularly as a structural ceramic. It was also in the 1980s that a global effort started to expand the use of silicon nitride in internal combustion engines and high-temperature gas turbines. Throughout the years, further improvements to its synthesis, processing, and properties resulted in it being one of the most studied ceramics in history. Because its material properties are well studied and understood, silicon nitride commercial use has significantly expanded greatly in recent years.

Silicon nitride has been commercially produced and synthesized by the reaction of various silicon carriers with nitrogen or ammonia. Further R&D in the 1980s led to the development of a number of industrial applications for silicon nitride-based materials, paving the way to manufacture different types of silicon nitride – reaction-bonded silicon nitride (RBSN), hot-pressed silicon nitride (HPSN), sintered reaction-bonded silicon nitride (SRBSN), sintered silicon nitride (SSN), partial pressure sintered silicon nitride (PSSN) and hot isostatically pressed silicon nitride (HIPSN). These methods of fabrication have governed the resulting properties and applications of silicon nitride, allowing for a great deal of flexibility and customization to create precisely the material needed for an application.

Key Properties of Silicon Nitride

Silicon nitride is considered a very important engineering ceramic due to its adaptability to many different forms, with each form having distinctive properties. At high temperature, silicon nitride shows excellent mechanical properties including low density, high bending strength, high elastic modulus and fracture toughness, and high abrasion wear, as well as solid particle erosion resistance. In other words, this material is extremely strong and extremely tough. The material also shows excellent thermal properties, with minimal expansion and contraction due to temperature and the ability to withstand thermal shock (fast, significant changes in temperature). Finally, silicon nitride possesses exceptional chemical properties including stability against most acids and bases, corrosive gases and liquid metals.

Rolling contact fatigue (RCF) tests conducted on several ceramic-based materials subjected to loads of high-performance bearings have shown that only fully dense silicon nitride could outperform bearing steels. Fully dense Si₃N₄ bearing materials have shown RCF has ten times the longevity of high-performance bearing steel. Rotating bodies at high speed could lead to significant centrifugal stress. Being a low-density material makes silicon nitride as light as aluminum. However, this property also gives the material another benefit. The low density of silicon nitride reduces the centrifugal stress on the outer races of these rotating bodies at high speeds. The high tensile strengths of silicon nitride ceramics can resist elongation and offer outstanding flexural strengths to withstand yielding or rupturing at elevated transverse stresses. Fully dense Si₃N₄ also exhibits high fracture toughness and high moduli properties, giving the material an excellent resistance to multiple wearing phenomena. This enables it to withstand severe operating conditions that may cause other ceramic materials to generate flaws, deform, or collapse.

Aside from its superior mechanical properties, silicon nitride also exhibits an array of exceptional thermal properties that makes it suitable for demanding industrial applications. Thermal conductivity is the intrinsic ability of a material to transfer or conduct heat. The heat transfer coefficient is a critical factor that characterizes the applicability of engineered materials to be used in any industrial application under extreme temperature requirements. Because of its unique chemical composition and microstructure, silicon nitride offers similarly low thermal conductivity as compared to metals.

Such properties have enabled silicon nitride to reduce thermal conductivity in severe temperature applications significantly. Thermal expansion is another concern and occurs when materials are heated and their size and volume increase in small increments. This expansion varies depending on the material being heated. The degree of expansion of a material per 1°C rise in temperature is indicated by its coefficient ratio of thermal expansion. The strong atomic bonds of silicon nitride are what give this material low coefficients of thermal expansion, making its distortion values very low with respect to changes in temperature.

Owing to its exceptional thermal qualities, silicon nitride radio frequency (RF) properties are not considerably affected during high-velocity applications as compared to other ceramics. Silicon nitride is the preferred material for various RF applications due to its moderate dielectric constant (the ability of a substance to store electrical energy in an electric field) and low RF loss in combination with its superior strength and thermal resistance.

It is the unique combination of properties possessed by silicon nitride that led to further research for its use as a structural ceramic in biomedical applications. The biocompatibility of silicon nitride was already established in the late 1980s, as confirmed by an initial in vitro study and followed by an in vivo investigation involving silicon nitride implantation in animals. A study in 1999 further supported the claim of the biocompatibility of silicon nitride for the propagation of functional human bone cells performed outside a living organism (in vitro). These findings further propelled silicon nitride as an emerging biomedical material. Aside from its biocompatibility, silicon nitride is known to have a surface chemistry favorable for bone formation (osteogenesis) and increased bone-to-implant contact, resulting in the improved structural and functional integration between the living bone and the surface of an artificial implant (osseointegration).

Silicon nitride’s excellent stability due to its strong atomic bonding makes the material highly resistant to corrosion by acidic and basic solutions at room temperature. This is of utmost importance when considering long term implants inside the aqueous, salty environment of the human body. Corrosion resistance is primarily attributed to the formation of the oxide layer at the surface of the material. The same resistance was observed when corrosion tests were carried out subjecting silicon nitride to hot gases, molten salts and metals and in complex environments. This formation of the oxide layer plays a central, complex role in the corrosion resistance of the material.

Due to its self-reinforced microstructure, exceptionally high strength and toughness and many excellent properties have made silicon nitride an attractive structural component for numerous applications in various industries including biomedical applications.

Silicon Nitride Uses & Applications

As one of the significant structural ceramics that have developed, silicon nitride has found valuable use in wear-resistant and high-temperature applications.

Automotive Industry

Currently, the predominant application of silicon nitride is in the automotive industry. The material is found in applications for engine parts and engine accessory units including turbochargers for lower inertia and reduced engine lag and emissions, glow plugs for faster startup, exhaust gas control valves for increased acceleration, and rocker arm pads for gas engines to lower wear. Regulatory restrictions on engine emissions and higher fuel costs have driven the use of silicon nitride in the automotive industry. Each application within the automotive industry requires subtly different yet tightly controlled attributes to be able to meet the requirements and attain the greatest improvement in performance versus other materials.

Bearing Industry

Owing to its excellent shock resistance compared to other ceramics, silicon nitride is considered an extremely promising material for the fabrication of high-performance all-ceramic or hybrid steel-ceramic rolling contact bearings. Due to its extreme strength, toughness, and resistance to chemical and thermal factors, silicon nitride offers significant benefits by extending contact fatigue life. As a low-density material, silicon nitride can greatly reduce the dynamic loading during ball contacts in very high-speed applications such as those in gas turbine engines. The material also has notable applications in severe lubrication and wear conditions including extreme temperature, large temperature differential, ultra-high vacuum as well as in safety-critical applications, enabling the material to respond to the specific requirements, i.e. aircraft maintenance operations. As evidenced by their outstanding performance in extreme environments, silicon nitride bearings are expected to continue to gain wide acceptance in many industrial applications.

Aviation and Aerospace Industry

In the aerospace industry, traditional materials like metals and composites have typically been used for aircraft production. The need for new materials that can withstand extreme conditions has led to the use of silicon nitride in various aerospace applications.  Its mechanical robustness and ability to perform at high temperatures make it a material of choice for replacing legacy materials used in ball bearings, radomes, and RF windows. Customization of silicon nitride to specific applications is important for optimizing its use in the aerospace industry. Silicon nitride is incredibly light for the strength it provides, making it ideal for aerospace and other applications where both weight and strength are critically important.

Hypersonic Industry

To meet the increasing demands of the hypersonic industry, cutting-edge materials are required. Silicon nitride stands out as a top choice for meeting these demands, boasting a range of properties that set it apart from other materials. Its high strength and fracture resistance are unparalleled among advanced ceramics. Silicon nitride has proven itself to be a valuable asset in the field of hypersonic technology, with its unique combination of lightweight, strength, and thermal resistance.

Electronics Industry

The unique electrical properties of silicon nitride have caused an increasing usage in microelectronics applications as an insulator and chemical barrier in the manufacture of integrated circuits for the protective packaging of devices. Silicon nitride is used as a passivation layer with a high diffusion barrier against water and sodium ions, both of which are major sources of corrosion and instability in microelectronics. The material is also used as an electrical insulator between polysilicon layers in capacitors of analog chips. Silicon nitride also found use in the xerographic process as one of the photo drum layers. Owing to its excellent elastic properties, silicon nitride has been the most accepted material for cantilevers, which are the sensing elements for atomic force microscopes.

The use of silicon nitride has also been recognized in the field of optics, having great transparency in the spectral range, giving rise to Si₃N₄ photonics. The broadband nature of Si₃N₄ has allowed it to be used in biochemical and biomedical optical applications, biophotonics, tele- and data communications, and optical signal processing, sensing from visible through near to mid-infrared wavelengths.

Welding Industry

Silicon nitride’s strength, toughness, and resistance to thermal shock have played a vital role in the development of welding technology. This advanced ceramic has recently been utilized in the electric resistance welding industry as a replacement for traditional steel components, specifically welding rollers. The use of silicon nitride in these rollers has resulted in significant benefits for welding facilities, including increased efficiency, longer service life, and reduced maintenance. Silicon nitride’s unique properties make it an attractive choice for companies looking to improve the performance and reliability of their welding equipment.

Biomedical Applications

There is a surprising array of material properties that makes silicon nitride the ideal biomaterial. Further scientific investigations have produced innovative methods in the potential use of silicon nitride in a variety of biomedical applications.

Biosensors

The last three decades have seen significant growth in the development of biosensing devices and their utilization in various fields of applications. While the biosensor technology has already reached maturity and has established a global market, problems surrounding stability, sensitivity, and size have limited the general use of optical biosensors for real field applications. Silicon-based integrated photonic biosensors have the potential to solve these shortcomings by offering early diagnostic tools with better sensitivity, specificity, and reliability and possibility of improving effectiveness of in-vitro and in-vivo diagnostics.

Recently, silicon nitride-based fabrication technology has been successfully integrated with biochemistry, facilitating the creation of innovative biosensing devices with high sensitivity and selectivity . Silicon nitride offers other advantages compared to other materials, with the absence of impurities and excellent control of film composition and thickness. These features proved important for ultra-thin layer applications in gate and tunnel dielectrics in the fabrication of biosensing devices. Silicon nitride’s high-grade electronic and mechanical properties have made the material exceptionally attractive for biosensor applications.

Spinal and Orthopedic Implants

With its superior mechanical, thermal and chemical properties, silicon nitride has other unique properties that may make it a valuable material for spinal implants and prosthetic replacements for hip and knee joints. As a bioinert material, silicon nitride is biocompatible per ISO 10993-01 standards (Internal data on file). The material has demonstrated antibacterial and osseointegrative properties to support bone formation. As a spinal implant, its partially radiolucent property produces no image distortions in plain radiography, allowing a more precise view of the implant during surgery and postsurgical evaluation.

SINTX, as the only contract manufacturer of biomedical silicon nitride implants, has had great success in the spinal implant arena with favorable results.

Dental Applications

Having demonstrated itself as an beneficial implant material for spinal implants , researchers have turned to the potential of silicon nitride for dental implants and craniomaxillofacial implants as well. In an article posted by The American Ceramic Society, silicon nitride was labeled as a “killer ceramic material,” due to its antibacterial property that inhibits Porphyromonas gingivalis, a bacterium found in oral cavities that causes gum disease. In this joint research invitro study, the bacteria underwent lysis (breaking down of the cell, often by viral, enzymic, or osmotic mechanisms that compromise its integrity) on polished surfaces of silicon nitride material. Silicon nitride demonstrated the ability to degrade the bacteria’s biological makeup in six days. This breakdown of cell function was primarily due to the formation of peroxynitrite, an oxidizing and nitrating agent capable of damaging molecules in cells, including DNA and proteins. The research study also found out that altering the surface chemistry of silicon nitride will influence the formation of peroxynitrite and thus affect bacteria metabolism in various ways. The unique properties of silicon nitride demonstrate potential in oral health applications.

There has been an increasing demand for metal-free dental implants and has contributed to the interest in silicon nitride material for the potential dental implant global market.

SINTX Technologies – Leading the Way in Silicon Nitride Manufacturing

Medical Manufacturing

As a leading manufacturer of silicon nitride-based biomaterials for medical applications, SINTX Technologies is the only FDA registered and ISO 13485:2016 certified silicon nitride medical device manufacturing facility in the world. SINTX has more than 20 years of industry experience combining scientific, technical, medical, and manufacturing expertise in silicon nitride. SINTX Technologies’ innovative technology has been published in more than 85 peer-reviewed papers. Recognized for its product versatility, the company has produced over 50,000 silicon nitride implants of different shapes and compositions since 2008.

Industrial Manufacturing

As a highly innovative silicon nitride manufacturer, SINTX has been recognized with 13 US patents and has additional patents pending internationally. With its 30,000 sq. ft. facility designed for rapid prototyping and development, equipped with dedicated research and development, product development laboratories, and vertically integrated manufacturing capabilities, SINTX is poised to lead pioneering work in industrial product design and biomaterial formulation.

 

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