Polyetheretherketone Research Articles

In vitro assessment of corrosion, antibacterial properties, and degradation behavior of zirconia-coated polyetheretherketone (PEEK)

The medical industry often uses ceramic and polymeric coatings to safeguard metal substrates. However, more investigation is required to explore the implementation of ceramic coatings on polymer substrates and to determine their degradation and in vitro characteristics. This work involves applying zirconia coating onto the 3D-printed PEEK polymer substrate using the RF magnetron sputtering technique. With varying layer thickness and printing speed parameters, PEEK samples (S1, S2, S3, and S4) were 3D printed and coated with zirconia. The coated and uncoated samples were immersed in Fusayama artificial saliva solution for 30 days. Following immersion in artificial saliva, this study examined the corrosion of 3D-printed PEEK samples with and without coatings. Elemental mapping, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to evaluate sample morphology and estimate the binding energy of possible compounds generated in the artificial saliva solution. In vitro assessments such as antibacterial studies were performed against E. coli and S. aureus, and cytotoxic analysis was performed using Human Wharton’s jelly-derived mesenchymal stem cells (WJ-MSCs) to determine cell proliferation. The results indicated that sample S3, printed with 0.15 mm layer thickness and 20 mm/s print speed coated with zirconia showed a better degradation rate of 9.01% whereas the other three samples S1, S2, and S4 coated with zirconia showed deterioration rates of 36.4%, 33% and 16% respectively. Sample S3 showed a better antibacterial activity as biofilm formation was absent and also showed cell viability of about 79% and hence can be considered as a viable option for dental applications.

The Anisotropic Mechanical and Tribological Behaviors of Additively Manufactured (Material Extrusion) Implant-Grade Polyether Ether Ketone (PEEK)

In this study, we investigated the mechanical and tribological properties of the layer-by-layer structure of additively manufactured implant-grade Polyether Ether Ketone (PEEK) through the Material Extrusion (ME) process as a potential substitute for artificial joints. The effective elasticity modulus of the anisotropic 3D-printed PEEK was determined to be 2.505 GPa along the vertical and horizontal build orientations. The lubricated friction and wear performance were assessed using a pin-on-disk test under various loads, including 14, 30, 50, and 70 N, with a sliding speed of 50 mm/s over a total distance of 1 km at 37 °C. The contact parameters between the hemispherical steel pin and 3D-printed PEEK disks, involving contact pressures over the circle of contact, were observed to increase as the load increased. The results indicated that the wear coefficient exhibited a rise from 1.418 × 10−5 to 2.089 × 10−1 as the applied loads increased, signaling a shift from mild to severe wear regimes. Fetal Bovine Serum (FBS) as a lubricant exhibited a mixed mechanism, ascertained through the Stribeck curve, as well as a minimum fluid film thickness of 1.346 nm under an isoviscous–elastic regime, as calculated by the maximum load. Moreover, the mechanism governing wear during sliding, influenced by both normal axial and shear loads, primarily involved adhesion.

Additive manufacturing and in vitro study of biological characteristics of sulfonated polyetheretherketone-bioactive glass porous bone scaffolds

Polyetheretherketone (PEEK), a high-performance special engineering plastic, has gradually been used in bone substitutes due to its wear resistance, acid and alkali resistance, non-toxicity, radiolucency, and modulus close to that of human bone. However, its stable biphenyl structure determines strong biological inertness, thus artificial interventions are required to improve the biological activity of fabricated PEEK parts for better clinical applications. This study developed a novel strategy for grafting bioactive glass (BAG) onto the surface of PEEK through sulfonation reaction with concentrated sulfuric acid (H2SO4), aiming to improve the bioactivity of printed porous bone scaffolds manufactured by fused deposition modeling (FDM) to meet clinical individual needs. In vitro biological study was conducted on sulfonated polyetheretherketone-bioactive glass (SPEEK-BAG) scaffolds obtained by this strategy. The results demonstrated that the optimal modification condition was a 4-hour sulfonation reaction with 1 mol/L concentrated H2SO4 at high temperature and high pressure. The scaffold obtained under this condition showed minimal cytotoxicity, and the Ca/P molar ratio, yield compressive strength, and compressive modulus of this scaffold were 2.94 ± 0.02, 62.78 MPa, and 0.186 GPa respectively. The hydrophilicity and the biomineralization ability of PEEK modified by the proposed strategy were substantially improved. The SPEEK-BAG bone scaffolds exhibited excellent biocompatible properties, suggesting that the sulfonation reaction and BAG effectively enhanced the proliferation and differentiation of osteoblasts. The presented method provides an innovative, highly effective, and customized strategy to improve the biocompatibility and bone repair ability of printed PEEK bone scaffolds for virous biomedical applications.

A novel printing strategy to fabricate polyetheretherketone (PEEK)-based composites via hollow filaments filled with multiple reinforcements

ABSTRACT Polyetheretherketone (PEEK)-based composites fabricated by material extrusion (ME) have attracted broad research attention; however, the complex pre-made composite filament process makes them inflexible. In this work, a novel composite printing strategy was proposed by filling composite powder into hollow filaments to construct composite filaments for printing. This strategy eliminated the screw extrusion composite filament process and fabricated composite parts directly using composite powders. Hydroxyapatite-reinforced polyetheretherketone (HA-PEEK) and carbon fibre-reinforced polyetheretherketone (CF-PEEK) composite specimens were fabricated based on the proposed printing method, and their chemical, physical, and mechanical properties were investigated. To improve the mechanical performance of the specimens, annealing was conducted. It was found that the printed composite specimens had excellent mechanical properties. The highest flexural strengths of the 10% HA-PEEK-R and 5% CF-PEEK-R specimens were detected as 352.9 and 399.4 MPa, respectively. The compression strengths of the 10% HA-PEEK-R and 20% CF-PEEK-R specimens peaked, representing 123.0 and 137.2 MPa, respectively. Furthermore, adding different functional reinforcement fillers or various filler contents to different segments of hollow filaments, sandwich structures and gradient structures were successfully fabricated.

Study on hybrid 3D printing and milling process for customized polyether-ether-ketone components.

Polyether-ether-ketone (PEEK) has been widely applied in various fields due to its excellent mechanical properties and biocompatibility. The efficient and high-quality customized manufacturing of PEEK components are investigated in this study by the hybrid 3D printing and milling process. At first, the alternating hybrid process is selected and verified by comparing two typical hybrid process categories and conducting experiments, respectively. Second, a set of procedures are designed to automate the engineering application of the hybrid process trying to avoid the disadvantages of manual programing. Then, considering the tool length and possible interferences during the hybrid process, a model segmentation algorithm, namely, the exchange principle of avoiding interference (EPAI) is proposed. Based on the introduced EPAI and the programing language Python, the additive and subtractive hybrid manufacturing (ASHM) data processing procedure is proposed and realized by post-processing of the conventional 3D printing codes. Finally, the feasibility experiments have been conducted. The experimental results verify the hybrid manufacturing process in the fabrication of parts with complex internal features. The surface roughness Ra and dimensional error L of the parts have been reduced by 75.5% and 85.2%, respectively, while the shear strength τ has been increased by 14.1%. Compared with conventional milling process, the material consumption is reduced by 48.7%.

3D-Printed high performance PEEK/CF-PEEK polymer composites—An investigation on microstructural characteristics and mechanical performance

This study investigates the microstructural characteristics and mechanical properties of 3D-printed polyether ether ketone (PEEK) and carbon fiber-reinforced PEEK (PEEK CF20) composites. Using a specifically optimized 3D printing process parametric condition, samples of pure PEEK and PEEK CF20 (containing 20% carbon fiber) were fabricated. Mechanical properties were estimated by tensile, flexural, and interlaminar shear strength (ILSS) tests, performed as per ISO and DIN standards. Results indicated that PEEK CF20 exhibits significantly enhanced mechanical properties compared to pure PEEK. The tensile strength of PEEK CF20 was 81.069 MPa, compared to 76.070 MPa for pure PEEK. Maximum load values were 1456.608 N for PEEK CF20 and 1286.137 N for pure PEEK, while ILSS values were 15.76 MPa for PEEK CF20 and 11.82 MPa for pure PEEK. Microstructural analysis through field emission scanning electron microscopy (FESEM) revealed that PEEK CF20 had better fiber-matrix bonding and fewer defects compared to pure PEEK.

Laser-assisted automated tape laying: Effects of placement rate and heated tooling on layer bonding and tensile properties

This paper investigates the processing parameters placement rate and tooling temperature of laser-assisted automated tape laying (ATL). Plates with carbon fiber-reinforced polyether ether ketone (CF/PEEK) were produced at 6 m/min, 9 m/min and 18 m/min, and 23°C and 250°C tooling temperature, respectively. Correlations of processing conditions with micrographs, void content, thickness, the degree of crystallinity and the shear strength of the compression shear test, including a fractographic analysis, were derived. Processing conditions that increase the degree of crystallinity were only found to improve the compression shear strength at 6 m/min placement rates, primarily due to a void content below 3.4 % and degree of crystallinity above 26 %. The fractographic analysis derived from the compression shear test revealed a strong correlation between the degree of crystallinity and the size of ductile drawings. In contrast, the transverse tensile test showed no influences on the ATL processing conditions, whereas the tensile strength in fiber direction decreased by 11 % from a placement rate of 6 m/min to 18 m/min. ATL with a 250°C tooling temperature increased the strengths by 14 % compared to those at room temperature. A further tensile strength improvement of 0° and 90° to 1754 MPa and 75 MPa was obtained by a subsequent out-of-autoclave consolidation using vacuum bagging.

Mechanical and tribological assessment of PEEK and PEEK based polymer composites for artificial hip joints

Abstract Human hip failure remains a significant issue, and constructing artificial joints is imperative for affected individuals. This study examined the mechanical and wear behavior of polyether ether ketone (PEEK) polymers, including bare PEEK (BP), HA (Hydroxyapatite)-infused PEEK (HA-PEEK), and GO (Graphene oxide)-infused HA-PEEK (GO-HA-PEEK). The samples were prepared using compression molding, and wear characteristics were evaluated using a linear reciprocating tribo-tester against a stainless-steel counterface under a load 50 N, frequency 5 Hz, stroke length 20 mm, and time 30 min. The 10 % w/w HA inclusions slightly elevate the PEEK’s tensile strength from 29.85 ± 1.11 MPa (BP) to 34.23 ± 1.09 MPa, and the 0.5 % w/w GO with 10 % w/w HA encapsulations have significantly improved tensile properties (65.10 ± 1.12 MPa), which is 2.2 fold higher than the BP. However, the attained impact properties fall below the satisfactory level. Coefficient of friction and wear rate are significantly reduced. The wear rate reduced from 3.39 × 10−6 mm3 N−1 m−1 (BP) to 2.54 × 10−6 mm3 N−1 m−1 on HA-PEEK, and more than two times reduction (1.69 × 10−6 mm3 N−1 m−1) with 0.5 % w/w GO incorporating HA-PEEK. The results show that the reinforcements significantly reduced wear and improved the mechanical strength of PEEK polymers. Unlike BP and HA with lowered impact resistance, GO integrated HA-PEEK exhibited outstanding mechanical and wear performance. Therefore, HA and GO-infused PEEKs are suitable alternatives for hip repair applications.

Development of ANN model for predicting mechanical properties of 3D printed PEEK polymer using FDM and optimization of process parameters for better mechanical properties

Additive manufacturing (AM) has evolved from a proven technology to a rapid prototyping tool with great potential. This technology is widely used in many industries such as automotive, aerospace, and medical; fused deposition modeling (FDM) is a popular 3D printing technique for producing PEEK (polyether ether ketone) parts, including implant prosthetic teeth. In this study, artificial neural network (ANN) modeling, parametric optimization, and experimental examination of PEEK 3D printing were conducted to enhance 3D printing processes. In this study, four critical process factors (infill density, layer height, printing speed, and infill pattern) influence the surface roughness, mechanical strength, and elastic modulus of the printed samples. Utilizing a 4–12–3 network design, this study demonstrates that an ANN model with an average error of less than 5% is optimal for all three responses. Furthermore, the study employed a teaching and learning based optimization algorithm (TLBO) and a non-dominated sorting genetic algorithm (NSGA) to optimize the printing process to obtain improved mechanical properties. The findings highlight TLBO’s ability to minimize surface roughness to 6.01 μm and NSGA’s capability to maximize the elastic modulus to 1253.35 MPa and ultimate tensile strength to 65.55 MPa. Microstructural studies supported the results obtained through parametric analysis and optimization.

In Vitro Comparison of Titanium Disc Surface Roughness and Bacterial Colonization After Ultrasonic Instrumentation With Three Different Tips.

During implant maintenance, preserving a smooth surface on the machined transmucosal abutment is critical to reduce biofilm attachment and colonization. The present study compared the surface roughness and bacterial colonization of machined titanium surfaces after instrumentation with various materials. Forty-four machined grade 23 titanium discs were instrumented with a round polyether ether ketone (PEEK) tip, a plastic curette tip, or a pure titanium curette tip with piezoelectric devices. Before and after instrumentation, the surface roughness (Ra and Rz) values were analyzed with a profilometer and scanning electron microscopy (SEM). Streptococcus sanguinis was cultured and incubated for 24 hours on the instrumented discs, and colony-forming units per milliliter were obtained for each group. Samples instrumented with the metal ultrasonic tip significantly increased surface roughness compared with the other groups. This resulted in greater colonization by S. sanguinis than surfaces instrumented with PEEK tips or the negative control. Samples instrumented with PEEK and plastic tips did not exhibit any statistically significant increase in surface roughness, and SEM analysis revealed a significantly rougher surface of discs instrumented with metal compared with discs instrumented with plastic or PEEK tips despite the possibility of debris from tip dissolution. Our results suggest that instrumentation with metal ultrasonic tips with piezoelectric devices significantly increased machined titanium's surface roughness and elicited higher biofilm formation in vitro. Meanwhile, instrumentation of machined titanium with PEEK or plastic ultrasonic tips did not affect the surface roughness or bacterial adhesion.

A “sizing-free” strategy to improve the interfacial property of PEEK/CF composites based on “grafting-bridging” bifunctional diazonium salt

Achieving simple and efficient interfacial modification between carbon fiber and polyether ether ketone (PEEK) has been the pursuit of researchers. In this study, by comparing the nucleophilicity of various aromatic amines, a direct Schiff base reaction with polyether ether ketone (PEEK) has been achieved. Based on this, a “grafting-bridging” bifunctional diazonium salt containing a phenylethylamine structure was designed and synthesized to enhance the interfacial strength through covalent bonding without the use of sizing agents. The diazonium salt was grafted onto the surface of carbon fiber through electrochemical reduction, while the PEEK resin and phenylethylamine could achieve bridging through heat treatment, thus a PEEK/CF interface with enhanced covalent bonds was constructed. The reaction and conversion rate between phenylethylamine and PEEK resin were confirmed through IR and NMR. The successful grafting of the diazonium salt on the carbon fiber was determined through XPS and cyclic voltammetry. The bridging reaction on the surface of carbon fiber was verified through XPS and the use of 6F-PEEK with characteristic elements. As a result, the interfacial shear strength (IFSS) of the modified PEEK/CF interface reached 86.2 MPa, representing a 102.8 % improvement compared to the untreated interface of 42.5 MPa, fully demonstrating the excellent effect of the bifunctional diazonium salt.

Poly-ether-ether-ketone (PEEK) versus dead-soft coaxial bonded retainers: a randomized clinical trial. Part 1. Stability, retainer failure, and participant satisfaction.

Poly-ether-ether-ketone (PEEK) was introduced in dentistry as an alternative to metal alloys. To assess the effectiveness of PEEK-fixed retainers in preserving the stability of mandibular anterior and participant satisfaction as compared to the Dead-soft coaxial fixed retainer (DSC). A single-centre, two-arm parallel groups randomized clinical trial. The patients treated with pre-adjusted orthodontic appliances who have a Little's Irregularity Index (LII) ≤ 0.5mm have been enrolled in the trial. PEEK retainers were prepared to round 0.8mm wire by computer-aided design and manufacturing, and the DSC wire was carefully adapted to the lingual surface of the lower anterior teeth. The primary outcome was the stability of lower anterior teeth as assessed by LII, while the secondary outcomes were changes in occlusal parameters, retainer failure, and patient satisfaction. The data were collected at the debonding stage (T0), 1 month (T1), 3 months (T3), and 6 months (T6) after starting the trial, except for patient's satisfaction, which was recorded using an electronic form at T1 and T6. Single blinding of participants. A total of 46 participants with an age range of 12-28 years old were randomly allocated to the two groups (n = 23 in each). Only one participant dropped out; therefore, 45 participants were analysed. The DSC group showed a significant increase in LII at T3. Both retainer groups had comparable occlusal measurements, failure frequency, and survival time, with no significant difference. The patients in the DSC group reported a statistically significant perception of change in the position of their teeth compared to those in the PEEK group. No harmful effects have been reported. Limited follow-up duration and the inability to blind the operator due to the nature of the intervention. After 6-month retention, the PEEK retainer was equally effective to DSC retainers in maintaining the teeth alignment, with no significant differences regarding the failure frequency, survival rate, and general patient satisfaction. https://register.clinicaltrials.gov. (NCT05557136).

Injection over-molding process of PEEK composites

Abstract This study utilizes experimental and microscopic characterization methods to investigate the prospects and feasibility of using the Injection Over-Molding (IOM) process to replace traditional adhesives in the manufacturing of complex ribbed panel structures with Polyether Ether Ketone (PEEK) composites. The results indicate that the IOM process can achieve the optimal bonding strength of adhesives while significantly reducing the processing cycle, demonstrating substantial potential. Additionally, enhancing the melt temperature and mold temperature can further improve interface bonding quality and increase bonding strength. Based on the experimental results, it is inferred that increasing the melt temperature can elevate the interface temperature while raising the mold temperature can slow down the interface cooling rate, suggesting mechanisms by which these parameters influence interface bonding quality.

Understanding the deposition of multilayered hydroxyapatite-bioactive glass/hydroxyapatite/titanium dioxide coatings on PEEK substrates by plasma spray

Poly-ether-ether-ketone (PEEK) is a polymeric material that is often used in biomedical applications due to its excellent mechanical properties and radiolucency; this material is, in general, biologically inert. In recent decades, thermally sprayed biocompatible coatings have been widely employed in metallic implants to improve the osseointegration process in the human body. Thus, not surprisingly, thermally sprayed biocompatible coatings can be envisaged as an excellent alternative to improve the material's surface properties. However, there is little information in the literature about the deposition of thermally sprayed bioactive coatings on polymeric substrates. In the present study, a titanium dioxide (TiO2) powder was plasma-sprayed on PEEK substrates acting as a bond coat to further deposition of hydroxyapatite (HA)/bioactive glass multilayered coatings. The design of experiments methodology was employed to produce coatings with tailored properties. A key aspect in this work is how the experiments were carried out to understand the effect of powder features, such as chemical composition, on the deposition of the ceramic coatings on the PEEK substrate. Heating/cooling physical laws were employed to discuss the results obtained. The methodology employed in this work allowed to deposit a multilayered coating with adhesion strength of about 50 MPa on PEEK substrates measured using scratch test. The coatings' structural, morphological, chemical, thermal, and mechanical evaluation was performed using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, differential scanning calorimetry, and micro indentation test, respectively. In-vitro tests were also performed on these coatings under static simulated conditions. The results show that the PEEK's surface can be successfully functionalized, turning it from showing an inert behavior to displaying bioactivity by applying a HA-based bilayer or multilayered coating.

Impact of Substrate Material, Esthetic Material Thickness, and Cement on Color Reproduction in Implant-Supported Fixed Restorations.

Purpose This study aimed to evaluate the impact of substrate material, esthetic material type and thickness, and cement shade on the final color reproduction of implant-supported fixed restorations. The goal was to identify optimal combinations for achieving clinically acceptable esthetic outcomes. Material and methods An in vitro study was conducted using four substrate materials, hybrid polyetherketoneketone (PEEK)-based ceramic-reinforced polymer (BioHPP), chromium-cobalt alloy (CrCo), grade 5 titanium (Ti), and white zirconium oxide ceramic (WZirCAD), and three esthetic materials, lithium disilicate ceramic (e.max CAD), polymethyl methacrylate (PMMA), and zirconia oxide ceramic (e.max ZirCAD), at five different thicknesses (0.5, 1, 1.5, 2, and 2.5 mm). Color differences (ΔE*) were measured using a spectrophotometer, both with and without cement application. Statistical analysis was performed using the Kruskal-Wallis test and Bonferroni correction to assess the effects of material combinations on color reproduction. Results The study found that a 1 mm thickness of e.max CAD on BioHPP and CrCo substrates provided the best color matching, with ΔE* values closest to clinical acceptability. PMMA showed higher ΔE* values, indicating lower color stability compared to e.max CAD and e.max ZirCAD. Cement shade had a near-significant influence on final color perception, particularly with e.max ZirCAD on CrCo substrates. Conclusions The study suggests that using e.max CAD at 1 mm thickness on BioHPP or CrCo substrates provides superior esthetic results, underscoring the need for careful material selection in clinical practice. Further in vivo research is recommended to validate these findings and explore long-term outcomes.

A 3D printing-based hybrid manufacturing method for high-strength polymeric medical implant fabrication

This paper presents a novel 3D printing-based hybrid manufacturing method to fabricate high-strength polymeric medical implants. Poly-ether-ether-ketone (PEEK) and polyether sulfone (PES) are blended to make filament for use with the fused filament fabrication technique to print custom designed implants. After printing and annealing, PES is removed by leaching to create interconnected porous PEEK structure with suitable pore size and porosity for bone tissue ingrowth. The proposed method provides a versatile approach to fabricating medical implants that are both mechanically strong and microstructurally inducive to osseointegration. The polymeric implants are also X-ray transparent to allow post-surgery evaluations using an imaging method. An intervertebral spacer implant example is used to demonstrate the proposed fabrication method.

Laser powder bed fusion printed poly-ether-ether-ketone/bioactive glass composite scaffolds with dual-scale pores for enhanced osseointegration and bone ingrowth

Although poly-ether-ether-ketone (PEEK) implants hold significant medical promise, their bioinert nature presents challenges in osseointegration and bone ingrowth within clinical contexts. To mitigate these challenges, the present study introduces Diamond PEEK/bioactive glass (BG) composite scaffolds, characterized by macro/micro dual-porous structures, precisely fabricated via laser powder bed fusion (LPBF) technology. The findings indicate that an increase in BG content within these scaffolds significantly augments their hydrophilicity and hydroxyapatite formation capacities. Stress-strain curve analysis demonstrates reliable load-bearing stability across all scaffold types. In vitro assessments confirmed the non-cytotoxicity of PEEK/BG samples and demonstrated improved osteogenic differentiation and mineralization with increased BG incorporation. Further, in vivo experiments illustrated that the Diamond porous structure of these scaffolds facilitated bone growth, an effect notably amplified with higher BG content. Particularly in groups with 15 wt% and 25 wt% BG scaffolds, new bone formation was observed not only within the macropores of the Diamond structure but also within the micropores inside the scaffold rod, suggesting an almost seamless fusion with the new bone. This demonstrates the scaffolds’ effective osteointegration and bone ingrowth properties. This study conclusively established the effectiveness of Diamond-structured PEEK/BG composite scaffolds, fabricated via LPBF, in bone repair. It highlights the crucial role of BG in enhancing osteogenic potential through interaction with the macro/micro pores of the scaffold. Statement of significanceThis study addresses the bioinert nature of PEEK implants by developing Diamond-structured PEEK/bioactive glass (BG) composite scaffolds by laser powder bed fusion. The dual-porous macro/microstructure enhances hydrophilicity and hydroxyapatite formation, vital for bone regeneration. By adjusting the BG content, we controlled the melt viscosity and sintering rate, leading to the formation of beneficial microscale pores. These pores resolve the issue of ineffective bioactive fillers in previous LPBF-fabricated scaffolds, enhancing the osteogenic potential of BG and inducing superior bone ingrowth and osseointegration. In vitro and in vivo analyses show enhanced osteogenic differentiation, mineralization, and bone growth, underscoring the clinical potential of these scaffolds for bone repair.

Influence of defocusing of UV pulse laser radiation on LIG synthesis on Polyetheretherketone

Laser-induced graphene (LIG) technology, a technique for preparing three-dimensional porous graphene by laser direct writing on carbon precursors under ambient condition, has been widely used due to its low cost and high efficiency. However, there is still a lack of research on the influence of the defocusing on LIG synthesis. In this paper, LIG is prepared by UV laser on Polyetheretherketone (PEEK) film, and a finite element simulation of this process is established to infer the temperature field. The influence of the defocusing on the structure, morphology, specific surface area SSA, and electrical properties of PEEK-LIG is investigated while maintaining the same energy radiated per unit area. The results show that the defocusing changes the structure and morphology of PEEK-LIG by affecting the temperature field distribution in both the surface and thickness directions, which affects the properties of LIG, where the surface area ratio Sdr does not depend on the defocusing amount monotonically. As the UV laser nears the beam waist at the threshold of LIG formation, Sdr has its maximum value and improves its electrical conductivity.

Correlation of proton conductivity and free volume in sulfonated polyether ether ketone electrolytes: A positron annihilation lifetime spectroscopy study

Proton-conducting polymers play a pivotal role in clean energy technologies and various industrial applications, with a significant emphasis on enhancing energy efficiency and minimizing environmental impact. Sulfonated polyether ether ketone (SPEEK), which is renowned for its proton conductivity, has emerged as a key material in electrochemical processes, notably in proton exchange membrane (PEM) fuel cells. This study investigated the proton conductivity and dielectric behavior of SPEEK electrolytes at varying degree of sulfonation (DS) of 65% and 80%, correlating these properties with free volume profiles determined by positron annihilation lifetime spectroscopy (PALS). The SPEEK-65 and SPEEK-80 electrolytes were prepared via a controlled sulfonation process and characterized by FTIR, TGA, and SEM analyses. Proton conductivity and dielectric measurements were conducted at temperatures ranging from 300-370 K and frequencies ranging from 20 Hz to 1 MHz. The results revealed that SPEEK-80 exhibited a maximum proton conductivity of 3.4×10-2 S/m at 300 K and 1 MHz, which was significantly greater than the 4.38×10-3 S/m observed for SPEEK-65 under the same conditions. PALS analysis demonstrated a notable increase in free volume with increasing DS, with SPEEK-80 showing a higher o-Ps lifetime and intensity, indicating larger free volume sizes and fractions. These findings underscore the critical interplay between DS, free volume, and proton conductivity, offering insights into optimizing SPEEK-based electrolytes for advanced electrochemical applications.

Intelligent Supramolecular Modification for Implants: Endogenous Regulation of Bone Defect Repair in Osteoporosis.

Addressing osteoporosis-related bone defects, a supramolecular strategy is innovated for modifying carbon fiber reinforced polyether ether ketone (CF/PEEK) composites. By covalently attaching intelligent macromolecules via in situ RAFT polymerization, leveraging the unique pathological microenvironment in patients with iron-overloaded osteoporosis, intelligent supramolecular modified implant surface possesses multiple endogenous modulation capabilities. After implantation, surface brush-like macromolecules initially resist macrophage adhesion, thereby reducing the level of immune inflammation. Over time, the molecular chains undergo conformational changes due to Fe (III) mediated supramolecular self-assembly, transforming into mechanistic signals. These signals are then specifically transmitted to pre-osteoblast cell through the binding capacity of the KRSR short peptide at the molecular terminus, induced their osteogenic differentiation via the YAP/β-catenin signaling axis. Furthermore, osteoblasts secrete alkaline phosphatase (ALP), which significantly hydrolyzes phosphate ester bonds in surface macromolecular side groups, resulting in the release of alendronate (ALN). This process further improves the local osteoporotic microenvironment. This intelligent surface modification tailors bone repair to individual conditions, automatically realize multiple endogenous regulation once implanted, and truly realize spontaneous activation of a series of responses conducive to bone repair in vivo. It is evidenced by improved bone regeneration in iron-overloaded osteoporotic rabbits and supported by in vitro validations.