Owing to its superior bulk mechanical properties, poly (ether ether ketone) (PEEK) has gained popularity over the past 15 years as a metal substitute in biomedical implants. Low surface energy is a fundamental issue with PEEK implants. This low surface energy caused by a moderately hydrophobic surface may be able to inhibit cellular adherence and result in the development of an inflammatory response, which may result in cell necrosis and apoptosis. In this work, plasma and ozone treatments have been utilized to surface activate PEEK and graft ionic bioactive polymer polyNaSS (poly (sodium styrene sulfonate)) successfully on the surface to promote cellular attachment and biomineralization. The main goal of our research has been to find a stable green process for surface modification of PEEK by plasma/ozone approaches to increase PolyNaSS grafting efficiency and biomineralization. To further the field of bioactive orthopedic and dental implant technology, this research attempts to address a significant constraint of PEEK implants while preserving their favorable mechanical properties.
Osteoblastic and chemical responses to Poly (ether ether ketone) (PEEK) material have been improved using a variety of low-temperature plasmas (LTPs). Surface chemical properties are modified, and can be used, using low-temperature plasma (LTP) treatments which change surface functional groups. These functional groups increase biomineralization, in simulated body fluid conditions, and cellular viability. PEEK scaffolds were treated, with a variety of LTPs, incubated in simulated body fluids, and then analyzed using multiple techniques. First, scanning electron microscopy (SEM) showed morphological changes in the biomineralization for all samples. Calcein staining, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) confirmed that all low-temperature plasma-treated groups showed higher levels of biomineralization than the control group. MTT cell viability assays showed LTP-treated groups had increased cell viability in comparison to non-LTP-treated controls. PEEK treated with triethyl phosphate plasma (TEP) showed higher levels of cellular viability at 82.91% ± 5.00 (n = 6) and mineralization. These were significantly different to both the methyl methacrylate (MMA) 77.38% ± 1.27, ethylene diamine (EDA) 64.75% ± 6.43 plasma-treated PEEK groups, and the control, non-plasma-treated group 58.80 ± 2.84. FTIR showed higher levels of carbonate and phosphate formation on the TEP-treated PEEK than the other samples; however, calcein staining fluorescence of MMA and TEP-treated PEEK had the highest levels of biomineralization measured by pixel intensity quantification of 101.17 ± 4.63 and 96.35 ± 3.58, respectively, while EDA and control PEEK samples were 89.53 ± 1.74 and 90.49 ± 2.33, respectively. Comparing different LTPs, we showed that modified surface chemistry has quantitatively measurable effects that are favorable to the cellular, biomineralization, and chemical properties of PEEK.
more » « less- Award ID(s):
- 2148653
- PAR ID:
- 10490441
- Publisher / Repository:
- Materials
- Date Published:
- Journal Name:
- Materials
- Volume:
- 17
- Issue:
- 1
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 171
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract Poly(ether ether ketone) (PEEK) is a semi‐crystalline thermoplastic with excellent mechanical and chemical properties. PEEK exhibits a high degree of resistance to thermal, chemical, and bio‐degradation. PEEK is used as a biomaterial in the field of orthopedic and dental implants; however, due to its intrinsic hydrophobicity and inert surface, PEEK does not effectively support bone growth. Therefore, new methods to modify PEEK's surface to improve osseointegration are key to next‐generation polymer implant materials. Unfortunately, PEEK is a challenging material to both modify and subsequently characterize thus stymieing efforts to improve PEEK osseointegration. In this manuscript, we demonstrate how surface‐initiated atom transfer radical polymerization can be used to modify novel PEEK microparticles (PMP). The hard core‐soft shell microparticles were synthesized and characterized by dynamic light scattering, attenuated total reflection‐infrared, X‐ray photoelectron spectroscopy, and transmission electron microscopy, indicating the grafted materials increased solubility and stability in a range of solvents. The discovered surface grafted PMP can be used as compatibilizers for the polymer‐tissue interface.
-
The engineering thermoplastic poly(ether ether ketone) (PEEK) has a rigid backbone that crystallizes relatively slowly upon cooling the melt. In this study, fast scanning chip calorimetry (FSC) was used to analyze isothermal crystallization between 170 and 285 °C, a range from about 27 K above the glass transition temperature up to the melting temperature. Incorporation of carbon nanotubes (CNT) enhances nucleation at all crystallization temperatures, including low temperatures. FSC also was employed to study crystallization at cooling rates spanning 0.33 to 8000 K/s, important as PEEK is subject to these conditions during melt processing. The critical cooling rate to produce a vitrified sample was increased from 500 K/s in the neat PEEK to 4000 K/s in a 5% CNT/PEEK nanocomposite due to faster nucleation rate caused by heterogeneous nucleation.more » « less
-
more » « less
Poly(ether ether ketone) (PEEK) was found to form gels in the benign solvent 1,3-diphenylacetone (DPA). Gelation of PEEK in DPA was found to form an interconnected, strut-like morphology composed of polymer axialites. To our knowledge, this is the first report of a strut-like morphology for PEEK aerogels. PEEK/DPA gels were prepared by first dissolving PEEK in DPA at 320 °C. Upon cooling to 50 °C, PEEK crystallizes and forms a gel in DPA. The PEEK/DPA phase diagram indicated that phase separation occurs by solid–liquid phase separation, implying that DPA is a good solvent for PEEK. The Flory–Huggins interaction parameter, calculated as χ12 = 0.093 for the PEEK/DPA system, confirmed that DPA is a good solvent for PEEK. PEEK aerogels were prepared by solvent exchanging DPA to water then freeze-drying. PEEK aerogels were found to have densities between 0.09 and 0.25 g/cm3, porosities between 80 and 93%, and surface areas between 200 and 225 m2/g, depending on the initial gel concentration. Using nitrogen adsorption analyses, PEEK aerogels were found to be mesoporous adsorbents, with mesopore sizes of about 8 nm, which formed between stacks of platelike crystalline lamellae. Scanning electron microscopy and X-ray scattering were utilized to elucidate the hierarchical structure of the PEEK aerogels. Morphological analysis found that the PEEK/DPA gels were composed of a highly nucleated network of PEEK axialites (i.e., aggregates of stacked crystalline lamellae). The highly connected axialite network imparted robust mechanical properties on PEEK aerogels, which were found to densify less upon freeze-drying than globular PEEK aerogel counterparts gelled from dichloroacetic acid (DCA) or 4-chlorphenol (4CP). PEEK aerogels formed from DPA were also found to have a modulus–density scaling that was far more efficient in supporting loads than the poorly connected aerogels formed from PEEK/DCA or PEEK/4CP solutions. The strut-like morphology in these new PEEK aerogels also significantly improved the modulus to a degree that is comparable to high-performance crosslinked aerogels based on polyimide and polyurea of comparable densities.
-
more » « less
Abstract The surface chemistry of silicon‐incorporated diamond‐like carbon (Si‐DLC) was tailored utilizing oxygen and fluorine plasma treatments. Successful anchoring of oxygen and fluorine functional groups to the surface of Si‐DLC was verified using X‐ray photoelectron spectroscopy. The impact of surface modification of Si‐DLC on hydrophobicity was correlated with the viability of L929 mouse fibroblasts. The confocal microscopy and viability results indicated that oxygen‐treated Si‐DLC showed increased cell viability compared to untreated Si‐DLC and fluorine‐treated Si‐DLC samples 5 days after seeding. The increased cell viability was correlated with the conversion of the hydrophobic surface of Si‐DLC into a hydrophilic surface by oxygen plasma treatment.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/ma17010171
