Surface ionization state and nanoscale chemical composition of UV-irradiated poly(dimethylsiloxane) probed by chemical force microscopy, force titration, and electrokinetic measurements

The surface chemistry and ionization state of cross-linked poly(dimethylsiloxane) (PDMS) exposed to UV/ozone were studied as a function of treatment time. Various complementary and independent experimental techniques were utilized, which yielded information on the macroscopic as well as the nanometric scale. The average chemical composition of the PDMS surface was quantitatively investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS). It was found that the top 1-2 nm surface layer was dominated by silanol groups (-SiOH) for which the concentration increased with increasing treatment dose. The lateral distributions of the silanol groups were analyzed on the nanometer scale by means of atomic force microscopy (AFM) with chemically functionalized tip probes in aqueous buffer solutions at varying pHs. Spatially dependent pull-off force curves (also called "force volume" imaging) indicated the presence of strong chemical heterogeneity of the probed surface. This heterogeneity took the form of patches of silanol functionalities with high local concentration surrounded by a matrix of predominantly hydrophobic domains at low pH. The average pull-off forces for the entire surface scanned were significantly reduced for pH values larger than a characteristic pK(a) constant (in the range between 4.5 and 5.5). The extent of the decrease in the pull-off force and the particular value of pK(a) were found to be a function of treatment time and to differ from the commonly reported values for silanol functional groups on a homogeneous silica surface. These dependences were ascribed to the evoking of a protonation/deprotonation process of the surface silanol groups which was sensitive to the hydrophobic/hydrophilic balance of their close molecular environment. Intermolecular hydrogen bonding may also account for the shifts in the surface pK(a). Furthermore, depending on the nature of the electrolyte, a third effect related to double layer composition, as determined by specific ion adsorption, was quantitatively analyzed by streaming potential measurements in the presence of sodium chloride and phosphate electrolytes.     

Exploiting poly(dimethylsiloxane)-modified tips to evaluate frictional behavior by friction force microscopy

With the aim of investigating the effect of the surface properties on the friction behavior of self-assembled monolayers, we have modified tipless atomic force microscopy (AFM) cantilevers with a poly(dimethylsiloxane) (PDMS) lens. The friction coefficient using the silicon tip is strongly influenced by the mechanical properties of the substrate monolayer because hard, sharp silicon tips penetrate the surface of organic monolayers. However, the friction coefficient obtained for the PDMS-modified AFM cantilever is mostly due to the surface properties of the monolayer functional end group, rather than the viscoelastic deformation of the monolayer. The use of the PDMS tip was demonstrated as a novel means to investigate the effect of surface properties on the frictional behavior of self-assembled monolayers with various functional groups with less mechanical deformation.     

Masterless soft lithography: patterning UV/ozone-induced adhesion on poly(dimethylsiloxane) surfaces

A novel microreactor-based photomask capable of effecting high resolution, large area patterning of UV/ozone (UVO) treatments of poly(dimethylsiloxane) (PDMS) surfaces is described. This tool forms the basis of two new soft lithographic patterning techniques that significantly extend the design rules of decal transfer lithography (DTL). The first technique, photodefined cohesive mechanical failure, fuses the design rules of photolithography with the contact-based adhesive transfer of PDMS in DTL. In a second powerful variation, the UVO masks described in this work enable a masterless soft lithographic patterning process. This latter method, UVO-patterned adhesive transfer, allows the direct transfer of PDMS-based polymer microstructures from a slab of polymer to silicon and other material surfaces. Both methods exploit the improved process qualities that result from the use of a deuterium discharge lamp to affect the UVO treatment to pattern complex, large area PDMS patterns with limiting feature sizes extending well below 1 microm (> or = 0.3 microm). The use of these structures as resists is demonstrated for the patterning of metal thin films. A time-of-flight secondary ion mass spectroscopy study of the process provides new insights into the mechanisms that contribute to the chemistry responsible for the interfacial adhesion of DTL transfers.     

Observations on the swelling of cross-linked poly(dimethylsiloxane) networks by solvents

The Flory Huggins Solvent parameter (χ) previously published for a range of solvents and a cross-linked silicone polymer, have been recalculated using the original swelling data, but including a term representing the loss of configurational entropy consequent on crosslinking. From the Shore hardness of the polymer, the Young’s modulus E was calculated. E = 6(C₁ + C₂), where C₁ and C₂ are the parameters from the Mooney Rivlin equation for the elastic deformation of an elastomer. Since C₁ is related to M_c, the average molecular weight between crosslinks, revised χ values could be calculated for various values of C₂/C₁. These showed that for good solvents for the silicone polymer, the values published previously were too high.     

UV‐curable bismaleimides containing poly(dimethylsiloxane): Use as hydrophobic agent

The synthesis and characterization of poly(dimethylsiloxanes) bearing maleimides end‐groups (PDMSM) were carried out through imidization of maleic anhydride with three poly(dimethylsiloxanes) diamines of different molecular weights. Self‐photopolymerization of PDMSM was studied by Real‐Time Fourier Transform infrared spectroscopy (RT‐FTIR) and was possible even without photoinitiator (Darocur 1173). The reaction was found to proceed within seconds upon exposure to ultraviolet (UV) radiation to generate highly crosslinked polymer networks. The results indicated that these polymerizations were less sensitive to oxygen inhibition than the radical processes carried out on conventional UV‐curable acrylate resins. The thermal and mechanical properties of these resulting materials were studied starting from PDMS precursors with different molecular weights. These materials exhibit a low glass transition temperature (相似文献   

Chemical force titrations of amine- and sulfonic acid-modified poly(dimethylsiloxane)

Chemical force titrations-measurements of the adhesive interaction between a pair of suitably chemically modified atomic force microscopy (AFM) tip and sample surfaces as a function of pH-have been carried out for various combinations of silanol, amine, carboxylic acid, and sulfonic acid functional groups on both tip and sample. The primary surface material studied was poly(dimethylsiloxane) (PDMS). Surface modification was carried out using a plasma oxidation process to form silanol sites; further modification with amine or sulfonic acid sites was carried out by reaction of the silanol sites with the appropriate trialkoxysilane derivative. AFM tips were also modified using trialkoxysilane compounds. In the cases of tip/sample combinations with the same functional group on each, surface pK(1/2) values could be determined. In several "mixed" tip/sample combinations, a peak appeared in the titration curve midway between the surface pK(1/2) values of the tip and sample, consistent with an ionic H-bonding model for the interactions. The amine/sulfonic acid pair showed more complex behavior; the amine-terminated tip/sulfonic acid-terminated PDMS surface force titration curve consisted of two peaks centered at pH 4 and pH 8. Reversing the tip/sample pair resulted in the peak positions being shifted upward by 1.0 pH unit. The peak appearing at lower pH is assigned to electrostatic interactions between the two oppositely charged surfaces, whereas the higher pH peak is believed to arise due to ionic H-bonding interactions. AFM images show the effects on surface patterning of amine- and sulfonic acid-modified PDMS surfaces that have undergone two different oxidation methods (air plasma oxidation and Tesla coil oxidation). The surface morphologies of freshly prepared and 24 h aged air plasma oxidized PDMS are also discussed in this study.     

High efficiency micellar electrokinetic chromatography of hydrophobic analytes on poly(dimethylsiloxane) microchips

This paper describes a simple method for the effective and rapid separation of hydrophobic molecules on polydimethylsiloxane (PDMS) microfluidic devices using Micellar Electrokinetic Chromatography (MEKC). For these separations the addition of sodium dodecyl sulfate (SDS) served two critical roles - it provided a dynamic coating on the channel wall surfaces and formed a pseudo-stationary chromatographic phase. The SDS coating generated an EOF of 7.1 x 10(-4) cm(2) V(-1) s(-1) (1.6% relative standard deviation (RSD), n = 5), and eliminated the absorption of Rhodamine B into the bulk PDMS. High efficiency separations of Rhodamine B, TAMRA (6-carboxytetramethylrhodamine, succinimidyl ester) labeled amino acids (AA), BODIPY FL CASE (N-(4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacene-3-propionyl)cysteic acid, succinimidyl ester) labeled AA's, and AlexaFluor 488 labeled Escherichia coli bacterial homogenates on PDMS chips were performed using this method. Separations of Rhodamine B and TAMRA labeled AA's using 25 mM SDS, 20% acetonitrile, and 10 mM sodium tetraborate generated efficiencies > 100,000 plates (N) or 3.3 x 10(6) N m(-1) in <25 s with run-to-run migration time reproducibilities <1% RSD over 3 h. Microchips with 30 cm long serpentine separation channels were used to separate 17 BODIPY FL CASE labeled AA's yielding efficiencies of up to 837,000 plates or 3.0 x 10(6) N m(-1). Homogenates of E. coli yielded approximately 30 resolved peaks with separation efficiencies of up to 600,000 plates or 2.4 x 10(6) N m(-1) and run-to-run migration time reproducibilities of <1% RSD over 3 h.     

Vibrational spectroscopic study of poly(dimethylsiloxane)-ZnO nanocomposites

A series of poly(dimethylsiloxane)-zinc oxide (PDMS-ZnO) nanocomposites having different concentrations of ZnO nanoparticles (0, 1, 5, 10 and 20 wt%) have been prepared. Raman and FTIR-ATR spectroscopic analysis was performed in order to determine the interaction between the ZnO nanoparticles and PDMS polymer matrix. Density functional theory (DFT) using the (B3-LYP)/6-311++G(2df,2p) method was used to investigate the vibrational spectra of PDMS. A complete vibrational assignment is supported by the normal coordinate analysis, calculated Raman activities as well as IR intensities.The presence of ZnO nanoparticles in PDMS gives rise to significant differences in relative intensities of the characteristic vibrational bands with respect to the cross-linked polymer. The changes in relative intensities of Raman bands, as well as swelling measurements, were used to explain the effect of ZnO nanoparticles on the cross-linked structure of PDMS nanocomposites. It is established that ZnO nanoparticles influence the cross-linking density of the polymer matrix.     

A novel method for static equation-of state-development: equation of state of a cross-linked poly(dimethylsiloxane) (PDMS) network to 10 GPa

Pressure-volume-temperature (PVT) equation-of-state (EOS) information for polymers and polymeric composites is valuable for predicting their response to extreme conditions. An obstacle in determining equations of state for polymeric materials is the lack of a simple, static experimental method for acquiring PVT data for solid networks and liquids at pressures greater than several kilobars. Here, we report a novel approach in determining static EOS for polymers using high-pressure diamond-anvil cells coupled with optical microscopy and image analysis. Results are presented for a cross-linked poly(dimethylsiloxane) polymer, Sylgard 184. Static isothermal results were fitted to empirical and semiempirical equations of state, including the Tait, Birch-Murnaghan, and Vinet forms. Static PV data were also converted to pseudoshock velocity-pseudoparticle velocity (U(s)-u(p)) for comparison to dynamic Hugoniot data. A linear Rankine-Hugoniot fit U(s)=s(T)u(p)+c(T) gives c(T)=1.572 km/s and s(T)=1.703. s(T) is related to the pressure derivative of the bulk modulus B(0) (') by s(T)=(B(0) (')+1)/4 and B(0) (')=5.8. A comparison of the static and shock data is given, along with an estimate of the Grüneisen parameter, and a discussion of the free volume content in the polymer network, and limitations of this novel method.     

Neutron reflectometry and spectroscopic ellipsometry studies of cross-linked poly(dimethylsiloxane) after irradiation at 172 nm

Poly(dimethylsiloxane) (PDMS) was irradiated under ambient conditions in air with a Xe2-excimer lamp. The formation of atomic oxygen and ozone during irradiation in air by V-UV photons results in the transformation of PDMS to silicon oxide. The irradiated surfaces were studied by spectroscopic ellipsometry and neutron reflectometry. The measurements revealed the formation of a rough, i.e., between 11 and 20 nm, oxidized surface layer and a decrease of the total layer thickness. The thickness of the oxidized layer decreased for a given PDMS thickness when the polymer was irradiated for longer times and/or higher intensities. The composition of the oxidized layer after irradiation was not uniform through the layer and consisted of a mixture of original polymer and silicon bonded to three or four oxygen atoms (SiOx). The refractive index n determined by ellipsometry reaches a value similar to values reported for SiO2.     

Corrosion studies and interfacial bonding of urea/poly(dimethylsiloxane) sol/gel hydrophobic coatings on AA 2024 aluminum alloy

Bis[(ureapropyl)triethoxysilane] bis(propyl)-terminated-polydimethylsiloxane 1000 (PDMSU), an organic-inorganic hybrid, diluted in either EtOH or a mixture of EtOH-PrOH, was used in thin film form (<200 nm) to inhibit the corrosion of AA 2024 alloy. Potentiodynamic, time-dependent cyclovoltammetric measurements and salt spray tests showed that the corrosion inhibition of the latter was 10 times higher than that of the former films. This was correlated with the higher degree of hydrolysis and the formation of more open polyhedral silsesquioxane species (T2) in the bulk heat-treated PDMSU/EtOH-PrOH xerogels (29Si NMR spectra). The structure of the coatings deposited on AA 2024 Al alloy was deduced from the infrared reflection-absorption (IR RA) spectra, which revealed more extensive urea-urea interactions and more efficient silane-Al interface bonding for the PDMSU/EtOH-PrOH coatings with higher corrosion inhibition. Ex situ IR RA potentiodynamic spectroelectrochemical measurements of PDMSU coatings revealed that their degradation did not proceed via the formation of silanol groups and consequent hydration of the coatings but that they decomposed above E(corr) by forming fragments composed of -CH2- segments in an all-trans conformation.     

Pervaporation characteristics of cross-linked poly(dimethylsiloxane) membranes for removal of various volatile organic compounds from water

The permeation and separation characteristics of volatile organic compounds (VOCs), such as chloroform, benzene, and toluene, from water by pervaporation through cross-linked poly(dimethylsiloxane) membranes prepared from poly(dimethylsiloxane) dimethylmethacrylate macromonomer (PDMSDMMA) and divinyl compounds, such as ethylene glycol dimethylmethacrylate (EGDM), divinyl benzene (DVB), divinyl siloxane (DVS), and divinyl perfluoro-n-hexane (DVF) are described. When aqueous solutions containing 0.05 wt.% VOCs were permeated through cross-linked PDMSDMMA membranes, these membranes showed high VOC/water selectivity and permeability. Both VOC/water selectivity and permeability were affected significantly by the divinyl compound. Furthermore cross-linked PDMSDMMA membranes showed the highest chloroform/water selectivity. The VOC/water selectivity was mainly governed by the sorption selectivity rather than the diffusion selectivity. However, the difference in the selectivity between different types of VOCs depended on differences in the diffusivity of permeants. With increasing downstream pressure, the VOC/water selectivity of all cross-linked PDMSDMMA membranes increased, but the permeability decreased. A PDMSDMMA–DVF membrane exhibited a normalized permeation rate of 1.9 × 10⁻⁵ kg m/m² h and a separation factor for chloroform/water of 4850, yielding a separation index of 9110. The pervaporation characteristics of the cross-linked PDMSDMMA membranes are discussed based on their chemical and physical structures as well as the chemical and physical properties of the permeants.     

Light-induced water swelling/shrinking recovery of hydrogels based on chemically cross-linked poly (vinyl alcohol)

Photoresponsive hydrogels with high performance are of considerable interest because of their wide application. In this paper, a kind of smart poly (vinyl alcohol) (PVA) hydrogel is obtained using 4, 4′-azodibenzoic acid as cross-link agent. The hydrogels have the ability of swelling and shrinking reversibly under irradiation by ultraviolet or visible light because azobenzene groups show trans–cis isomerization under suitable light wavenumber. Under UV irradiation, azobenzene takes the cis structure which leads to volume decreases; macroscopically, shrinking can be observed. Under visible light irradiation, the volume recovers, and swelling can be observed macroscopically. Hydrogels have excellent swelling/shrinking recovery properties even after 12 cycles. The procedure achieves loop control of the transformation from light energy to mechanical energy.     

Electrostatic force microscopy measurements of CdSe-PS nanoparticles and CdSe-PS/poly(styrene-b-butadiene-b-styrene) nanocomposites

Electrostatic force microscopy (EFM) measurements were performed to analyze the conductive properties of CdSe nanoparticles functionalized with polystyrene (PS) brushes and embedded in a poly(styrene-b-butadiene-b-styrene) triblock copolymer. CdSe nanoparticles were synthesized aqueously and functionalized with polystyrene chains by the grafting through technique. CdSe-PS nanoparticles obtained after 5 and 8 h of polymerization were analyzed, in order to study the effect of the molecular weight of PS chains on conductive properties. EFM results showed the maintenance of the conductive properties of CdSe nanoparticles through functionalization reactions and even when they were confined in the block copolymer. Due to the low differences between the values obtained in the response of the samples to the charged tip, no effect of the molecular weight of brushes was confirmed.     

Atomic force microscopy of human serum albumin (HSA) on poly(styrene/acrolein) microspheres

Atomic Force Microscopy (AFM) in the tapping mode was used for the observation of bare poly (styrene/acrolein) P(SA) microspheres and microspheres with attached HSA. Prior to the AFM observations the P(SA) microspheres were immobilized covalently on the surface of quartz slides modified with -aminopropyltriethoxysilane. Atomic Force Microscopy pictures were registered for the dry samples. The partial coalescence of the P(SA) microspheres connected to the quartz surface with amino groups has been observed. The AFM pictures of the single P(SA) microspheres revealed that the surface of these particles is smooth and that any irregularities, if present, do not exceed 1 nm. The surface of microspheres with attached HSA has very clearly different morphology with regular pattern of HSA macromolecules. Cracks on the surfaces of some microspheres with HSA revealed that protein macromolecules are attached to these particles in several layers. In the case of some other microspheres the defects in protein attachment allowed the observation of the border between the bare surface of the P(SA) microspheres and the surface covered with protein macromolecules. Comparison of the thickness of the HSA layers on the P(SA) microspheres with the dimensions of HSA macromolecules, determined earlier from the x-ray studies, suggests that the first layer, 3.0±0.2 nm thick, is formed of the HSA macromolecules arranged flatly on the surface whereas protein macromolecules in the subsequent layers, each 8.6±1 nm thick, are adsorbed protruding from the surface.     

Block copolymer compatibilizers for polystyrene/poly(dimethylsiloxane) blends

Symmetric polystyrene (PS)–poly(dimethylsiloxane) (PDMS) diblock copolymers were mixed into a 20% dispersion of PDMS in PS. The effect of adding the block copolymer on the blend morphology was examined as a function of the block copolymer molecular weight (M_n,bcp), concentration, and viscosity ratio (η_r). When blended together with the PS and PDMS homopolymers, most of the block copolymer appeared as micelles in the PS matrix. Even when the copolymer was preblended into the PDMS dispersed phase, block copolymer micelles in the PS matrix phase were observed with transmission electron microscopy after mixing. Adding 16 kg/mol PS–PDMS block copolymer dramatically reduced the PDMS particle size, but the morphology, as examined by scanning electron microscopy, was unstable upon thermal annealing. Adding 156 kg/mol block copolymer yielded particle sizes similar to those of blends with 40 or 83 kg/mol block copolymers, but only blends with 83 kg/mol block copolymer were stable after annealing. For a given value of M_n,bcp, a minimum PDMS particle size was observed when η_r ～ 1. When η_r = 2.6, thermally stable, submicrometer particles as small as 0.6 μm were observed after the addition of only 3% PS–PDMS diblock (number‐average molecular weight = 83 kg/mol) to the blend. As little as 1% 83 kg/mol block copolymer was sufficient to stabilize a 20% dispersion of 1.1‐μm PDMS particles in PS. Droplet size reduction was attributed to the prevention of coalescence caused by small amounts of block copolymer at the interface. The conditions under which block copolymer interfacial adsorption and interpenetration were facilitated were explained with Leibler's brush theory. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 346–357, 2002; DOI 10.1002/polb.10098     

Single molecule force spectroscopy on poly(vinyl alcohol) by atomic force microscopy

The elastic properties of poly(vinyl alcohol) (PVA) were investigated on the nanoscale using the new technique of single molecule force spectroscopy by atomic force microscopy (AFM). It was found that the elastic properties of PVA molecules scale linearly with their contour lengths. This finding corroborates that the deformation of individual PVA chains is measured. The force spectra of PVA show a kink at around 200 pN and cannot be fitted by an extended Langevin function. The deviation of the elastic behavior of PVA from a freely jointed chain model may indicate the presence of a suprastructure of PVA in NaCl solution.     

The effect of compatibilization and rheological properties of polystyrene and poly(dimethylsiloxane) on phase structure of polystyrene/poly(dimethylsiloxane) blends

The compatibilization effect of polystyrene (PS)‐poly(dimethylsiloxane) (PDMS) diblock copolymer (PS‐b‐PDMS) and the effect of rheological properties of PS and PDMS on phase structure of PS/PDMS blends were investigated using a selective extraction technique and scanning electron microscopy (SEM). The dual‐phase continuity of PS/PDMS blends takes place in a wide composition range. The formation and the onset of a cocontinuous phase structure largely depend on blend composition, viscosity ratio of the constituent components, and addition of diblock copolymers. The width of the concentration region of the cocontinuous structure is narrowed with increasing the viscosity ratio of the blends and in the presence of the small amount diblock copolymers. Quiescent annealing shifts the onset values of continuity. The experimental results are compared with the volume fraction of phase inversion calculated with various theoretical models, but none of the models can account quantitatively for the observed data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 898–913, 2004     

Connecting the wetting and rheological behaviors of poly(dimethylsiloxane)-grafted silica spheres in poly(dimethylsiloxane) melts

Using dynamic light scattering, mechanical rheometry, and visual observation, the static wetting behavior of PDMS-grafted silica spheres (PDMS-g-silica) in PDMS melts is related to their rheology. A phase diagram is mapped out for a constant grafted chain length as a function of grafting density and free polymer chain length. The transition between stable and aggregated regions is determined optically and with dynamic light scattering. It is associated with a first-order wetting transition. In the stable region Newtonian behavior is observed for semidilute suspensions. The hydrodynamic brush thicknesses, deduced from viscosity measurements, correspond closely to values obtained from self-consistent field calculations for the various parameter values. At the transition, the brush collapses suddenly and shear-thinning and thixotropy appear. The rheology indicates a degree of aggregation that increases with increasing length of the free polymer, as suggested by the theory.