Sulfonated Poly Ether Ether Ketone Research Articles

The sulfonated polyetheretherketone with 3D structure modified by two bio-inspired methods shows osteogenic and antibacterial functions

Implant loosening and infection around the prosthesis are the most common and serious complications in orthopedics, especially in joint surgery. To fundamentally solve these two problems, the surface of polyetheretherketone (PEEK), commonly used in orthopedic implants, is modified. PEEK is sulfonated to obtain a 3D porous structure surface. Then, polydopamine is used as an intermediary to embed SrCO3 nanoparticles into the micropores on the surface of sulfonated PEEK, so that the material can stably release strontium ions. Finally, a gentamicin-silk protein coating is added on the surface of the material to make the material release gentamicin stably. Experiments conducted on the modified material show that SrCO3 nanoparticles combined with the gentamicin-silk protein sulfonated PEEK(GS-Silk@SrCO3-PDA@SPEEK) material have strong osteogenic and antibacterial abilities both in vitro and in vivo. Our findings indicate that GS-Silk@SrCO3-PDA@SPEEK may be a potential candidate for orthopedic implant. This study also provides a novel approach for the surface modification of PEEK materials.

Sulfonated poly(ether ether ketone) reinforced with polystyrene sulfonic acid functionalized micelle templated mesoporous MCM-41 for direct methanol fuel cells

A composite membrane comprising sulfonated polyether ether ketone (sPEEK) and polystyrene sulfonic acid functionalized micelle templated MCM-41 (PSSA-f-MCM-41) is realized as a potential alternative to the Nafion membrane for direct methanol fuel cells (DMFC). PSSA-f-MCM-41 incorporation in sPEEK leads to improvement in the physio-chemical properties such as ionic conductivity, methanol permeability, tensile strength, water uptake and ion exchange capacity. The methanol permeability of the composite membrane i.e. PSSA-f-MCM-41 (1.5 wt %)-sPEEK is reduced by 60% in comparison to pristine sPEEK. Moreover, the electrochemical selectivity of the aforesaid composite membrane is four times higher than sPEEK. The DMFC performance shows the peak power density of 147 mW cm−2 for the composite membrane which is higher than the pristine sPEEK and Nafion 117 membranes. Stability test for the composite membranes confirm less degradation in OCV in comparison to pristine sPEEK.

Enhancing antibacterial capability and osseointegration of polyetheretherketone (PEEK) implants by dual-functional surface modification

The overall aim of the current study is to develop a dual-functional PEEK implant to simultaneously fight off bacterial contamination and promote osseointegration by sustained release of moxifloxacin hydrochloride (MOX) and osteogenic growth peptide (OGP) from mussel-inspired polydopamine (PDA)-coated porous sulfonated PEEK (SPK) surface. Our study revealed that the MOX/OGP PDA-modified SPK (SPD-MOX/OGP) surface exhibited a durable and excellent antibacterial effect against planktonic/adherent Staphylococcus aureus and Escherichia coli in vitro. A remarkable enhancement in specific cell adhesion, proliferation and osteogenicity were observed on the SPD-MOX/OGP substrate due to the presence of OGP and PDA molecules compared to all other groups. More significantly, using the infected and non-infected rat tibia models confirmed the in vivo antimicrobial and osteogenesis abilities of SPD-MOX/OGP. Therefore, we are confident that such dual-functional PEEK surface with both antibacterial and osseointegrative capacities in this study would give a positive answer to periprosthetic joint infection-related issues.

Preparation of an Amidated Graphene Oxide/Sulfonated Poly Ether Ether Ketone (AGO/SPEEK) Modified Atmosphere Packaging for the Storage of Cherry Tomatoes.

The shelf life of cherry tomatoes is short so that new and efficient preservation techniques or procedures are required to reduce postharvest losses. This study focused on the development of a sulfonated poly ether ether ketone (SPEEK) film incorporated with amidated graphene oxide (AGO), for the storage of cherry tomatoes in modified atmosphere packaging. The mechanical properties, gas permeability, and moisture permeability were subsequently tested. The evolution of attributes related to shelf life, such as gas composition, physicochemical properties, and sensory properties were also monitored during storage trials. AGO, as an inorganic filler, increases the thermal stability and mechanical properties of SPEEK-based films, while it reduces the water absorption, swelling rate, and moisture permeability. Importantly, all the AGO/SPEEK films exhibited enhanced gas permeability and selective permeability of CO2/O2 relative to the SPEEK film. Moreover, 0.9% (w/w) AGO/SPEEK film showed an enhanced permeability coefficient of CO2, corresponding to an increase of 50.7%. It could further improve the selective coefficient of CO2/O2 to 67.1%. The results of preservation at 8 °C revealed that: 0.9% (w/w) AGO/SPEEK film was significantly effective at maintaining the quality and extending the shelf life of cherry tomatoes from 15 to 30 days, thereby suggesting the potential for applying AGO-incorporated SPEEK films for food packaging materials.

Mesoscale Simulation on the Hydrated Morphologies of SPEEK Membrane

AbstractProton transport in proton exchange membrane is considered to depend on the hydrophilic domain formed by the microphase separation between hydrophobic and hydrophilic segments of the membrane. Therefore, the study of hydrated morphologies is crucial to understand proton transport. Here, the mesoscopic structure of sulfonated polyether ether ketone (SPEEK) membrane and SPEEK/polyethersulfone (PES) blend membrane is investigated by dissipative particle dynamics (DPD) simulation. The degree of sulfonation, water content, and PES content are considered to affect proton transport. Results show that the hydrophilic particles combine with water and are separated from hydrophobic particles to form clusters of different sizes. For the SPEEK membrane, with the increase in the sulfonation degree, clusters become large and begin to connect. Compared with isolated clusters at low water content, water clusters become large with increased water content. When water content λ = 16, the cluster size is the largest. The addition of PES accelerates the phase separation in the membrane and increases the size of water clusters. When SPEEK/PES = 4:6, the cluster size is the largest and provides the best proton transport pathway.

Exosome-functionalized polyetheretherketone-based implant with immunomodulatory property for enhancing osseointegration

The host immune response effecting on biomaterials is critical to determine implant fates and bone regeneration property. Bone marrow stem cells (BMSCs) derived exosomes (Exos) contain multiple biosignal molecules and have been demonstrated to exhibit immunomodulatory functions. Herein, we develop a BMSC-derived Exos–functionalized implant to accelerate bone integration by immunoregulation. BMSC-derived Exos were reversibly incorporated on tannic acid (TA) modified sulfonated polyetheretherketone (SPEEK) via the strong interaction of TA with biomacromolecules. The slowly released Exos from SPEEK can be phagocytosed by co-cultured cells, which could efficiently improve the biocompatibilities of SPEEK. In vitro results showed the Exos loaded SPEEK promoted macrophage M2 polarization via the NF-κB pathway to enhance BMSCs osteogenic differentiation. Further in vivo rat air-pouch model and rat femoral drilling model assessment of Exos loaded SPEEK revealed efficient macrophage M2 polarization, desirable new bone formation, and satisfactory osseointegration. Thus, BMSC-derived Exos–functionalized implant exerted osteoimmunomodulation effect to promote osteogenesis.

Investigation on the sulfonated poly(ether ether ketone)/poly(amide‐imide)/barium cerate‐based nanocomposite membrane for proton exchange membrane fuel cells

The fluorinated Nafion is replaceable by the non-fluorinated clean sulfonated poly (ether ether ketone) for hydrogen-based fuel cell. The acid-base blending of PAI to clean sulfonated poly ether ether ketone (SPEEK) increased the thermal, mechanical, and oxidative properties and decreased the conductivity. It interpreted that higher stability properties appeared on the blended membrane. The loading of BaCeO3 nanoparticles in the SPEEK/poly (amide-imide) (PAI) matrices was done via solution casting process. This outcome provides improved conductivity, ion-exchange property, water uptake (WU) with controlled stability due to the good interfacial interplay among nanoparticles and polymer. The high conductivity (14.98 × 10−3 S cm−1 at 80°C) was reached by SPEEK/PAI /BaCeO3 (90/10/06 wt%) membrane (B3) measured in the electrochemical four-probe impedance spectroscopy. Its current density and power density values are 269 mA cm−2 and 66 mW cm−2, respectively. The voltage retention of the B3 membrane was maintained almost at 0.92 V and degradation of voltage after 20 hours in the durability study was about 0.01 V.

Sulfonated poly ether ether ketone (SPEEK) based composite cation exchange membranes for salt removal from brackish water

Availability of fresh water is a serious concern due water pollution in these days. Several efforts have been made for water desalination where membrane based technology is considered prominently. Here, we synthesised sulfonated poly ether ether ketone (SPEEK) based functionalized hexagonal boron nitride (SBN) composite cation exchange membranes for water desalination. The morphology of BN and presence of sulfonic acid group are confirmed by TEM analysis. Ionic conductivity for SPEEK membrane is found to be 2.02 × 10−2 S. cm−1, which reaches to 4.05 × 10−2 S. cm−1 for SBN-10/SPEEK composite membrane. Ion exchange capacity of the SBN-10/SPEEK composite membrane also increased by 40 % and reaches to 1.66 meq.g-1 as compared to SPEEK membrane. Incorporation of SBN in membrane matrix not only improve the ion exchange capacity and ionic conductivity as well as expand the stability of the membranes. SEM micrograph confirm the uniform distribution of SBN in SPEEK membrane matrix. The composite membranes show the better ion transport properties in term of current efficiency and power consumption during salt removal from brackish water by electrodialysis. For SBN-10/SPEEK composite membrane power consumption was 0.75 kW h.Kg-1 with 98.5 % current efficiency.

Sulfonated 2D Covalent Organic Frameworks for Efficient Proton Conduction.

Open 1D channels found in covalent organic frameworks are unique and promising to serve as pathways for proton conduction; how to develop high-rate yet stable transporting systems remains a substantial challenge. Herein, this work reports a strategy for exploring proton-conducting frameworks by engineering pore walls and installing proton-containing polymers into the pores. Amide-linked and sulfonated frameworks were synthesized from imine-linked precursors via sequentially engineering to oxidize into amide linkages and to further anchor sulfonic acid groups onto the pore walls, enabling the creation of sulfonated frameworks with high crystallinity and channel ordering. Integrating sulfonated polyether ether ketone chains into the open channels enables proton hopping to across the channels, greatly increases proton conductivity and enables a stable continuous run. These results suggest a way to explore proton-conducting COFs via systematic engineering of the wall and space of the open nanochannels.

Improved performance of sulfonated poly ether ether ketone/three-dimensional hierarchical molybdenum disulfide nanoflower composite proton exchange membrane for fuel cells

As one of the most essential components of fuel cells, the commercialized Nafion-based proton exchange membranes(PEMs) suffer from several drawbacks like high cost and methanol permeability. The aim of this work is to fabricate a high performance PEM with combined low cost and methanol permeability together with high proton conductivity. Three-dimensional hierarchical molybdenum disulfide (MoS2) nanoflower is synthesized via a facile one-pot hydrothermal method, and then was embedd into sulfonated poly ether ether ketone (SPEEK) matrix to prepare composite PEM. The three-dimensional hierarchical architectures of MoS2 nanoflower can not only avoid the aggregation of MoS2 nanosheets but also provide abundant surface area and active sites, which are of benefit to fully take advantage of the intrinsic water absorption and methanol diffusion resistance ability of MoS2 nanosheets. The formed hydrogen bond network with water passway contributes to the improvement in proton conduction of composite membrane. As a consequence, composite membrane with 1 wt% MoS2 nanoflower loading content achieves optimized proton conductivity (0.123 S cm−1, 80 °C) and methanol permeability (21.5 × 10–7 cm2 s−1, 70 °C), which is 59.7% higher and 79.1% lower than that of SPEEK control membrane. Owing to increased proton conductivity and decreased methanol permeability, the maximum power density of the SPEEK/MoS2-1 composite membrane is 82.7 mW cm−2 at 70 °C, which is nearly 64.7% higher than that of pure SPEEK membrane (only 50.2 mW cm−2). Furthermore, the durability test confirms that the SPEEK/MoS2 composite membrane still possesses satisfactory stability even after continuous operation at 70 °C for 100 h.

Microbial fuel cell for oilfield produced water treatment and reuse: Modelling and process optimization

Oilfield produced water is one of the vast amounts of wastewater that pollute the environment and cause serious problems. In this study, the produced water was treated in a microbial fuel cell (MFC), and response surface methodology and central composite design (RSM/CCD) were used as powerful tools to optimize the process. The results of two separate parameters of sulfonated poly ether ether ketone (SPEEK) as well as nanocomposite composition (CNT/Pt) on the chemical oxygen demand (COD) removal and power generation were discussed. The nanocomposite was analyzed using XRD, SEM, and TEM. Moreover, the degree of sulfonation (DS) was measured by NMR. A quadratic model was utilized to forecast the removal of COD and power generation under distinct circumstances. To obtain the maximum COD removal along with maximum power generation, favorable conditions were achieved by statistical and mathematical techniques. The findings proved that MFC could remove 92% of COD and generate 545 mW/m2 of power density at optimum conditions of DS=80; and CNT/Pt of 14 wt% CNT- 86 wt% Pt.

Dual-functional coordination polymers with high proton conduction behaviour and good luminescence properties.

Two coordination polymers, [M(5-hip)(H2O)3]n (M = Cd2+ (1), Zn2+ (2), 5-hip = 5-hydroxyisophthalic acid), have been synthesized under hydrothermal conditions. The crystal structure reveals that complexes 1 and 2 have 1D chain structures by the coordination of metal ions and 5-hip. 1D chains are connected by hydrogen bonds to form a 3D structure. AC impedance analysis shows that the proton conductivity of complexes 1 and 2 comes up to 1.58 × 10-3 S cm-1 (98%RH, 343 K) and 5.27 × 10-4 S cm-1 (98%RH, 353 K), respectively. To further improve the proton conductivity, a hybrid membrane was prepared by the solution casting method with complexes as fillers and sulfonated polyether ether ketone (SPEEK) as the organic matrix. The proton conductivity of hybrid membranes 1@SPEEK-5 and 2@SPEEK-5 is 1.97 and 1.58 times higher than that of pure SPEEK membranes, respectively. Furthermore, the two complexes are excellent fluorescent sensors, which could detect Cr2O72- in aqueous solution with high sensitivity and selectivity. Both of them have low detection limits for Cr2O72- in aqueous solution, where the detection limit of complex 1 is 0.8 μM and that of complex 2 is 1 μM. The above work demonstrates that the two complexes are dual-functional materials with high proton conduction and good fluorescence properties.

Nanocomposite membrane by incorporating graphene oxide in sulfonated polyether ether ketone for direct methanol fuel cell

Few-layers graphene oxide enriched with oxygen functional groups is successfully obtained and incorporated into sulfonated polyether ether ketone (SPEEK) matrix. The functional groups and the surface modification of membranes were identified using FTIR spectroscopy, and X-ray Photoelectron Spectroscopy (XPS). Subsequently, FESEM was employed to study the surface morphology changes, and the X-Ray diffraction (XRD) was performed to ascertain the crystallinity of the fabricated membrane. The distribution of carbonaceous fillers GO in SPEEK matrix was found to actively improved the ion exchange capacity (IEC), and concurrently obstructed the methanol crossover, thus making them intriguing candidates as proton exchange membranes (PEMs).

MXene potassium titanate nanowire/sulfonated polyether ether ketone (SPEEK) hybrid composite proton exchange membrane for photocatalytic water splitting.

A cross-linked sulfonated polyether ether ketone (C-SPEEK) was incorporated with MXene/potassium titanate nanowire (MKT-NW) as a filler and applied as a proton exchange membrane for photocatalytic water splitting. The prepared hybrid composite PEM had proton conductivity of 0.0097 S cm−1 at room temperature with an ion exchange capacity of 1.88 meq g−1. The hybrid composite proton exchange membrane is a reactive membrane which was able to generate hydrogen gas under UV light irradiation. The efficiency of hydrogen gas production was 0.185066 μmol within 5 h for 12% wt of MKT-NW loading. The results indicated that the MKT-NW/C-SPEEK membrane is a promising candidate for ion exchange with hydrogen gas evolution in photocatalytic water splitting and could be applied as a renewable source of energy to use in various fields of applications.

Performance of the sulfonated poly ether ether ketone proton exchange membrane modified with sulfonated polystyrene and phosphotungstic acid for microbial fuel cell applications

AbstractIn this research, the preparation of low cost proton exchange membranes (PEMs) based on sulfonated poly ether ether ketone (SPEEK) for application in the microbial fuel cells (MFCs) is studied. Sulfonated polystyrene (SPS) and phosphotungstic acid (PWA) were employed to improve the performance of PEM through the creation of more proton pathways. At first, the sulfonation of PEEK and polystyrene were performed through two modified methods to obtain uniform and high degree of sulfonation (DS) of the polymers and then, the PEMs were prepared through the solution casting method. Accordingly, the formation of uniform skin layer was confirmed by the SEM micrographs. Blending the aforementioned additives to the SPEEK polymer solution significantly enhanced the proton conductivity, water uptake and durability of the modified membranes. The proton conductivities of SPEEK/SPS and SPEEK/PWA membranes at additive/SPEEK weight ratio of 0.15 were 45.3% and 26.2% higher than that of the commercial Nafion117 membrane, respectively. Moreover, the degradation times for the abovementioned modified membranes were 140 and 350 min which indicated satisfactory oxidation stability. Besides, the aforementioned membranes exhibited two times more water uptake compared to the neat SPEEK membrane. Finally, SPEEK/SPS and SPEEK/PWA membranes produced 68% and 36% higher maximum power in the MFC, compared to the commercial Nafion117 membrane. Therefore, the fabricated PEMs are potentially suitable alternatives to be used in the fuel cell applications.

Influence of surface-modified glass fibers on interfacial properties of GF/PEEK composites using molecular dynamics

In this paper, molecular dynamics (MD) simulations are carried out to explore the influence of surface modification of glass fiber on interfacial binding energy and failure behavior of GF/PEEK composites. The silane coupling agent and sulfonated PEEK (SPEEK) are employed to modify the surface of glass fibers (GF), and the results reveal that the SPEEK can be employed as an adhesive sizing agent to improve the interfacial bonding strength of GF/PEEK composites. In addition, the synergistic mechanism of non-bonding and mechanical interlocking is investigated by using MD simulations. The interface shear simulation results demonstrate that the interfacial shear strength of composite increased and more resin molecules are found on the surface after SPEEK is incorporated into the GF surface. Moreover, compared with surface-untreated short GF-reinforced PEEK composite, the experimental results demonstrate that the tensile and bending strength of SGF/PEEK composite are improved after interface modification with SPEEK by 21.4% and 30.2%, respectively. The current study presents the utilization of MD simulation for interface design to enhance the mechanical properties of fiber-reinforced PEEK composites.

Dual-Functional Phosphorene Nanocomposite Membranes for the Treatment of Perfluorinated Water: An Investigation of Perfluorooctanoic Acid Removal via Filtration Combined with Ultraviolet Irradiation or Oxygenation.

Nanomaterials with tunable properties show promise because of their size-dependent electronic structure and controllable physical properties. The purpose of this research was to develop and validate environmentally safe nanomaterial-based approach for treatment of drinking water including removal and degradation of per- and polyfluorinated chemicals (PFAS). PFAS are surfactant chemicals with broad uses that are now recognized as contaminants with a significant risk to human health. They are commonly used in household and industrial products. They are extremely persistent in the environment because they possess both hydrophobic fluorine-saturated carbon chains and hydrophilic functional groups, along with being oleophobic. Traditional drinking water treatment technologies are usually ineffective for the removal of PFAS from contaminated waters, because they are normally present in exiguous concentrations and have unique properties that make them persistent. Therefore, there is a critical need for safe and efficient remediation methods for PFAS, particularly in drinking water. The proposed novel approach has also a potential application for decreasing PFAS background levels in analytical systems. In this study, nanocomposite membranes composed of sulfonated poly ether ether ketone (SPEEK) and two-dimensional phosphorene were fabricated, and they obtained on average 99% rejection of perfluorooctanoic acid (PFOA) alongside with a 99% removal from the PFOA that accumulated on surface of the membrane. The removal of PFOA accumulated on the membrane surface achieved 99% after the membranes were treated with ultraviolet (UV) photolysis and liquid aerobic oxidation.

Enhanced Performance of Sulfonated GO in SPEEK Proton-Exchange Membrane for Microbial Fuel-Cell Application

AbstractSulfonated graphene oxide (SGO) was prepared using sulfuric acid and used as a nanofiller at various concentrations in self-fabricated sulfonated polyetheretherketone (SPEEK) to produce nan...

Strontium ranelate incorporated 3D porous sulfonated PEEK simulating MC3T3-E1 cell differentiation.

Polyetheretherketone (PEEK) has been used as an implant material because it has similar mechanical properties to natural bone. However, inferior osseointegration and bioinertness hamper the clinical application of PEEK. In this study, the surfaces of sulfonated three-dimensional (3D) PEEK porous structures were loaded with different concentrations of strontium ranelate, a compound commonly used in the treatment or prevention of osteoporosis by promoting bone formation and inhibiting bone resorption. Field-emission scanning electron microscopy was used to characterize the topography of the structures, elemental carbon, oxygen and strontium contents were measured by X-ray photoelectron spectroscopy, and surface zeta potentials and water-contact angle were also measured. The results indicated that strontium ranelate was successfully loaded onto the 3D porous structures. In vitro cellular results showed that strontium ranelate-treated sulfonated PEEK (SP-SR) strengthened the adhesion of MC3T3-E1 cells. The activity of alkaline phosphatase, collagen secretion and extracellular matrix mineralization deposition of MC3T3-E1 cells were also improved on the surface of SP-SR. These results indicate that SP-SR could serve a new implant candidate for surgical treatment.

MXene-Based Hydrogels Endow Polyetheretherketone with Effective Osteogenicity and Combined Treatment of Osteosarcoma and Bacterial Infection.

After an osteosarcoma resection, the risks of cancer recurrence, postoperative infection, and large bone loss still threaten patients' health. Conventional treatment relies on implanting orthopedic materials to fill bone defects after surgery, but it has no ability of destroying residual tumor cells and preventing bacterial invasion. To tackle this challenge, here, we develop a novel multifunctional implant (SP@MX/GelMA) that mainly consists of MXene nanosheets, gelatin methacrylate (GelMA) hydrogels, and bioinert sulfonated polyetheretherketone (SP) with the purpose of facilitating tumor cell death, combating pathogenic bacteria, and promoting osteogenicity. Because of the synergistic photothermal effects of MXene and polydopamine (pDA), osteosarcoma cells are effectively killed on the multifunctional coatings under 808 nm near-infrared (NIR) irradiation through thermal ablation. After loading tobramycin (TOB), the SP@MX-TOB/GelMA implants display robust antibacterial properties against Gram-negative/Gram-positive bacteria. More importantly, the multifunctional implants are demonstrated to have superior cytocompatibility and osteogenesis-promoting capability in terms of cell replication, spreading, alkaline phosphatase activity, calcium matrix mineralization, and in vivo osseointegration. Accordingly, such photothermally controlled multifunctional implants not only defeat osteosarcoma cells and bacteria but also intensify osteogenicity, which hold a greatly promising countermeasure for curing postoperative tissue lesion from an osteosarcoma excision.