Polyhedral Oligomeric Silsesquioxane Molecules Research Articles

Effect of semifluoroalkyl substituents in the POSS on atomic oxygen exposure

Due to the many recent Earth observation missions, very low Earth orbit (VLEO) have become a pressing topic for satellite research. Since the density of atomic oxygen (AO) in VLEO is higher than in low Earth orbit (LEO), the need for AO-resistant materials based on polyhedral oligomeric silsesquioxane (POSS) is strong. However, the effects of the side-chain groups in the POSS on AO exposure are unclear. In this study, we focused on POSS molecules modified with semifluoroalkyl groups as side chains because fluorocarbon groups, such as fluorinated ethylene propylene (FEP), are known to have high AO resistance. Semifluoroalkyl- and alkyl-substituted POSS films were fabricated and exposed to a laser-detonation AO source. Microbalance measurements showed that the mass losses of the semifluoroalkyl-substituted POSS films were larger than those of alkyl-substituted POSS films. X-ray photoelectron spectroscopy measurements showed that the silica layers formed on the semifluoroalkyl-substituted POSS were thicker than on alkyl-substituted POSS films. Surface observation using a field emission scanning electron microscope revealed microscale cracks on the surface of the semifluoroalkyl-substituted POSS. These findings indicate that POSS molecules with fluorine substituents warrant careful consideration of the AO-barrier performance of the silica layer formed during AO exposure.

Exciplex Emission in the POSS Possessing Two Kinds of Luminophores

Here we report the synthesis and luminescent properties of the modified polyhedral oligomeric silsesquioxane (POSS) that possesses two types of luminophores, cyanobenzene and N,N‐diethylaniline for inducing significant emission not only from each dye but also from molecular interactions on the POSS core. From the optical measurements in the diluted solution, we observed both locally‐excited emission and excimer emission originating from intramolecular interactions assisted by POSS. Moreover, highly‐efficient exciplex emission was observed from the thin film, indicating that the interaction between luminophores easily occurs in the solid state by accumulating two kinds of molecules in the single POSS molecule. Finally, we also found that the modified POSS showed a unique acid responsiveness which can be caused by protonation at two types of amino moieties. In this manuscript, it is shown that POSS is able to play various roles at the same time: recruiting excited molecules to form exciplexes, suppressing concentration quenching in the solid state, and imparting stimulus responsiveness to exciplexes.

Liquid crystalline polyurethane/POSS hybrid nanocomposites pyrolysis studies by Py-GC/MS and TG/FTIR techniques

The process of pyrolysis of liquid crystalline polyurethane (LCPU) composites with polyhedral oligomeric silsesquioxanes (POSS) has been studied using pyrolysis - gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetry/Fourier transform infrared spectroscopy (TG/FTIR) coupled thermoanalytical techniques. LCPU elastomers modified with POSS molecules with different architectures, bearing aromatic, isobutyl and cycloaliphatic moieties, yield various volatile products of pyrolysis that were collected and characterized. The TG study showed significant differences in the thermal behavior of composites studied, evidencing the influence of the silsesquioxane type on the polyurethane pyrolysis paths. FTIR study of volatile products of thermal decomposition showed the presence of characteristic bands originated from carbonyl, amine, ether, methylene, and unsaturated hydrocarbon linkages. GC/MS investigation confirmed the existence of compounds identified by the IR method. The application of both thermoanalytical methods made it possible to postulate the thermal decomposition routes of PU/POSS hybrids and to point out the main factors responsible for changes in the thermal stability.

Ab initio molecular dynamics study of interactions between isolated polyhedral oligomeric silsesquioxane trisilanols and aluminum

Trisilanol polyhedral oligomeric silsesquioxane (POSS) are a category of inorganic–organic material that comprise an inorganic open cage silica structure, organic attachments, and silanol (SiOH) groups. Recently, trisilanol POSS was added to Al-based alloys, and found to promote substantial microstructural refinement, and improved mechanical strength and fatigue life compared to conventional compositions. Such microstructural modifications and property enhancements are usually attributed to silanolAl bonds that formed within the liquid-state, prior to solidification. However, details of such high-temperature chemical interactions remain unclear. Here, we performed ab initio molecular dynamics simulations at 1500 K, to probe the chemical interactions between isolated trisilanol POSS molecule and discreet Al atoms. Al atoms modified the silanol groups to form, two energetically favorable coordinate complexes: monodentate SiOAl and bidentate (SiO)2Al. Such complexes were formed by Al atoms attracting electrons towards themselves from the POSS molecule. Crucially, this bonding mechanism allowed trisilanol POSS to organize the neighboring Al atoms into geometric motifs that can potentially serve as nucleation sites within liquid-Al, and facilitate microstructural refinement.

Unlocking Synthesis of Polyhedral Oligomeric Silsesquioxane-Based Three-Dimensional Polycubane Covalent Organic Frameworks.

Reticular chemistry effectively yields porous structures with distinct topological lattices for a broad range of applications. Polyhedral oligomeric silsesquioxane (POSS)-based octatopic building blocks with a rare Oh symmetric configuration and attracting inorganic features have great potential for creating three-dimensional (3D) covalent organic frameworks (COFs) with new topologies. However, the intrinsic flexibility and intensive motion of cubane-type POSS molecules make the construction of 3D regular frameworks challenging. Herein, by fastening three or four POSS cores with per aromatic rigid linker from rational steric directions, we successfully developed serial crystalline 3D COFs with unpresented "the" and scu topologies. Both the experimental and theoretical results proved the formation of target 3D POSS-based COFs. The resultant hybrid networks with designable chemical skeletons and high surface areas maintain the superiorities of both the inorganic and organic components, such as their high compatibility with inorganic salts, abundant periodic electroactive sites, excellent thermal stability, and open multilevel nanochannels. Consequently, the polycubane COFs could serve as outstanding solid electrolytes with a high ionic conductivity of 1.23 × 10-4 S cm-1 and a lithium-ion transference number of 0.86 at room temperature. This work offers a pathway to generate ordered lattices with multiconnected flexible cube motifs and enrich the topologies of 3D COFs for potential applications.

Processing and Characterization of UV Irradiated HDPE/POSS Fibers.

High-performance polyethylene fibers, renowned for their superior attributes encompassing a high strength, modulus, and lightness, are conventionally manufactured through the gel spinning method. However, this method is encumbered by several drawbacks, including the requisite application of a separate process to eliminate solvents from the fibers and the utilization of chemicals deleterious to both the environment and human health. Alternatively, the adoption of the melt spinning method presents a cleaner and environmentally friendly approach to attain high-performance fibers. In the present investigation, high-density polyethylene (HDPE) fibers were produced employing the melt spinning method. After the spinning process, strategic orientation procedures were implemented to enhance the crystallinity of the spun fibers. As a concluding step, seeking to elevate the overall performance of the oriented spun HDPE fibers, a cross-linking treatment was applied via UV irradiation. Notably, this study pioneers the incorporation of polyhedral oligomeric silsesquioxane (POSS) hybrid nanoparticles into HDPE during melt spinning, presenting a novel advancement aimed at further enhancing the mechanical properties of oriented HDPE fibers during UV irradiation. For this purpose, two distinct types of POSS, namely octavinyl POSS (OVPOSS) and methacryl POSS (MACPOSS), both having unsaturated double bonds capable of participating in the network structure of oriented HDPE spun during UV cross-linking, were used. The thermal, morphological, and mechanical properties, as well as the crystal structure of samples with and without POSS molecules, were investigated. The mechanical properties of the fibers exhibited higher values in the presence of OVPOSS. The incorporation of OVPOSS and MACPOSS resulted in a noteworthy improvement in the material's tensile strength, exhibiting a marked increase of 12.5 and 70.8%, respectively. This improvement can be attributed to the more homogeneous dispersion of OVPOSS in HDPE, actively participating in the three-dimensional network structure. After orientation and UV irradiation, the tensile strength of HDPE fibers incorporating OVPOSS increased to 293 MPa, accompanied by a concurrent increase in the modulus to 2.8 GPa. The addition of POSS nanoparticles thus yielded a substantial improvement in the overall performance of HDPE fibers.

Novel functionalized isocyanate groups polyhedral oligomeric silsesquioxanes/epoxy composites with advanced thermal and moisture resistance properties

AbstractThe rapid development of the electronic packaging industry has necessitated the production of epoxy resin insulation materials with high heat resistance and low water absorption. In this study a new cross‐linking composite composed of polyhedral oligomeric silsesquioxane (POSS) functionalized with isocyanate groups and epoxy resin (EP) containing phenolic hydroxyl groups. By employing an isocyanate‐hydroxyl process, the cage structure of Ph7POSS with isocyanate functionalization (MP) can be suspended on EP, leading to a significant improvement in the thermal and moisture resistance of the MP/EP composite. Our DSC and TGA studies revealed that the addition of 3% MP to the epoxy resin increased the glass transition temperature by 27.1°C and raised the initial thermal breakdown temperature to 334.5°C. We also utilized a novel quartz crystal microbalance (QCM) technique to continuously monitor the moisture resistance of the composite, and our results showed that the composite absorbed only 0.03% of water. Moreover, the porosity and cross‐linking of the POSS molecules further restricted the movement of the polymer chains, thereby reducing the dielectric constant and dielectric loss of the composite. Consequently, the MP‐modified epoxy composites exhibit excellent properties, which suggest promising applications in the field of electronic packaging.

Theoretical analysis of substituent- and cage-dependent electronic properties of POSS

Polyhedral Oligomeric Silsesquioxanes (POSS) molecules have emerged as promising alternatives to traditional silica nanoparticles and organosilicon molecules due to their ability to attach a variety of substituents to their central siloxane cages. The electronic features of POSS are dependent on the structures of substituents and cages, making them attractive for applications, such as drug nanocarriers, chemosensors, Janus particles, and inorganic–organic nanocomposites. However, the lack of detailed geometric data poses a difficulty in extending POSS studies using the force field method or beyond the quantum mechanical level. To lay a foundation for future experimental and computational studies, we present new theoretical insights into the influence of substituent and cage on the cage geometries (Si–O bond length, pore width, cage volume, etc.) of 16 substituted POSS molecules with various substituents and cages (T7, T8, T10, T12). Our results show that the mean Si–O bond length of the POSS cage can be in the range of 1.619–1.670 Å depending on the substituent and cage. Moreover, we show that the expansion or shrinkage of POSS depends on the types of substituents, rather than the inductive effect of substituents. Our results demonstrate that the conformational stability, dipole moment, and polarizability of POSS depend on the substituents’ size, substituents’ shape, type of functional moieties of substituents, and cage size. In addition, the HOMO-LUMO bandgap of POSS can be tuned by changing the hydrocarbon chain length, number of aromatic rings, and types of functional groups on the substituents. Finally, we report several sets of geometric data that are transferable to the existing parametrization methods of force field models.

R-Curve Behavior of Polyhedral Oligomeric Silsesquioxane (POSS)–Epoxy Nanocomposites

Polyhedral oligomeric silsesquioxane (POSS) is a suitable nanoscale reinforcement for thermosetting polymers, such as epoxy resin systems in order to modify its mechanical, thermal and chemical properties. The inclusion of POSS in the epoxy resin at higher loading (greater than 1 wt.%); however, it introduces the ductility during the fracture behavior of these nanocomposites. Consequently, the J-integral is used to quantify the fracture behavior of these materials and characterize the crack growth resistance curve against stable crack growth. A range of nanocomposites is prepared by adding 0.5, 1, 3, 5, and 8 wt.% of glycidyl POSS into DGEBF epoxy resin cured with an amine-based curing agent. From fracture toughness experiments, the load-displacement result confirms that when the POSS reinforcement is greater than 1 wt.%, the fracture behavior of the nanocomposite changes from brittle to ductile. For both brittle and ductile nanocomposites, the addition of POSS molecules improves the crack initiation toughness. The development of POSS–POSS compliant domains, reported previously, is responsible for this change in the failure behavior. The fractured images of POSS–epoxy nanocomposites, obtained by using scanning electron microscopy, show that the increase in fracture resistance at higher values of POSS loading occurs due to the extensive shear yielding. Meanwhile, the increased fracture toughness at lower values of POSS loading occurs due to crack pinning and crack deflection.

Effect of POSS on the Dielectric Properties of Thermally Aged Epoxy Resin Insulating Materials

Polyhedral oligomeric silsesquioxane (POSS) can significantly improve the short-term insulation ability of epoxy materials under high electric field, which makes epoxy/POSS composites show a wide application prospect in high-voltage power equipment. The changes in performance due to aging is the concern of the long-term application of epoxy materials in power equipment. Therefore, the influence of Glycidyl POSS on the insulation performance of epoxy materials in the aging process needs to be investigated. In this article, different mass fractions of epoxy/POSS composites were prepared and the effect of POSS on the dielectric loss of epoxy materials after thermal aging was investigated. The results show that the addition of a small amount of POSS can effectively inhibit the low-frequency dielectric loss of epoxy insulating materials during thermal aging. Combined with the dc volume resistivity test of epoxy composites and the quantum chemical calculation results of POSS molecules, a possible mechanism of POSS inhibiting the dielectric loss of epoxy resin during thermal aging was proposed. The present work provides a reference for further development of POSS in the field of electrical insulation and the application of POSS modified composites in power equipment such as low-frequency transmission and dc transmission equipment.

Self-Healing Silsesquioxane-Based Materials

This review is devoted to self-healing materials (SHM) containing polyhedral oligomeric silsesquioxanes (POSS) as building blocks. The synthetic approach can vary depending on the role POSS are expected to play in a given system. POSS (especially double-decker silsesquioxanes) can be grafted in side chains of a polymer backbone or used as segments of the main chain. Appropriate functionalization allows the formation of dynamic bonds with POSS molecules and makes them an active component of SHM, both as crosslinking agents and as factors that enhance the dynamics of macromolecules in the polymer matrix. The latter effect can be achieved by reversible release of bulky POSS cages or by the formation of separated inclusions in the polymer matrix through hydrophobic interactions and POSS aggregation. The unique properties of POSS-based self-healing systems make them interesting and versatile materials for various applications (e.g., repairable coatings, sealants, sensors, soft materials for tissue engineering, drug delivery, and wound healing).

Influence of POSS Type on the Space Environment Durability of Epoxy-POSS Nanocomposites.

In order to use polymers at low Earth orbit (LEO) environment, they must be protected against atomic oxygen (AO) erosion. A promising protection strategy is to incorporate polyhedral oligomeric silsesquioxane (POSS) molecules into the polymer backbone. In this study, the space durability of epoxy-POSS (EPOSS) nanocomposites was investigated. Two types of POSS molecules were incorporated separately—amine-based and epoxy-based. The outgassing properties of the EPOSS, in terms of total mass loss, collected volatile condensable material, and water vapor regain were measured as a function of POSS type and content. The AO durability was studied using a ground-based AO simulation system. Surface compositions of EPOSS were studied using high-resolution scanning electron microscopy and X-ray photoelectron spectroscopy. It was found that with respect to the outgassing properties, only some of the EPOSS compositions were suitable for the ultrahigh vacuum space environment, and that the POSS type and content had a strong effect on their outgassing properties. Regardless of the POSS type being used, the AO durability improved significantly. This improvement is attributed to the formation of a self-passivated AO durable SiO2 layer, and demonstrates the potential use of EPOSS as a qualified nanocomposite for space applications.

Biocompatibility Computation of Muscle Cells on Polyhedral Oligomeric Silsesquioxane-Grafted Polyurethane Nanomatrix.

This study was performed to appraise the biocompatibility of polyhedral oligomeric silsesquioxane (POSS)-grafted polyurethane (PU) nanocomposites as potential materials for muscle tissue renewal. POSS nanoparticles demonstrate effectual nucleation and cause noteworthy enhancement in mechanical and thermal steadiness as well as biocompatibility of resultant composites. Electrospun, well-aligned, POSS-grafted PU nanofibers were prepared. Physicochemical investigation was conducted using several experimental techniques, including scanning electron microscopy, energy dispersive X-ray spectroscopy, electron probe microanalysis, Fourier transform infrared spectroscopy, and X-ray diffraction pattern. Adding POSS molecules to PU did not influence the processability and morphology of the nanocomposite; however, we observed an obvious mean reduction in fiber diameter, which amplified specific areas of the POSS-grafted PU. Prospective biomedical uses of nanocomposite were also appraised for myoblast cell differentiation in vitro. Little is known about C2C12 cellular responses to PU, and there is no information regarding their interaction with POSS-grafted PU. The antimicrobial potential, anchorage, proliferation, communication, and differentiation of C2C12 on PU and POSS-grafted PU were investigated in this study. In conclusion, preliminary nanocomposites depicted superior cell adhesion due to the elevated free energy of POSS molecules and anti-inflammatory potential. These nanofibers were non-hazardous, and, as such, biomimetic scaffolds show high potential for cellular studies and muscle regeneration.

The effect of polyhedral oligomeric silsesquioxanes (POSSs) incorporation in ethylene-propylene-diene-terpolymer (EPDM): a thermal study

A series of ethylene-propylene-diene-terpolymer (EPDM)/polyhedral oligomeric silsesquioxane (POSS) composites at different percentage of POSS were prepared and subjected to γ-irradiation. Both irradiated and non-irradiated EPDM and composites were investigated by the means of thermal analysis to verify if the presence of POSS molecules is able to reduce the oxidation level of free radicals generated during the degradation and to evaluate the effects of the irradiation. EPDM composites at 1, 3 and 5 mass% of POSS were thus degraded in a thermogravimetric (TG) balance in dynamic heating conditions (25–700 °C), in both inert and oxidative atmosphere by flowing nitrogen and air respectively. Thermal characterization was then completed by carrying out Differential Scanning Calorimetry (DSC) analysis from sub-ambient to better highlight the melting of the polymer and polymer composites occurring just above the room temperature. FTIR spectroscopy was also performed for the prepared samples to check the presence of the molecular filler in the composites and for the TG’s residue at 700 °C, in order to evaluate its nature. DSC and TGA parameters were detected and discussed to have information about the effect of the degradation’s environment, the effect of irradiation on polymer stabilization and the effect of POSS content in the polymer matrix.

Chiral Silica with Preferred-Handed Helical Structure via Chiral Transfer.

A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.

Kinetic Study of the Thermal and Thermo-Oxidative Degradations of Polystyrene Reinforced with Multiple-Cages POSS.

A comprehensive kinetics degradation study is carried out on novel multiple cages polyhedral oligomeric silsesquioxane (POSS)/polystyrene (PS) composites at 5% (w/w) of POSS to assess their thermal behavior with respect to the control PS and other similar POSS/PS systems studied in the past. The composites are synthesized by in situ polymerization of styrene in the presence of POSSs and characterized by 1H-NMR. The characteristics of thermal parameters are determined using kinetics literature methods, such as those developed by Kissinger and Flynn, Wall, and Ozawa (FWO), and discussed and compared with each other and with those obtained in the past for similar POSS/PS composites. A good improvement in the thermal stability with respect to neat polymer is found, but not with respect to those obtained in the past for polystyrene reinforced with single- or double-POSS cages. This behavior is attributed to the greater steric hindrance of the three-cages POSS compared with those of single- or double-cage POSS molecules.

Efficient Synthesis of Low-Polydispersity UHMWPE by Elevating Active Sites on Anchored POSS Molecules

Ultrahigh-molecular-weight polyethylene (UHMWPE) with a low polydispersity exhibits excellently physical and mechanical properties. In this work, a polyhedral oligomeric silsesquioxane (POSS)-modif...

Polyurethane–POSS hybrid materials: by solution blending and in-situ polymerization processes

Polyhedral oligomeric silsesquioxane (POSS) is a nanostructured soft material that tremendously influences the properties of polymers. This paper delineates the preparation of polyurethane–POSS hybrid materials by physical blending and in-situ polymerization, and studies their properties. In the physical blending method, a polyurethane (BDO–PU) was prepared by using polycaprolactone diol (PCL-diol) as a soft segment, 4,4 $$^\prime $$ -methylenebis(phenyl isocyanate) (MDI) as a diisocyanate and 1,4-butanediol (BDO) as a chain extender. The PU–POSS hybrid material (BDO–PU/POSS) was then prepared by the dispersion of POSS (octahydroxy POSS) molecules in the synthesized BDO–PU matrix by the solution mixing method. In the in-situ polymerization method, POSS–PU and POSS–BDO–PU hybrid materials were prepared using POSS and the combination of POSS and BDO as a crosslinker or a chain extender. The formation of PU and PU–POSS hybrid materials was confirmed by Fourier transform infrared and differential scanning calorimetry analyses. The introduction of octahydroxy POSS molecules into the PU matrix resulted in a reduction of glass transition temperature ( $$T_{\mathrm {g}})$$ . However, POSS–PU hybrid materials prepared by the in-situ polymerization method had significantly less $$T_{\mathrm {g}}$$ compared to the hybrid materials prepared by the solution or physical blending method. The incorporation of POSS molecules by using the in-situ polymerization process resulted in an increase in the surface hydrophobicity (water contact angle, WCA $$=$$ 125 $$^{\circ }$$ ) compared to the same prepared by using the solution blending process (WCA $$=$$ 106 $$^{\circ }$$ ). Moreover, the WCA values of all hybrid materials (WCA $$=$$ 106–125 $$^{\circ }$$ ) are much higher than those of the pristine BDO–PU (WCA $$=$$ 84 $$^{\circ }$$ ). The higher WCA value of the hybrid materials is due to the combined effect of the hydrophobic nature of POSS molecules as well as the increased surface roughness, as evidenced by the AFM 3D images. The hybrid materials prepared by the in-situ polymerization method exhibited improved mechanical and thermal properties compared to those prepared by the solution blending method.

Polyhedral oligomeric silsesquioxane/epoxy coatings: a review

Nowadays, there is a need for a paradigm shift in material selection for surface coatings so as to meet the requirements of advanced systems. Polyhedral oligomeric silsesquioxanes (POSS) are three-dimensional networks with a silica-like core covered by an organic shell, a promising nanosized structure for organic coatings. The use of POSS structures in coating materials has experienced an almost erratic period over the past decade, mainly because of the synthesis of POSS being exclusive and, to some extent, expressive. However, there has been a big return to the use of POSS in coatings during the last years. Epoxy is best known for its versatility of usage as an organic coating. Hybrid organic–inorganic POSS nanostructures with unique properties are a complement to the epoxy for coating applications. The tailorable compatibility and considerable reactivity of POSS molecules towards organic groups have made them promising candidates for emerging multifunctional epoxy coatings. In this sense, the focus of this review is placed on POSS/epoxy nanocomposite coatings. The thermal, mechanical, anti-corrosion and dielectric properties of POSS/epoxy coatings have been comprehensively studied and discussed.

PDMS mixed‐matrix membranes with molecular fillers via reactive incorporation and their application for bio‐butanol recovery from aqueous solution

AbstractMixed‐matrix membrane (MMM) consisting of fillers in polymeric matrix offers a promising approach to develop high‐performance membranes, while remain challenges in achieving ideal filler dispersion and interfacial morphology. Herein, we reported on a new kind of MMM with molecular‐level dispersion of filler via a proposed reactive incorporation approach. Specifically, polyhedral oligomeric silsesquioxanes (POSS) with vinyl groups was grafted with ethoxy groups to build covalent bond with hydroxyl‐terminated polydimethylsiloxane (PDMS) chains to fabricate PDMS MMMs uniformly dispersed with POSS molecules. The molecular dispersion of POSS in PDMS matrix was visualized by SEM, AFM, and TEM characterizations, as well as reflected by XRD analysis. The PDMS chain conformation affected by the reactive incorporation of POSS was investigated by analyzing the thermal and mechanical properties of the POSS/PDMS MMMs using DSC, TGA, and DMA measurements. Contact angle test was used to study the surface affinity and positron annihilation technique was employed to probe the free volumes, which are respectively associated with the sorption and diffusion behavior in the POSS/PDMS MMMs. The results demonstrated that molecular cages and crosslinking effect of POSS led to an increase of large free volumes while a decline of small free volumes. Therefore, the PDMS MMM with reactive incorporation of only 2 wt.% POSS simultaneously enhanced the butanol permeability (by 78%) and butanol/water selectivity (by 124%) for pristine PDMS membrane, transcending the performance limit of state‐of‐the‐arts organophilic membranes. The proposed reactive incorporation approach may provide a platform of developing highly efficient membranes for molecular separation.