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Orthopaedic Proceedings
Vol. 102-B, Issue SUPP_1 | Pages 28 - 28
1 Feb 2020
Kamada K Takahashi Y Tateiwa T Shishido T Masaoka T Pezzotti G Yamamoto K
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Introduction

Highly crosslinked, ultra-high molecular weight polyethylene (HXLPE) acetabular liners inherently have a risk of fatigue failure associated with femoral neck impingement. One of the potential reasons for liner failure was reported as crosslinking formulations of polyethylene, increasing the brittleness and structural rigidity. In addition, the acetabular component designs greatly affect the mechanical loading scenario, such as the offset (lateralized) liners with protruded rim above the metal shells, which commonly induce a weak resistance to rim impingement. The purpose of the present study was to compare the influence of the liner offset length on the impingement resistance in the annealed (first generation) and vitamin E-blended (second-generation) HXLPE liners with a commercial design.

Materials and Methods

The materials tested were the 95-kGy irradiated annealed GUR1020, and the 300-kGy irradiated vitamin E-blended GUR1050 HXLPE offset liners, which were referred to as “20_95” and “50E_300”, respectively. These liners had 2, 3, 4-mm rim offset, 2.45-mm rim thickness, and 36-mm internal diameter. Their rims were protruded above the metal rim at 2, 3, 4mm. Rim impingement testing was performed using an electrodynamic axial-torsional machine. The cyclic impingement load of 25–250N was applied on the rims through the necks of the femoral stems at 1Hz. The rotational torque was simultaneously generated by swinging the stem necks on the rims at 1Hz and its rotational angle was set at the range of 0–10˚. The percent crystallinity was analyzed on the as-received (intact) and impinged HXLPE acetabular rims by confocal Raman microspectroscopy.


Orthopaedic Proceedings
Vol. 101-B, Issue SUPP_5 | Pages 25 - 25
1 Apr 2019
Cazzola M Ferraris S Stella B Orlygsson G Ng CH Cempura G Scolaro C Prenesti E Yamaguchi S Pezzotti G Cochis A Rimondini L Spriano S
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In order to improve fast osseointegration, to modulate inflammatory response and to avoid biofilm formation, several attempts of surface modifications of titanium alloy in term of surface topography and chemistry have been performed over years, but this is still an open issue.

In our research work, a patented chemical treatment was developed and tailored to improve fast osseointegration and to allow further surface functionalization in order to get a multifunctional surface.

After the chemical treatment, Ti6Al4V shows a micro and nano-textured surface oxide layer with high density of hydroxyls groups, as summarized Figure 1: it is able to induce apatite precipitation (during soaking in Simulated Body Fluid), high wettability by blood, specific protein adsorption, positive osteoblast response and surface mechanical resistance to implantation friction.

Hydroxyl groups exposed by the treated surface also allow binding natural biomolecules such as polyphenols, which can further improve the rate and quality of osseointegration by adding anti-inflammatory, antibacterial and antitumoral effects suitable for implants in critical situations. Polyphenols have the further added value of being a low cost and eco-sustainable product, extractable from byproducts of wine and food industry.

On the chemically treated and functionalized samples, the surface characterization was performed using Folin&Ciocalteu test, fluorescence microscopy and XPS analysis in order to check the presence and activity of the grafted biomolecules (polyphenols from red grape pomace and green tea leaves). Cell tests were performed with Kusa A-1 cells highlighting the ability of polyphenols to improve osteoblasts differentiation and deposition of mineralized extracellular matrix.

Surface functionalization can also be performed with chitin derived biomolecules to reduce inflammation.

With the purpose of obtaining the antibacterial effect, during the chemical treatment a silver precursor can also be added to obtain in situ reduced silver nanoparticles embedded in the nano-structured oxide layer. The samples containing nanoparticles on the surface were characterized by means of TEM and FESEM observation highlighting the presence of well distributed and small-sized nanoparticles on the surface and through the thickness of the oxide layer. A long-lasting release in water was observed up to 14 days and antibacterial tests on Staphylococcus aureus showed the ability of the surface to reduce bacteria viability avoiding biofilm formation.

The results showed that the patented chemical treatment can improve the response of osteoblasts to titanium alloy implants, but is also a promising way to obtain multifunctional surfaces with antibacterial, antioxidant, anti-inflammatory and antitumoral properties that can be the future of orthopedic implants.


Orthopaedic Proceedings
Vol. 101-B, Issue SUPP_5 | Pages 116 - 116
1 Apr 2019
Bock R Pezzotti G Zhu W Marin E Rondinella A Boschetto F McEntire B Bal BS
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Introduction

Support of appositional bone ingrowth and resistance to bacterial adhesion and biofilm formation are preferred properties for biomaterials used in spinal fusion surgery. Although polyetheretherketone (PEEK) is a widely used interbody spacer material, it exhibits poor osteoconductive and bacteriostatic properties. In contrast, monolithic silicon nitride (Si3N4) has shown enhanced osteogenic and antimicrobial behavior. Therefore, it was hypothesized that incorporation of Si3N4 into a PEEK matrix might improve upon PEEK's inherently poor ability to bond with bone and also impart resistance to biofilm formation.

Methods

A PEEK polymer was melted and compounded with three different silicon nitride powders at 15% (by volume, vol.%), including: (i) α-Si3N4; (ii) a liquid phase sintered (LPS) ß-Si3N4; and (iii) a melt-derived SiYAlON mixture. These three ceramic powders exhibited different solubilities, polymorphic structures, and/or chemical compositions. Osteoconductivity was assessed by seeding specimens with 5 × 105/ml of SaOS-2 osteosarcoma cells within an osteogenic media for 7 days. Antibacterial behavior was determined by inoculating samples with 1 × 107 CFU/ml of Staphylococcus epidermidis (S. epi.) in a 1 × 108/ml brain heart infusion (BHI) agar culture for 24 h. After staining with PureBlu™ Hoechst 33342 or with DAPI and CFDA for SaOS-2 cell adhesion or bacterial presence, respectively, samples were examined with a confocal fluorescence microscope using a 488 nm Krypton/Argon laser source. Images were also acquired using a FEG-SEM in secondary and backscattered modes on gold sputter-coated specimens (∼20–30Å). Hydroxyapatite (HAp) deposition was measured using a laser microscope. Raman spectra were collected for samples in backscattering mode using a triple monochromator using a 532 nm excitation source (Nd:YVO4 diode-pumped solid-state laser).


Orthopaedic Proceedings
Vol. 99-B, Issue SUPP_3 | Pages 25 - 25
1 Feb 2017
McEntire B Zhu W Pezzotti G Marin E Sugano N Bal B
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Introduction

Femoral heads made from zirconia-toughened alumina (ZTA) are the most advanced bioceramic available for total hip arthroplasty. ZTA's superior mechanical properties result from the polymorphic transformation of its zirconia (ZrO2) phase in the presence of a propagating crack. In vitro derived activation energies predict that several human lifetimes are needed to reach a state of significant transformation;1 but in vivo confirmation of material stability is still lacking. This investigation determined if transition metal ions might be responsible for triggering the tetragonal to monoclinic (t®m-ZrO2) phase transformation in this bioceramic.

Materials and Methods

BIOLOX®delta femoral heads (CeramTec GmbH, Plochingen, Germany) were acquired and characterized for their surface monoclinic content, Vm, using Raman spectroscopy. Then they were physiologically scratched with different metals (i.e., Ti, CoCr, and Fe, n=3 each) to simulate in vivo staining as a result of acetabular shell impingement due to subluxation or dislocation. They were subsequently hydrothermally aged for up to 100 h in an autoclave at 98∼132°C and 1 bar pressure. Raman maps, each consisting of 120 spectra, were compiled and monoclinic contents, Vm, calculated for zones adjacent to and away from the metal stains.2 Activation energies for the t®m transformation in stained and non-stained zones were derived and compared to retrieved heads having service lives of between ∼45 days and ∼8 years.


Orthopaedic Proceedings
Vol. 99-B, Issue SUPP_3 | Pages 26 - 26
1 Feb 2017
Bal B Puppulin L McEntire B Pezzotti G
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Introduction

The longevity of highly cross-linked polyethylene (XLPE) bearings is primarily determined by its resistance to long-term oxidative degradation. Addition of vitamin E to XLPE is designed to extend in vivo life, although it has unintended consequences of inducing higher frictional torque and increased wear when articulating against metallic femoral heads.1–3 Conversely, lower friction was observed when oxide ceramic heads were utilized.3 Previous studies suggest that oxide ceramics may contribute to XLPE oxidation, whereas a non-oxide ceramic, silicon nitride (Si3N4), might limit XLPE's degradation.4 To corroborate this observation, an accelerated hydrothermal ageing experiment was conducted using static hydrothermal contact between XLPE and commercially-available ceramic femoral heads.

Materials and Methods

Two sets of four types of ceramic femoral heads, consisting of three oxides (Al2O3 BIOLOX®forte, and ZTA BIOLOX®delta, CeramTec, GmbH, Plochingen, Germany; and m-ZrO2 OXINIUMTM, Smith & Nephew, Memphis, TN, USA) and one non-oxide (MCSi3N4, Amedica Corp., Salt Lake City, UT, USA) were cut into hemispherical sections. Six highly crosslinked polyethylene liners (X3TM Stryker Orthopedics, Inc., Mahwah, New Jersey, USA) were also sectioned, gamma irradiated (32 kGy), and mechanically clamped (25 kN) to the convex surfaces of the ceramic heads (Figure 1(a)). All surfaces were dipped in water and placed into an autoclave at 121°C under adiabatic conditions for 24 hr. The test was repeated three times using two couples for each material along with XLPE-on-XLPE controls. Each XLPE sample was characterized before and after ageing using Raman spectroscopy for variations in their crystalline phase and oxidation indices using the intensities of unpolarized vibrational bands at 1296, 1305, and 1418 cm−1. Significance (p<0.05) was determined using Student's t-test with a sample size of n=18.


Orthopaedic Proceedings
Vol. 99-B, Issue SUPP_3 | Pages 47 - 47
1 Feb 2017
McEntire B Pezzotti G Bock R Zhu W Marin E Adachi T Bal B
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Introduction

Due to its remarkable stoichiometric flexibility and surface chemistry, hydroxyapatite (HAp) is the fundamental structural material in all vertebrates. Natural HAp's properties inspired an investigation into silicon nitride (Si3N4) to see if similar functionality could be engineered into this bioceramic. Biological and in situ spectroscopic analyses were used to monitor the response of osteosarcoma cells (SaOS-2) to surface-modulated Si3N4 and a titanium alloy after long-term in vitro exposure.

Materials and Methods

Four groups of Si3N4 discs, Ø12.7×1.0mm, (Amedica Corporation, Salt Lake City, UT USA) were subjected to surface treatments: (i) “As-fired;” (ii) HF-etched (5% HF solution for 45 s); (iii) Oxidized (1070°C for 7 h); and (iv) Nitrogen-annealed (1400°C for 30 min, 1.1 bar N2 gas).1 Titanium alloy discs (Ti6Al4V, ASTM F136) were used as a control group. SaOS-2 cells cultured for 24 h at 37°C were deposited (5×105 cells/ml) and incubated on the UV sterilized discs in an osteogenic medium for 7 days at 37°C. Cell proliferation was monitored using scanning electron and laser microscopy. The Receptor Activator of NF-kB Ligand (sRANKL) and the insulin growth factor 1 (IGF-1) were used to evaluate osteoclast formation and cell proliferation efficiency, respectively. In situ Raman spectroscopy was employed to monitor metabolic cell activity. Statistics (n≥3) were analyzed using the Student's t-test or one-way Analysis of Variance with p<0.05 considered significant.


Orthopaedic Proceedings
Vol. 99-B, Issue SUPP_4 | Pages 146 - 146
1 Feb 2017
McEntire B Jones E Bock R Ray D Bal B Pezzotti G
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Introduction

Periprosthetic infections are leading causes of revision surgery resulting in significant increased patient comorbidities and costs. Considerable research has targeted development of biomaterials that may eliminate implant-related infections.1 This in vitro study was developed to compare biofilm formation on three materials used in spinal fusion surgery – silicon nitride, PEEK, and titanium – using one gram-positive and one gram-negative bacterial species.

Materials and Methods

Several surface treated silicon nitride (Si3N4, MC2®, Amedica Corporation, Salt Lake City, UT), poly-ether-ether-ketone (PEEK, ASTM D6262), and medical grade titanium (Ti6Al4V, ASTM F136) discs Ø12.7 × 1mm were prepared or acquired for use in this well-plate study. Each group of discs (n=3) were ultrasonically cleaned, UV-sterilized, inoculated with 105Staphylococcus epidermidis (ATCC® 25922™) or Escherichia coli (ATCC® 14990™) and placed in a culture medium of phosphate buffered saline (PBS) containing 7% glucose and 10% human plasma on a shaking incubator at 37°C and 120 rpm for 24 or 48 hrs. Coupons were retrieved, rinsed in PBS to remove planktonic bacteria, placed in a centrifuge with fresh PBS, and vortexed. The bacterial solutions were serially diluted, plated, and incubated at 37°C for 24 to 48 hrs. Colony forming units (CFU/mm2) were counted using applicable dilution factors and surface areas. A two-tailed, heteroscedastic Student's t-test (95% confidence) was used to determine statistical significance.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_7 | Pages 28 - 28
1 May 2016
Bal B McEntire B Rahaman M Pezzotti G
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Introduction

Oxide-based alumina (Al2O3) is used to manufacture femoral heads for total hip arthroplasty (THA). Silicon nitride (Si3N4) is a non-oxide ceramic used to make spinal implants. Ceramic materials are believed to be bioinert, (i.e., stable under hydrothermal conditions). Indeed, clinical data have shown 15–20 year longevity of Al2O3 bearings in THA. In this work, we examined the surfaces of Al2O3 and Si3N4 after exposure to physiologic conditions to see if these ceramics are truly inert.

Materials and Methods

Four self-mated Ø28 mm diameter Al2O3 femoral heads (n=2 each of BIOLOX®forte, CeramTec, Plochingen, Germany; and BIOCERAM®, Kyocera Co., Kyoto, Japan), were retrieved during revision THA, between 7.7–10.7 years post-implantation. To simulate in vivo material aging, comparable, new Al2O3 and Si3N4 femoral heads (AMEDICA Corporation, Salt Lake City, UT, USA) were exposed to autoclave conditions (100°C-121°C; 300 hrs; n=3 heads, per material). Advanced Raman and cathodoluminescence spectroscopy, and electron microscopy were used to examine surface characteristics of each specimen, and quantify oxygen ion vacancy formation and composition.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_9 | Pages 130 - 130
1 May 2016
Pezzotti G Puppulin L Boffelli M McEntire B Rahaman M Yamamoto K Bal B
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Introduction

In total hip arthroplasty (THA), polyethylene (PE) liner oxidation leads to material degradation and increased wear, with many strategies targeting its delay or prevention. However, the effect of femoral head material composition on PE degradation for ceramic-PE articulation is yet unknown. Therefore, using two different ceramic materials, we compared PE surface alterations occurring during a series of standard ceramic-PE articulation tests.

Materials and Method

Ceramic-PE THA bearings were tested in a simulator, using ASTM F2003-02, ASTM F1714-96 (2013) and ISO 14242:1–3 standards. Acetabular liners (Apex-Link PolyTM, OMNI Life Science, East Taunton, MA, USA) were articulated against Ø28 mm Si3N4 femoral heads (Amedica Corp., Salt Lake City, UT, USA). For comparison, ArCom® PE liners (Biomet Inc. Warsaw, IN, USA) were also tested against Ø28 mm zirconia-toughened alumina (ZTA) femoral heads (BIOLOX®delta, CeramTec GmbH, Plochingen, Germany), under the same conditions. After 5 million cycles of wear, all specimens were examined using nano-spectroscopy tools. Evaluations were performed on six couples per group, plus 3 untested control couples; n= 6 (+3). Spectrographic examinations generated 8 maps of 400 points each randomly selected on the wear zones of each liner, with each map area being 20 µm2 at an in-plane spatial resolution of 1 µm.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_9 | Pages 29 - 29
1 May 2016
McEntire B Bal B Rahaman M Pezzotti G
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Introduction

The in vivo evolution of surface material properties is important in determining the longevity of bioceramics. Fracture toughness is particularly relevant because of its role in wear resistance. Some bioceramics, such as zirconia (ZrO2) undergo in vivo phase transformation, resulting in a marked reduction in toughness and commensurate increased wear. Here, we investigated the effect of accelerated aging on the surface toughness of alumina (Al2O3), zirconia-toughened alumina (ZTA), and silicon nitride (Si3N4) femoral heads, in order to identify the optimal ceramic material for in vivo implantation and long-term durability.

Materials

A newly developed Raman microprobe-assisted indentation method was applied to evaluate and compare surface fracture toughness mechanisms operative in Si3N4 (Amedica Corporation, Salt Lake City, UT, USA), Al2O3 and ZTA (BIOLOX® forte, and delta, respectively, CeramTec, GmbH, Plochingen, Germany) bioceramics. The Al2O3 and ZTA materials have long established histories in total hip arthroplasty; whereas Si3N4 has been newly developed for this purpose. The improved method proposed here consisted in coupling the “traditional” indentation technique with quantitative assessments of microscopic stress fields by confocal Raman microprobe piezo-spectroscopy. Concurrently, crack opening displacement (COD) profiles were also monitored by Raman spectroscopy. Toughness measurements were determined using both as-received and hydrothermally exposed (100–121°C for up to 300 hours) femoral heads.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_7 | Pages 45 - 45
1 May 2016
Bock R McEntire B Bal B Rahaman M Boffelli M Pezzotti G
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Introduction

Silicon nitride (Si3N4) is a ceramic material presently implanted during spine surgery. It has a fortunate combination of material properties such as high strength and fracture toughness, inherent phase stability, scratch resistance, low wear, biocompatibility, hydrophilic behavior, easier radiographic imaging and resistance to bacterial biofilm formation, all of which make it an attractive choice for orthopaedic applications beyond spine surgery. Unlike oxide ceramics, (e.g., alumina or Al2O3) the surface chemistry and topography of Si3N4 can be precisely engineered to address in vivo demands. Si3N4 can be manufactured to have an ultra-smooth, or highly fibrous, or porous morphology. Its chemistry can be varied from that of a silica-like surface composed of silanol moieties to one which is predominately comprised of silicon-amine functional groups.

Methods

In the present study, a Si3N4 bioceramic formulation was exposed to thermal, chemical, and mechanical treatments in order to induce changes in surface composition and features. The treatments included grinding and polishing, etching in hydrofluoric acid solution, and heating in nitrogen or air. Resulting surfaces were characterized using a variety of microscopy techniques to assess morphology. Surface chemical 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.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_1 | Pages 86 - 86
1 Jan 2016
Clarke I Pezzotti G Lakshminarayanan A Burgett-Moreno M Donaldson T
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Introduction

Looking for optimal solutions to wear risks evident in total hip arthroplasty (THA), silicon nitride ceramic bearings (Si3N4) are noted for demanding high-temperature applications such as diesel engines and aerospace bearings. As high-strength ceramic for orthopedic applications, Si3N4 offers improved fracture toughness and fracture strength over contemporary aluminas (Al2O3). Our pilot studies of Si3N4 in 28mm diameter THA showed promising results at ISTA meeting of 2007.1 In this simulator study, we compared the wear resistance of 40mm to 28mm diameter Si3N4 bearings.

The 28mm and 40mm bearings (Fig. 1) were fabricated from Si3N4 powder (Amedica Inc, Salt Lake City, UT).1 Wear tests run were run at 3kN peak load in an orbital hip simulator (SWM, Monrovia, CA) and. The lubricant was standard bovine serum (Hyclone: diluted to 17 mg/ml protein concentration). Wear was measured by gravimetric method and wear-rates calculated by linear regression. SEM and interferometic microscopic was performed at 3.5-million cycles (3.5Mc) to 12Mc.

The simulator was run to 3.5Mc duration with no consistent weight-loss trends. The bearings could show either small positive or negative weight fluctuations in an unpredictable manner (Fig. 2). Surface analysis showed protein layers up to 3μm thick, furrowed due to abrasion by small particles (Fig. 3). The low ceramic wear was camouflaged by protein contaminants alternatively forming and shedding. From 3.5 to 12.8Mc duration we experimented with various detergents and wash-procedures, all to no avail. Protein coatings were also more prevalent on 44 mm heads, likely due to frictional heating by the larger diameter effect. Selected heads were washed with a mild acid solution - the cumulative effect appeared to be removal of some protein layers, but not in a predictable manner.

The Si3N4 ceramic is used in demanding industrial applications and it is therefore unfortunate that we are yet not able to quantify the actual wear performance of Si3N4/ Si3N4 bearings (COC). The contaminating protein layers combined with low-wearing silicon nitride obscured the actual wear data. This has also been a problem in prior studies with alumina and zirconia bearings. Considerable challenges still stand in the way of the optimal biomaterials choices that will result in reduced risk of failure while providing extended lifetimes. Thus important issues remain unsolved and call for innovative solutions. Searching for a more effective ‘wear-measurement’ remedy, we noted that abrasive slurries of bone cement (PMMA) used in contemporary simulator studies were effective in promoting adverse wear in polyethylene bearings. These investigations also revealed that PMMA debris did not damage CoCr heads2,3, alumina heads4,5 or diffusion-hardened zirconia heads (ZrDH).6 We can therefore speculate at this ISTA meeting of 2014 that future ceramic wear tests should incorporate PMMA slurries. Here a new hypothesis can be formulated, that PMMA particulates will provide a continual and beneficial removal of contaminating proteins from the ceramic surfaces (see Fig. 3) and thereby aid definition of low-wearing COC bearings such as Si3N4.

The application of non-oxide ceramics such as silicon nitride presented here may become a viable alternative for THA designs of next decade.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_3 | Pages 32 - 32
1 Jan 2016
McEntire B Bock R Rahaman M Bal BS Webster T Pezzotti G
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Silicon nitride spinal fusion cages have been successfully used in the treatment or correction of stenosis, disc herniation, trauma, and other deformities of the spinal column since 2008. To date over 14,000 devices have been implanted with perioperative and postoperative complication rates of less than 0.2%. This remarkable achievement is due in part to the material itself. Silicon nitride is an ideal interbody material, possessing high strength and fracture toughness, inherent phase stability, biocompatibility, hydrophilicity, excellent radiographic imaging, and bacterial resistance. These characteristics can lead to implants that aid in prevention of nosocomial infections and achieve rapid osteointegration. In this paper, we will review the various in vitro and in vivo studies that demonstrate silicon nitride's effective bacteriostatic and osteointegration characteristics, and compare these to the two most common cage materials – titanium and poly-ether-ether-ketone (PEEK). Human case studies will be also reviewed to contrast the clinical performance of these biomaterials. In comparison to the traditional devices, silicon nitride shows lower infection rates, higher bone apposition, and essentially no fibrous tissue growth on or around the implant. To better understand the mechanisms underlying these benefits, surface characterization studies using scanning electron microscopy coupled with XPS chemical analyses, sessile water drop techniques and streaming zeta potential measurements will be reported. Data from these studies will be discussed in relation to the physiochemical reasons for the observed behavior. Silicon nitride is a non-oxide ceramic in its bulk; but possesses a protective Si-N-O transitional layer at its surface. It will be shown that the chemistry and morphology of this layer can be modified in composition, thickness and structure resulting in marked changes in chemical species, surface charge, isoelectric points and wetting behavior. It is postulated that the needle-like grain structure of silicon nitride coupled with its enhanced wettability play important roles in inhibiting biofilm formation, while its surface chemical environment consisting of silicon diimide Si(NH)2, silicic acid Si(OH)4, and derivatives of ammonia, NH3, NH4OH, lead to improved bone reformation and bacteriostasis, respectively. Few materials have this combination of properties, making silicon nitride a unique biomaterial that provides improved patient care and outcomes with low comorbidities.


Orthopaedic Proceedings
Vol. 98-B, Issue SUPP_4 | Pages 44 - 44
1 Jan 2016
Takahashi Y Pezzotti G Yamamoto K
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Introduction

Vitamin-E (VE, dl-α-tocopherol) is a powerful antioxidant for highly cross-linked polyethylene (XLPE). It was previously reported that VE-stabilized XLPE succeeded in retaining no measurable oxidation even after accelerated aging tests combined with cyclic loading or lipid absorption. Thus, VE-stabilized XLPE is nowadays recognized worldwide as one of the new standard materials in total hip arthroplasty (THA). However, the effects of such VE addition on physical behavior of polyethylene remain to be fully elucidated by contrast to the clear statement of its chemical role (i.e., the enhanced oxidation resistance) in the published literature. In this presentation, we shall attempt to provide those missing notations and to explore the microstructural and biomechanical role of VE in XLPE acetabular liner on the molecular scale.

Methods

The two different types of XLPE acetabular liners, VE-blended and VE-free (no VE-blended) component (n=3 for each sample), were investigated by means of laser-scanning confocal polarized micro-Raman spectroscopy. In both components, the cross-linking was achieved by electron-beam irradiation with a total dose of 300kGy in vacuum. Raman spectroscopy offers non-destructive, contactless, and high-resolution analyses of polymer morphologies. In this study, we performed an in-depth profiling of crystalline and non-crystalline phase (i.e., amorphous and intermediate phase between crystalline and amorphous regions) percentages and degree of molecular orientation in the above two liners before and after introducing the 10% plastic deformation via uniaxial compression loading at room temperature. These results were also compared to the morphological analyses under the same compression conditions performed on the virgin conventional polyethylene (Virgin liner) without radiation crosslinking as well as VE blending.


Orthopaedic Proceedings
Vol. 93-B, Issue SUPP_IV | Pages 455 - 455
1 Nov 2011
Pezzotti G
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Total hip arthroplasty (THA) represents a very spread and effective surgical procedure. Surgeons and technologists make daily efforts in improving the outcomes of THA, with the ultimate goal of creating a prosthesis that reliably lasts at least as long as a human lifetime. While the results of primary hip arthroplasty are generally very good, revision surgeries might score variable success with regards to their clinical outcomes. In addition, they invariably represent an expensive procedure and a severe burden to the patients. Thus, a reduction of the failure rates of only a few percents can, due to the large number of patients involved, have a vast influence on the accumulated costs and patient suffering. In other words, the key issue in hip arthroplasty resides in the improvement of the prostheses with regard to their long-term in vivo reliability. These circumstances amply justify a continuous search for new hip prostheses with improved structural characteristics and elongated lifetimes.

Most recent innovative trends in THA have focused on the improvement of the tribological behavior of hip joints and challenged the achievement of a longer durability, with the potential for a service-life spanning several decades. Such trends have naturally led to an increase in the use of ceramic materials, either as ceramic femoral heads yet coupled with advanced acetabular cups made of polyethylene (i.e., with improved molecular structure and quality), or as ceramic hip components for both acetabular and femoral bearing surfaces. The greater driving force in using ceramic bearings is their potential of systematically reducing periprosthetic osteolysis (i.e., mainly arising from polyethylene wear debris), which could potentially reduce the number of surgical revisions. The high inertness and biocompatibility of ceramic materials may also reduce to a minimum the collateral effects on the human body, as possibly observed with metallic prostheses (e.g., contamination by metal ions, hypersensitivity, etc.). Despite those advantages, chipping and fracturing have severely limited the popularity of ceramic components. As a further issue, it should be noted that ceramic-on-ceramic articulations strongly require high precision in setting the orientation of the components during surgery (in order to avoid excessive impingement on the ceramic surface). Partly fractured ceramic bearings necessarily dictate revision. The main reason is that the ceramic remnants in the articulation would give rise to severe third-body wear, especially in the presence of a softer bearing counterpart. Clearly, ceramic components offer a very high potential for further improving both structural performance and lifetime of hip joints but, being made of fragile materials, they also require significant progress in surgery technique, further advancements in joint design and materials manufacturing processes, as well as a peer non-destructive control of their structural reliability.

In this presentation, we shall first have a brief survey on the main cases of failure in the recent history of hip prostheses. Then, a description of the most advanced and recent technological approaches to material preparation, reliability control and non-destructive analysis of hip components will also be given. The main aim of this presentation is to drive the attention of the international orthopaedic community on the need for a highly interdisciplinary approach to the study of hip joint arthroplasty. In this context, we provide here some vivid examples of how newly developed Raman spectroscopic methods may provide final solutions to historical problems related to the chemical and structural reliability of materials widely employed in total hip arthroplasty.


Orthopaedic Proceedings
Vol. 93-B, Issue SUPP_IV | Pages 432 - 432
1 Nov 2011
Takahashi Y Pezzotti G Kakimoto A Hashimoto J Sugano N
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Multiaxial rotation of femoral component is generated in a wide range against UHMWPE tibial insert during ambulation or deep bending activities. Simultaneously, microscopic oscillation and twisting might accompany with such a wide-range motion.

Such a combined in-vivo kinetics is expected to bring more severe wear to the sliding surface of knee joint prostheses than that in a case of single macro-kinetics (i.e., that commonly reproduced by conventional wear simulators). In order to reproduce clinical surface degradation correctly and quantitatively in simulator tests, we have to consider microscopic motions at the joint bearing surfaces. The purpose of this study is to analyze the influence of the composite knee motion on wear using a non-destructive spectroscopic approach.

The crystalline phase in UHMWPE is pre-oriented in the tibial insert from the manufacturing process, but the orientation of crystalline lamellae is sensitive to mechanical loading. Therefore, the orientation of the crystalline lamellae on the surface of retrieved UHMWPE tibial inserts could reflect the local motions in vivo generated in the joint during ambulation. The visualization of (orthorhombic) crystalline lamellae might ultimately lead to the possibility of tracking back the wear history of the joint. In this study, polarized Raman spectroscopy was employed in order to non-destructively visualize the lamellar orientation in UHMWPE tibial inserts, which were retrieved after exposures in human body elapsing several years.

According to this Raman analysis and in comparison with an unused insert, the orientation of surface lamellae was found to have been clearly changed due to wear in accordance to the local motion of the femoral component. Additionally, we could obtain information about the origin of delamination from the in-depth profile for lamellae orientation angle. This study not only shows the possibility of optimizing the UHMWPE structure to minimize wear but also gives a hint for the development of knee simulators of the next generation.


Orthopaedic Proceedings
Vol. 92-B, Issue SUPP_I | Pages 167 - 167
1 Mar 2010
Pezzotti G
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Combined techniques of fracture mechanics and confocal Raman microprobe spectroscopy were applied to characterize, after increasing periods of environmental exposure, bulk and surface toughness values in an advanced alumina/zirconia composite. This material is used in joint prostheses (BIOLOX® delta femoral heads, manufactured by CeramTec AG). Besides conventional fracture mechanics characterizations, including different types of fracture toughness test, Raman and fluorescence microprobe spectroscopy provided a microscopic insight into the effect of environmentally assisted processes of zirconia phase transformation at the surface on the fracture toughness of the material. We have found that the tetragonal-to-monoclinic polymorphic transformation occurs in the studied composite material as a consequence of an environmentally assisted process, although severe exposures are needed for to obtain a substantial increase of the monoclinic content. Such severe exposures in vitro correspond to exposures in human body of several lifetimes. The effect of an exposure of 10 h in autoclave (in vitro accelerated test) was carefully examined, because this span of time corresponds:

to the period of time recommended for testing in vitro by ISO standard; and,

to approximately the lifetime expected for a prosthesis in vivo.

The main experimental outcomes of confocal Raman spectroscopy and fracture mechanics assessments can be summarized as follows:

the crack-tip toughness level measured in the as-received material was comprehensive of a tangible contribution by transformation toughening, thus showing that phase transformation in the zirconia dispersoids plays a positive role in the toughening behavior of the material;

after the material was environmentally aged in vitro for periods of the order of hundreds of hours, its surface toughness was reduced by about one-third; but, even in the case of such a severe exposure, the surface toughness of the composite was at least the same as that of monolithic alumina;

the observed decrease of fracture toughness by about one-third was limited to the very surface of the material (i.e., to a layer of the order of the tens of microns) and did not affect the bulk fracture behavior of the composite.

It appears that concerns arising from the brittleness of alumina-based materials and, thus, from their vulnerability to fracture due to unexpected load situation, can be successfully counteracted by properly adding a dispersion of zirconia particles to the alumina matrix. Such an addition enables the obtainment of a composite material, whose fracture resistance is greatly enhanced by a crack-shielding effect due to phase-transformation processes occurring in the zirconia dispersoids.


Orthopaedic Proceedings
Vol. 92-B, Issue SUPP_I | Pages 138 - 138
1 Mar 2010
Ikeda J Mabuchi M Murakami T Miyaji F Ueno M Pezzotti G
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Alumina and zirconia have been extensively used for orthopedic implants, such as hip and knee joint replacements. In 1982, Dr Hironobu Oonishi and Kyocera Corp. put the world’s first ceramic knee component, KOM, to practical use. This ceramic knee component shows excellent clinical results for long-time use. Now, the ceramic material of the knee component is changed from the alumina to the zirconia, and over 5000 ceramic components have been used in Japan so far.

The 3 mol% yttria stabilized polycrystalline zirconia (3Y-TZP) has been used as surgical grade zirconia. The 3Y-TZP possesses higher fracture strength and toughness as compared to monolithic alumina. However, it is generally known that spontaneous transformation may also occur at relatively low temperatures in hydrothermal environment as in the case of human body for the 3Y-TZP. Therefore, there is a concern of the degradation of mechanical and wear properties as a consequence of the transformation (low temperature degradation).

Our previous studies confirmed that low temperature degradation can be prevented by optimizing sintering temperature and adopting a Hot Isostatic Press process. In this study, we evaluated the effects of surface nature of ceramic material and heat treatment. Since grinding and polishing of the ceramic implants (e.g. femoral heads) might induce phase transformation, residual stress and microcracks, it is needed to examine the validity of the manufacturing process.

At first, the 3Y-TZP samples with grinded (#400) and mirror polished surfaces were prepared and exposed in saturated vapor in an autoclave at 121°C for 150 h (aging test). Some of the samples were subjected to a heat treatment and then to aging test. Before and after aging test, change in crystal structure was evaluated by X-ray diffraction. Then, for evaluation of the aging effects for microscopic area of the ceramic, a Vickers indentation was introduced on the surface before the aging test. Changes in crystal structure and residual stress were evaluated by a Raman spectroscopic technique.

In the results of the aging test, it was found that the degree of the increase in monoclinic fraction of both grinded and polished surfaces was lower in the samples with heat treatment than in those without heat treatment. These results indicate that the phase stability of the 3Y-TZP was improved by the heat treatment after machining.

Around the indentation, circular-like deformation zone and cracks extending from the four corners of the indentation were observed. After the aging test, the transformed area gradually spread towards neighborhood regions depending on the aging time. Besides, a distinct progress of phase transformation at around the crack was also observed. On the other hand, in the samples subjected to the heat treatment, no transformed area was observed around the indentation. These results suggest that low temperature degradation could be prevented by the heat treatment after the machining.

The residual stress fields induced in phase-transformed areas increased during aging test, and heat treatment after the machining was also able to prevent phase transformation even if surface damages, such as indentation or machining, were introduced on the samples.


Orthopaedic Proceedings
Vol. 90-B, Issue SUPP_I | Pages 162 - 162
1 Mar 2008
Della Gaspera O Pezzotti G Variola F Falcone G Sbaizero O De Santis V Clarke I Proietti L
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The experimental determination of residual stress fields on the surface of retrieved femoral heads represents a fundamental step in understanding their wear degradation behavior and the tribological mechanisms, which are operative on the femoral joint during its working life time. In this work, the surface of retrieved alumina and zirconia (Al2O3 and ZrO2) femoral heads were investigated by piezo-spectroscopic tecniques based both on photoluminescence and Raman effects. The high spatial resolution of the laser, impinging on the investigated surface (typically about 1 micron of lateral resolution), enabled us estimating patterns and magnitude of residual stress in extremely narrow zones, comparable with the grain size of the material.

Four retrieved ceramic femoral heads were analyzed. Two balls were made of alumina with a typical grain size of from 4 to 10 microns. Both alumina balls were retrieved after only few years from implantation, due to septic and aspetic loosening. The remaining two femoral heads were made of zirconia with a typical grain size of 1 micron. These latter balls were retrieved after 2 and 13 years, respectively (both for loosening problems). With a systematic collection of a large number of data on a microscopic level it was possible to assess the retrieved femoral heads in to to, thus extending the microscopic analysis to the entire joint.

In allumina balls retrieved after short time implantation, a macroscopic stress field was found, which arose from manufacturing, loading history, and the displacements acting on the femoral head during its lifetime. This stress field was completely overcome by a microscopic residual stress field due to local contacts (e.g., local shocks owing to microseparation, impinging and wear contacts). On the other hand, in zirconia femural heads, the major amount of surface deterioration after long-term exposure arose from tetragonal-to-monoclinic transformation in biological environment. These data allowed us to draw interesting considerations about the role of the material microstructure and the peculiar kinematic mechanisms involved with the use of femoral heads made of different materials.

Spectroscopic techniques, which are complementary to in vitro testing procedures and stress analyses based on finite-element methods, can be very useful for improving the design of the femoral head and for optimizing the microstructural characteristics of the ceramic materials employed. Based on this and previous fluorescence and Raman spectroscopic studies, we also propose that a systematic screening of the ceramic implants before implantation can strongly reduce the probability of failure of the implant.


Orthopaedic Proceedings
Vol. 90-B, Issue SUPP_I | Pages 188 - 188
1 Mar 2008
Variola F Pezzotti G Gaspera OD Falcone G De Santis V agliocchetti G Sakakura S Clarke I
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Alumina ceramic has been used in total hip arthoplasty since the 70’s and, in the last 30 years, a considerable evolution has occurred in designing the microstructural features of this material, taking advantage of improved processing techniques, as the hot isostatic pressing. As a result, a high degree of densification (> 99.5) has been achieved in materials with a high degree of purity and, especially, with a fine grain size ( 2 microns). The surface stress field acting on a femoral head inoperation is not only due to working conditions, but also to unexpected factors, as local impacts on the surface as a result of partial dislocations, formation of debris, etc. These additional factors greatly contribute to activate degradation mechanisms which, unfortunately, may lead to failure of the implant.

In this study, five alumina femoral heads were investigated, which were retrieved from patients after different periods of time. Among those investigated femoral heads, two belonged to a first-generation type of alumina material with a relatively coarse grainsize (average value 8 microns) and were retrieved due to surface degradation after long periods of implantation (19 and 17 years, respectively); the remaining three implants analyzed were instead recently manufactured implants with a fine grain size; they were retrieved after relatively short periods because of different causes as, for example, cup or stem loosening.

Surface stress analysis using the luminescence of Cr3+impurity in alumina was performed on the retrieved femoral heads and a statistical comparison was attempted among implants with different microstructural characteristics. The investigation led to estimate average residual stress and statistical stress distributions as a function of the location on the femoral head.

The analysis was performed both on the very surface and in the sub-surface of the head, using the confocal and the through-focus configurations of the optical spectrometer, respectively. Different statistical distributions of residual stress were observed in alumina femoral heads with different grain sizes and models were created to understand their dependence on processing and surface loading.