Bryan J. McEntire

Fabrication and characterization of Nasicon electrolytes

Abstract The processing and properties of Nasicon ceramic electrolytes are described for processes involving (1) the mechanical mixing of powder components, (2) gel formation, (3) hot-pressing, and (4) hot-gas isostatic pressing (HIP).

Surface modulation of silicon nitride ceramics for orthopaedic applications.

UNLABELLED Silicon nitride (Si3N4) has a distinctive combination of material properties such as high strength and fracture toughness, inherent phase stability, scratch resistance, low wear, biocompatibility, hydrophilic behavior, excellent radiographic imaging and resistance to bacterial adhesion, all of which make it an attractive choice for orthopaedic implants. Unlike oxide ceramics, the surface chemistry and topography of Si3N4 can be engineered to address potential in vivo needs. Morphologically, it can be manufactured to have an ultra-smooth or highly fibrous surface structure. Its chemistry can be varied from that of a silica-like surface to one which is predominately comprised of silicon-amines. In the present study, a Si3N4 bioceramic was subjected to thermal, chemical, and mechanical treatments in order to induce changes in surface composition and features. The treatments included grinding and polishing, etching in aqueous hydrofluoric acid, and heating in nitrogen or air. The treated surfaces were characterized using a variety of microscopy techniques to assess morphology. Surface chemistry and phase composition were determined using X-ray photoelectron and Raman spectroscopy, respectively. Streaming potential measurements evaluated surface charging, and sessile water drop techniques assessed wetting behavior. These treatments yielded significant differences in surface properties with isoelectric points ranging from 2 to 5.6, and moderate to extremely hydrophilic water contact angles from ∼65° to ∼8°. This work provides a basis for future in vitro and in vivo studies which will examine the effects of these treatments on important orthopaedic properties such as friction, wear, protein adsorption, bacteriostasis and osseointegration. STATEMENT OF SIGNIFICANCE Silicon nitride (Si3N4) exhibits a unique combination of bulk mechanical and surface chemical properties that make it an ideal biomaterial for orthopaedic implants. It is already being used for interbody spinal fusion cages and is being developed for total joint arthroplasty. Its surface texture and chemistry are both highly tunable, yielding physicochemical combinations that may lead to enhanced osseointegration and bacterial resistance without compromising bulk mechanical properties. This study demonstrates the ease with which significant changes to Si3N4s surface phase composition, charging, and wetting behavior can be induced, and represents an initial step towards a mechanistic understanding of the interaction between implant surfaces and the biologic environment.

Silicon Nitride Bioceramics Induce Chemically Driven Lysis in Porphyromonas gingivalis

Organisms of Gram-negative phylum bacteroidetes, Porphyromonas gingivalis, underwent lysis on polished surfaces of silicon nitride (Si3N4) bioceramics. The antibacterial activity of Si3N4 was mainly the result of chemically driven principles. The lytic activity, although not osmotic in nature, was related to the peculiar pH-dependent surface chemistry of Si3N4. A buffering effect via the formation of ammonium ions (NH4(+)) (and their modifications) was experimentally observed by pH microscopy. Lysis was confirmed by conventional fluorescence spectroscopy, and the bacterias metabolism was traced with the aid of in situ Raman microprobe spectroscopy. This latter technique revealed the formation of peroxynitrite within the bacterium itself. Degradation of the bacterias nucleic acid, drastic reduction in phenilalanine, and reduction of lipid concentration were observed due to short-term exposure (6 days) to Si3N4. Altering the surface chemistry of Si3N4 by either chemical etching or thermal oxidation influenced peroxynitrite formation and affected bacteria metabolism in different ways. Exploiting the peculiar surface chemistry of Si3N4 bioceramics could be helpful in counteracting Porphyromonas gingivalis in an alkaline pH environment.

Bioactive silicon nitride: A new therapeutic material for osteoarthropathy

While the reciprocity between bioceramics and living cells is complex, it is principally governed by the implant’s surface chemistry. Consequently, a deeper understanding of the chemical interactions of bioceramics with living tissue could ultimately lead to new therapeutic strategies. However, the physical and chemical principles that govern these interactions remain unclear. The intricacies of this biological synergy are explored within this paper by examining the peculiar surface chemistry of a relatively new bioceramic, silicon nitride (Si3N4). Building upon prior research, this paper aims at obtaining new insights into the biological interactions between Si3N4 and living cells, as a consequence of the off-stoichiometric chemical nature of its surface at the nanometer scale. We show here yet unveiled details of surface chemistry and, based on these new data, formulate a model on how, ultimately, Si3N4 influences cellular signal transduction functions and differentiation mechanisms. In other words, we interpret its reciprocity with living cells in chemical terms. These new findings suggest that Si3N4 might provide unique new medicinal therapies and effective remedies for various bone or joint maladies and diseases.

Silicon Nitride: A Synthetic Mineral for Vertebrate Biology

The remarkable stoichiometric flexibility of hydroxyapatite (HAp) enables the formation of a variety of charged structural sites at the material’s surface which facilitates bone remodeling due to binding of biomolecule moieties in zwitterionic fashion. In this paper, we report for the first time that an optimized biomedical grade silicon nitride (Si3N4) demonstrated cell adhesion and improved osteoconductivity comparable to highly defective, non-stoichiometric natural hydroxyapatite. Si3N4’s zwitterionic-like behavior is a function of the dualism between positive and negative charged off-stoichiometric sites (i.e., N-vacancies versus silanols groups, respectively). Lattice defects at the biomaterial’s surface greatly promote interaction with positively- and negatively-charged functional groups in biomolecules, and result in the biologically effective characteristics of silicon nitride. These findings are anticipated to be a starting point for further discoveries of therapeutic bone-graft substitute materials.

Bacteriostatic behavior of surface modulated silicon nitride in comparison to polyetheretherketone and titanium

Perioperative and latent infections are leading causes of revision surgery for orthopaedic devices resulting in significant increased patient care, comorbidities, and attendant costs. Identifying biomaterial surfaces that inherently resist biofilm adhesion and bacterial expression is an important emerging strategy in addressing implant-related infections. This in vitro study was designed to compare biofilm formation on three biomaterials commonly employed in spinal fusion surgery-silicon nitride (Si3 N4 ), polyetheretherketone (PEEK), and a titanium alloy (Ti6Al4V-ELI) -using one gram-positive and one gram-negative bacterial species. Disc samples from various surface treated Si3 N4 , PEEK, and Ti6Al4V were inoculated with 105 CFU/mm2 Staphylococcus epidermidis (ATCC®14990™) or Escherichia coli (ATCC® 25922™) and cultured in PBS, 7% glucose, and 10% human plasma for 24 and 48 h, followed by retrieval and rinsing. Vortexed solutions were diluted, plated, and incubated at 37 °C for 24 to 48 h. Colony forming units (CFU/mm2 ) were determined using applicable dilution factors and surface areas. A two-tailed, heteroscedastic Students t-test (95% confidence) was used to determine statistical significance. The various Si3 N4 samples showed the most favorable bacterial resistance for both bacilli tested. The mechanisms for the bacteriostatic behavior of Si3 N4 are likely due to multivariate surface effects including submicron-topography, negative charging, and chemical interactions which form peroxynitrite (an oxidative agent). Si3 N4 is a new biomaterial with the apparent potential to inhibit biofilm formation.

Human osteoblasts grow transitional Si/N apatite in quickly osteointegrated Si3N4 cervical insert

Silicon nitride (Si3N4) ceramics possesses surface chemistry that accelerates bone repair, as previously established by in vitro experiments using both osteosarcoma and mesenchymal cells. The release of silicic acid and nitrogen compounds from the surface Si3N4 enhanced in vitro cellular activity. The results of this study demonstrate for the first time that the osseointegration behavior previously observed is operative with a peculiar chemistry within the human milieu. Si and N elements stimulated progenitor cell differentiation and osteoblastic activity, which ultimately resulted in accelerated bone ingrowth. At the molecular scale, insight into the effect of silicon and nitrogen ions released from the Si3N4 surface was obtained through combined histomorphometric analyses, Raman, Fourier-transform-infrared, and X-ray photoelectron spectroscopies. Identical analyses conducted on a polyetheretherketone (PEEK) spinal explant showed no chemical changes and a lower propensity for osteogenic activity. Silicon and nitrogen are key elements in stimulating cells to generate bony apatite with crystallographic imperfections, leading to enhanced bioactivity of Si3N4 biomedical devices. STATEMENT OF SIGNIFICANCE This research studies osseointegration processes comparing results from explanted PEEK and Si3N4 spinal spacers. Data show that the formation of hydroxyapatite on silicon nitride bio-ceramic surfaces happens with a peculiar mechanism inside the human body. Silicon and nitrogen were incorporated inside the bony tissue structure allowing the developing of off-stoichiometric bony apatite and stimulating progenitor cell differentiation/osteoblastic activity. Silicon and nitrogen ions released from the Si3N4 surface were detected through combined histologic analyses, Raman microspectroscopy, Fourier-transform-infrared, and X-ray photoelectron spectroscopies.

Surface toughness of silicon nitride bioceramics: II, Comparison with commercial oxide materials.

Raman microprobe-assisted indentation, a micromechanics method validated in a companion paper, was used to compare the surface toughening behaviors of silicon nitride (Si3N4) and alumina-based bioceramics employed in joint arthroplasty (i.e., monolithic alumina, Al2O3, and yttria-stabilized zirconia (ZrO2)-toughened alumina, ZTA). Quantitative assessments of microscopic stress fields both ahead and behind the tip of Vickers indentation cracks propagated under increasing indentation loads were systematically made using a Raman microprobe with spatial resolution on the order of a single micrometer. Concurrently, crack opening displacement (COD) profiles were monitored on the same microcracks screened by Raman spectroscopy. The Raman eye clearly visualized different mechanisms operative in toughening Si3N4 and ZTA bioceramics (i.e., crack-face bridging and ZrO2 polymorphic transformation, respectively) as compared to the brittle behavior of monolithic Al2O3. Moreover, emphasis was placed on assessing not only the effectiveness but also the durability of such toughening effects when the biomaterials were aged in a hydrothermal environment. A significant degree of embrittlement at the biomaterial surface was recorded in the transformation-toughened ZTA, with the surface toughness reduced by exposure to the hydrothermal environment. Conversely, the Si3N4 biomaterial experienced a surface toughness value independent of hydrothermal attack. Crack-face bridging thus appears to be a durable surface toughening mechanism for biomaterials in joint arthroplasty.

Processing and Characterization of Silicon Nitride Bioceramics

As a relatively new biomaterial, silicon nitride (Si3N4) is currently used as an arthrodesis device in the cervical and thoracolumbar spine, and it is under consideration as a bearing material in total joint arthroplasty. In this paper, the development and validation of the manufacturing processes used in the production of Si3N4 biomedical implants are presented and discussed. Manufacturing was conducted in a facility specifically dedicated for this purpose using processes designed to yield net shape intervertebral spinal spacers by conventional dry-pressing, CNC machining of components in the green state, sintering, and hot isostatic pressing. These manufacturing methods were industrialized using Taguchi fractional factorial experimental designs, followed by implementation of statistical process controls. The roles of various processing parameters including raw materials, pressing, and firing conditions (i.e., time, temperature, and pressure) are elucidated. For these devices, it was demonstrated that acceptable physical, mechanical, and dimensional properties were consistently obtained from carefully designed and statistically controlled processes.

Surface toughness of silicon nitride bioceramics: I, Raman spectroscopy-assisted micromechanics.

Indentation micro-fracture is revisited as a tool for evaluating the surface toughness of silicon nitride (Si3N4) bioceramics for artificial joint applications. Despite being unique and practical from an experimental perspective, a quantitative assessment of surface fracture toughness using this method is challenging. An improved method has been developed, consisting of coupling indentation with confocal (spatially resolved) Raman piezo-spectroscopy. Empowered by the Raman microprobe, the indentation micro-fracture method was found to be capable of providing reliable surface toughness measurements in silicon nitride biomaterials. In designing the microstructures of bioceramic bearing couples for improved tribological performance, surface toughness must be considered as a fundamentally different and distinct parameter from bulk toughness. The coupling of indention crack opening displacements (COD) with local stress field assessments by spectroscopy paves the way to reliably compare the structural properties of bioceramics and to quantitatively monitor their evolution during environmental exposure.