Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M-n = 29,700g mol(-1) (M-PS = 9300 g mol(-1) M-PMMA = 20,100 g mol(-1), PD = 1.15, chi(PS) = 0.323, chi(PMMA) = 0.677) and M-n = 63,900 g mol(-1) (M-PS = 50,500 g mol(-1), M-PMMA = 13,400 g mol(-1), PD = 1.18, chi(PS) = 0.790, chi(PMMA) = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 degrees C for 24 h led to a change in surface structure

Fabrication of Embedded Microvalve on PMMA Microfluidic Devices through Surface Functionalization

The integration of a PDMS membrane within orthogonally placed PMMA microfluidic channels enables the pneumatic actuation of valves within bonded PMMA-PDMS-PMMA multilayer devices. Here, surface functionalization of PMMA substrates via acid catalyzed hydrolysis and air plasma corona treatment were investigated as possible techniques to permanently bond PMMA microfluidic channels to PDMS surfaces. FTIR and water contact angle analysis of functionalized PMMA substrates showed that air plasma corona treatment was most effective in inducing PMMA hydrophilicity. Subsequent fluidic tests showed that air plasma modified and bonded PMMA multilayer devices could withstand fluid pressure at an operational flow rate of 9 mircoliters/min. The pneumatic actuation of the embedded PDMS membrane was observed through optical microscopy and an electrical resistance based technique. PDMS membrane actuation occurred at pneumatic pressures of as low as 10kPa and complete valving occurred at 14kPa for 100 micrometers x 100 micrometers channel cross-sections.Comment: Submitted on behalf of EDA Publishing Association (http://irevues.inist.fr/handle/2042/16838

Experimental ex-vivo validation of PMMA-based bone cements loaded with magnetic nanoparticles enabling hyperthermia of metastatic bone tumors

Percutaneous vertebroplasty comprises the injection of Polymethylmethacrylate (PMMA) bone cement into vertebrae and can be used for the treatment of compression fractures of vertebrae. Metastatic bone tumors can cause such compression fractures but are not treated when injecting PMMA-based bone cement. Hyperthermia of tumors can on the other hand be attained by placing magnetic nanoparticles (MNPs) in an alternating magnetic field (AMF). Loading the PMMA-based bone cement with MNPs could both serve vertebra stabilization and metastatic bone tumor hyperthermia when subjecting this PMMA-MNP to an AMF. A dedicated pancake coil is designed with a self-inductance of 10 mu H in series with a capacitance of 0.1 mu F that acts as resonant inductor-capacitor circuit to generate the AMF. The thermal rise is appraised in beef vertebra placed at 10 cm from the AMF generating circuit using optical temperatures sensors, i. e. in the center of thePMMA-MNPbone cement, which is located in the vicinity of metastatic bone tumors in clinical applications; and in the spine, which needs to be safeguarded to high temperature exposures. Results show a temperature rise of about 7 degrees C in PMMA-MNP whereas the temperature rise in the spine remains limited to 1 degrees C. Moreover, multicycles heating of PMMA-MNP is experimentally verified, validating the technical feasibility of having PMMA-MNP as basic component for percutaneous vertebroplasty combined with hyperthermia treatment of metastatic bone tumors

Thermal Degradation Studies on PMMA–HET Acid Based Oligoesters Blends

Imparting thermal stability to polymethyl methacrylate (PMMA) without affecting its optical clarity is attempted by incorporating HET acid based oligoesters. Pure PMMA and PMMA containing five and 20 wt% of four different oligoesters are separately prepared using bulk polymerization. The thermal properties of the materials studied using DSC, TG, TG–FTIR and Pyr–GC–MS are presented. The main volatile degradation products identified are CO, HCl, CO2, H2O, hexachlorocyclopentadiene, hexachloroendomethylene tetrahydrophthalic acid/anhydride and methyl methacrylate. A detailed mechanism for the influence of the degradation products of HET acid based oligoesters on the thermal degradation of PMMA is also presented

Morphological and Tribological Properties of PMMA/Halloysite Nanocomposites

From an environmental and cost-effective perspective, a number of research challenges can be found for electronics, household, but especially in the automotive polymer parts industry. Reducing synthesis steps, parts coating and painting, or other solvent-assisted processes, have been identified as major constrains for the existing technologies. Therefore, simple polymer processing routes (mixing, extrusion, injection moulding) were used for obtaining PMMA/HNT nanocomposites. By these techniques, an automotive-grade polymethylmethacrylate (PMMA) was modified with halloysite nanotubes (HNT) and an eco-friendly additive N,N′-ethylenebis(stearamide) (EBS) to improve nanomechanical properties involved in scratch resistance, mechanical properties (balance between tensile strength and impact resistance) without diminishing other properties. The relationship between morphological/structural (XRD, TEM, FTIR) and tribological (friction) properties of PMMA nanocomposites were investigated. A synergistic effect was found between HNT and EBS in the PMMA matrix. The synergy was attained by the phase distribution resulted from the selective interaction between partners and favourable processing conditions. Modification of HNT with EBS improved the dispersion of nanoparticles in the polymer matrix by increasing their interfacial compatibility through hydrogen bonding established by amide groups with aluminol groups. The increased interfacial adhesion further improved the nanocomposite scratch resistance. The PMMA/HNT-EBS nanocomposite had a lower coefficient of friction and lower scratch penetration depth than PMMA/HNT nanocomposite.Financial support by the EU Commission through Project H2020-686165-IZADINANO2INDUSTRY is gratefully acknowledged

New Phosphated Poly(methyl Methacrylate) Polymers for the Prevention of Denture-induced Microbial Infection: an In Vitro Study

Purpose: Poly(methyl methacrylate) (PMMA) has been widely used as a denture-base acrylic resin due to its excellent physical and mechanical properties. However, the material is highly prone to microbial fouling that often leads to Candida-associated denture stomatitis. Incorporation of phosphate groups into PMMA could facilitate adsorption of salivary antimicrobials and inhibit microbial adherence on the polymer surface. An in vitro study evaluated PMMA polymers containing varying amounts of phosphate group for their efficacy to inhibit Candida albicans adhesion, adsorb salivary histatin 5, and exhibit candidacidal activity. Methods: Six PMMA polymers containing 0%, 5%, 15%, 10%, 20%, and 25% of phosphate group were synthesized by bead (suspension) polymerization technique using mixtures of methyl methacrylate and methallyl phosphate as monomers. The efficacy of the polymers to inhibit the adherence of C. albicans was examined by using human saliva-coated polymer beads and radio-labeled C. albicans cells, as compared with that of PMMA. The potency of the phosphated PMMA polymers to adsorb histatin 5 was determined by measuring the radioactivity of the adsorbed labeled-peptide on the polymer surface. The candidacidal activity of the histatin 5-adsorbed polymers was assessed by using the fluorescence technique. The percent release of the fluorescent probe calcein from the C. albicans membrane caused by the disruption of the cell membrane was determined. The data were analyzed statistically by one-way ANOVA followed by Scheffé’s test (α = 0.05 and n = 6). Results: The presence of ≥15% phosphate content in PMMA significantly reduced the saliva-mediated adhesion of C. albicans. Phosphated PMMA polymers showed significantly enhanced adsorption of histatin 5 in a phosphate density-dependent manner. The candidacidal activity of the histatin 5-bound polymers increased significantly with the increase in the phosphate content of the polymer. Conclusion: Phosphated PMMA polymers have the potential to serve as novel denture-base resins, which may reduce C. albicans colonization and prevent denture stomatitis

Thermooxidative stability of PMMA composites

Tato práce se zabývá studiem termooxidační stability kompozitů polymethylmethakrylátu (PMMA) plněného mikro a nanočásticemi siliky. V připravených vzorcích byly použity různé objemové zlomky a různé velikosti částic siliky. Studium stability bylo prováděno pomocí termogravimetrie, která umožňuje simulovat podmínky termooxidační degradace. Indukční perioda byla stanovena za použití různých rychlostí ohřevu a aplikací izokonverzních metod. Závislosti teplot degradací na rychlostech ohřevu sloužily pro určení parametrů odvozených ze čtyř různých teplotních funkcí, které dovolují předpověď stability materiálu (indukční periody) při zvoleném rozsahu teplot. Zjištěné výsledky ukazují, že větší částice siliky snižuji stabilitu PMMA, zatímco nanočástice v nízkých koncentracích ji nijak neovlivňují.In this work the thermooxidative stability of poly(methyl metacrylate) (PMMA) composites reinforced with silica micro and nanoparticles was studied. Different volume fractions and particles sizes of silica particles were used. PMMA/silica composites were analysed by thermogravimetry which simulated the conditions of thermooxidative degradation. The induction periods were determined using different heating rates and applying the isoconversional methods. The dependence of degradation temperatures on heating rates were used for the determination of adjustable parameters derived for four different temperature functions allowing the prediction of material stability (induction periods) at chosen temperatures. Results showed that the larger silica particles destabilized the PMMA structure while smallest nanoparticles at low concentration had no effect on the stability.

Nanoporous PMMA: A novel system with different acoustic properties

The acoustic properties of closed cell nanoporous and microporous poly(methyl methacrylate) (PMMA) foams have been well characterized, showing that nanoporous PMMA exhibit a different absorption coefficient and transmission loss behavior in comparison with microporous PMMA. Experimental differences may be explained by the different wave propagation mechanism in the micro and nanoscale, which is determined by the confinement of both the gas (Knudsen regime) and the solid phases. These results place nanoporous materials as a new class of polymeric porous material with potential properties in the field of acoustics, especially in multifunctional systems requiring a certain degree of soundproofing

Lithography-Free Route to Hierarchical Structuring of High-chi Block Copolymers on a Gradient Patterned Surface

A chemically defined patterned surface was created via a combined process of controlled evaporative self-assembly of concentric polymer stripes and the selective surface modification of polymer brush. The former process involved physical adsorption of poly (methyl methacrylate) (PMMA) segments into silicon oxide surface, thus forming ultrathin PMMA stripes, whereas the latter process was based on the brush treatment of silicon native oxide surface using a hydroxyl-terminated polystyrene (PS-OH). The resulting alternating PMMA- and PS-rich stripes provided energetically favorable regions for self-assembly of high <mml:semantics>chi</mml:semantics> polystyrene-block-polydimethylsiloxane (PS-b-PDMS) in a simple and facile manner, dispensing the need for conventional lithography techniques. Subsequently, deep reactive ion etching and oxygen plasma treatment enabled the transition of the PDMS blocks into oxidized groove-shaped nanostructures