Morphology and electrical conductivity of carbon-coated Nickel reinforced high-performance polymer nanocomposites.

Novel nanocomposites of poly (ether-ketone) (PEK) reinforced with carbon-coated Nickel nanoparticles (CCNi) were synthesized through a sequential process involving cost-effective ball milling and hot compaction. Scanning electron microscopy revealed an excellent dispersion and a three-dimensional network of CCNi nanoparticles in the matrix, causing a significant improvement in the electrical conductivity and electromagnetic interference shielding effectiveness (SE). Carbon coating of about 5 nm thick over Ni nanoparticle probably helps in uniform dispersion, avoids its oxidation and reduces its agglomeration in the matrix. An exceptionally low percolation threshold of 2.1 vol.% CCNi was found, and eight-orders of magnitude enhancement in the dc-electrical conductivity was achieved. The highest dc- and ac-electrical conductivities achieved were more than 0.01 S cm-1at 5.89 vol.% CCNi nanoparticles content which were the highest values amongst reported Ni-filled polymer composites and comparable with those of carbon nanotubes filled PEK nanocomposites. Electromagnetic interference SE of the CCNi/PEK nanocomposites was measured in the X-band, and a total SE (SET) of 17.52 dB was obtained for 5.89 vol.% CCNi reinforced PEK nanocomposite.

Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketone)s and Linear Poly(ether ketone)s.

Poly(ether ether ketone) dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4'-(4-fluorobenzoyl)diphenyl ether and 3,5-dihydroxy-4'-(4-fluorobenzoyl)diphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy)-3,5-bis(4-fluorobenzoyl)benzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketone)s having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

A Preclinical Trial Protocol Using an Ovine Model to Assess Scaffold Implant Biomaterials for Repair of Critical-Sized Mandibular Defects.

The present work describes a preclinical trial (in silico, in vivo and in vitro) protocol to assess the biomechanical performance and osteogenic capability of 3D-printed polymeric scaffolds implants used to repair partial defects in a sheep mandible. The protocol spans multiple steps of the medical device development pipeline, including initial concept design of the scaffold implant, digital twin in silico finite element modeling, manufacturing of the device prototype, in vivo device implantation, and in vitro laboratory mechanical testing. First, a patient-specific one-body scaffold implant used for reconstructing a critical-sized defect along the lower border of the sheep mandible ramus was designed using on computed-tomographic (CT) imagery and computer-aided design software. Next, the biomechanical performance of the implant was predicted numerically by simulating physiological load conditions in a digital twin in silico finite element model of the sheep mandible. This allowed for possible redesigning of the implant prior to commencing in vivo experimentation. Then, two types of polymeric biomaterials were used to manufacture the mandibular scaffold implants: poly ether ether ketone (PEEK) and poly ether ketone (PEK) printed with fused deposition modeling (FDM) and selective laser sintering (SLS), respectively. Then, after being implanted for 13 weeks in vivo, the implant and surrounding bone tissue was harvested and microCT scanned to visualize and quantify neo-tissue formation in the porous space of the scaffold. Finally, the implant and local bone tissue was assessed by in vitro laboratory mechanical testing to quantify the osteointegration. The protocol consists of six component procedures: (i) scaffold design and finite element analysis to predict its biomechanical response, (ii) scaffold fabrication with FDM and SLS 3D printing, (iii) surface treatment of the scaffold with plasma immersion ion implantation (PIII) techniques, (iv) ovine mandibular implantation, (v) postoperative sheep recovery, euthanasia, and harvesting of the scaffold and surrounding host bone, microCT scanning, and (vi) in vitro laboratory mechanical tests of the harvested scaffolds. The results of microCT imagery and 3-point mechanical bend testing demonstrate that PIII-SLS-PEK is a promising biomaterial for the manufacturing of scaffold implants to enhance the bone-scaffold contact and bone ingrowth in porous scaffold implants. MicroCT images of the harvested implant and surrounding bone tissue showed encouraging new bone growth at the scaffold-bone interface and inside the porous network of the lattice structure of the SLS-PEK scaffolds.

Semi-crystalline sulfonated poly(ether ketone) proton exchange membranes: The trade-off of facile synthesis and performance.

Improving the performance of proton exchange membranes (PEMs) through the synthesis of sulfonated polymers with elaborate molecular structures has received extensive approval. However, the tedious synthetic process and consequently high costs restrain their possible substitution for Nafion, a classic PEM material. Herein, a series of semi-crystalline sulfonated poly(ether ketone)s with fluorene-based units were prepared via direct copolymerization of commercially available monomers and followed post-sulfonation, namely SPEK-FD-x, where × represents the molar ratio of the fluorene-containing monomer to the employed bisphenol monomers. The entire synthetic pathway was facile without involving hardly accessible materials. Subsequently, various properties of SPEK-FD-x membranes were investigated and further compared with Nafion 117. Due to the formation of the well-defined hydrophilic-hydrophobic microphase separation morphology and the reinforcement of the PEK crystalline regions, the SPEK-FD-x membranes exhibited outstanding proton conductivity, resistance for methanol permeation, as well as dimensional, thermal, oxidative, and mechanical stability. Among them, the overall behavior of the SPEK-FD-25 membrane was comparable to or even greater than that of Nafion 117, most importantly, it also performed decently in both H2/air fuel cells and direct methanol fuel cells. Therefore, with the straightforward synthesis and superior performance, the SPEK-FD-x membranes may serve as a promising alternative to Nafion.

To Evaluate and Compare the Effect of Various Surface Treatment Modalities on Shear Bond Strength of Composite to Polyetherketoneketone and SEM Analysis: An In vitro Study.

Context: It is a challenge to bond resin materials with polyetherketoneketone (PEKK). To increase the bond strength, surface treatments using chemical adhesion, mechanical adhesion, or a combination of both can be used. Aims: The objective of the present study was to evaluate and compare the shear bond strength of PEKK to the composite resin after various surface treatments and to evaluate the fracture mode analyses. Materials and Methods: One hundred and twenty PEKK specimens were randomly divided into four groups (n = 30) after three different surface treatments (95% sulfuric acid etching, airborne abrasion with 110 µm aluminum-oxide, and 99% acetone). With the help of polytetrafluorethylene tube, resin composite (3M ESPE) was bonded on all the specimens, thermocycled, and subjected to shear bond strength testing. Thereafter, 15 samples from each group were assessed for fracture mode analyses using a scanning electron microscope. Statistical Analysis Used: Mean, Standard deviation, one-way analysis of variance (ANOVA) f-test, post hoc Tukey's test. Results: Statistical analysis using one-way ANOVA f-test revealed that the results were significant with a P < 0.05 with the maximum value obtained in the case of air abraded group and the minimum value obtained in the case of the untreated group. Adhesive failure mode was the most common among the air-abraded group. Conclusions: The mechanical surface treatment group (air abrasion) showed higher shear bond strength than the chemical surface treatment groups (sulfuric acid and acetone). The mixed-type fracture mode was most commonly noted in the air-abraded group.

Surface Modification of Poly(ether ether ketone) by Simple Chemical Grafting of Strontium Chondroitin Sulfate to Improve its Anti-Inflammation, Angiogenesis, Osteogenic Properties.

Besides inducing osteogenic differentiation, the surface modification of poly(ether ether ketone) (PEEK) is highly expected to improve its angiogenic activity and reduce the inflammatory response in the surrounding tissue. Herein, strontium chondroitin sulfate is first attempted to be introduced into the surface of sulfonated PEEK (SPEEK-CS@Sr) based on the Schiff base reaction between PEEK and ethylenediamine (EDA) and the amidation reaction between EDA and chondroitin sulfate (CS). The surface characteristics of SPEEK-CS@Sr implant are systematically investigated, and its biological properties in vitro and in vivo are also evaluated. The results show that the surface of SPEEK-CS@Sr implant exhibits a 3D microporous structure and good hydrophilicity, and can steadily release Sr ions. Importantly, the SPEEK-CS@Sr not only displays excellent biocompatibility, but also can remarkably promote cell adhesion and spread, improve osteogenic activity and angiogenic activity, and reduce the inflammatory response compared to the original PEEK. Therefore, this study presents the surface modification of PEEK material by simple chemical grafting of strontium chondroitin sulfate to improve its angiogenesis, anti-inflammation, and osteogenic properties, and the as-fabricated SPEEK-CS@Sr has the potential to serve as a promising orthopedic implant in bone tissue engineering.

Thermomechanical investigations of PEKK-HAp-CS composites.

In this experimental study, a composite of poly-ether-ketone-ketone by reinforcement of hydroxyapatite and chitosan has been prepared for possible applications as orthopaedic scaffolds. Initially, different weight percentages of hydroxyapatite and chitosan were reinforced in the poly-ether-ketone-ketone matrix and tested for melt flow index in order to check the flowability of different compositions/proportions. Suitable compositions revealed by the melt flow index test were then taken forward for the extrusion of filament required for fused deposition modelling. For thermomechanical investigations, Taguchi-based design of experiments has been used with input variables in the extrusion process as follows: temperature, load applied and different composition/proportions. The specimens in the form of feedstock filament produced by the extrusion process were made to undergo tensile testing. The specimens were also inspected by differential scanning calorimetry and photomicrographs. Finally, the specimen showing the best performance from the thermomechanical viewpoint has been selected to extrude the filament for the fused deposition modelling process.

High-Performance Semicrystalline Poly(ether ketone)-Based Proton Exchange Membrane.

A novel semicrystalline poly(ether ketone) (PEK)-based proton exchange membrane (semi-SPEK-x) has been developed. Through a one-step sulfonation and hydrolysis, a poly(ether ketimine) precursor transforms into PEK and ion-conducting groups are introduced. With an ion-exchange capacity ranging from 1.49 to 2.00 mequiv g-1, the semi-SPEK-x polymers exhibit a semicrystalline feature in both dry and hydrated states. Owing to the semicrystalline domains inside the polymer, the obtained membrane exhibits low water uptake and low volume swelling ratio. More importantly, the semicrystalline structure lowers methanol permeability and, consequently, improves the overall performances of direct methanol fuel cells.