Infrared-visible sum frequency generation spectroscopy (SFG) was used to measure the interfacial concentrations of poly(methyl methacrylate) (PMMA)/polystyrene (PS) blends next to a sapphire substrate. The acid-base interactions of carbonyl groups of PMMA with the hydroxyl groups on the sapphire drive the interfacial segregation of PMMA next to the sapphire substrate. Using the shift of sapphire surface OH peaks, we have determined the difference in interfacial energy between the PMMA/sapphire and the PS/sapphire to be ~44-45 mJ/m(2). These results highlight the importance of acid-base interactions and their role in controlling the interfacial segregation next to solid substrates in polymer blends.

The chemical composition and molecular structure of polymeric surfaces are important in understanding wetting, adhesion, and friction. Here, we combine interfacesensitive sum frequency generation spectroscopy (SFG), allatom molecular dynamics (MD) simulations, and ab initio calculations to understand the composition and the orientation of chemical groups on poly(methyl methacrylate) (PMMA) surface as a function of tacticity and temperature. The SFG spectral features for isotactic and syndiotactic PMMA surfaces are similar, and the dominant peak in the spectra corresponds to the ester-methyl groups. The SFG spectra for solid and melt states are very similar for both syndiotactic and isotactic PMMA. In comparison, the MD simulation results show that both the ester-methyl and the α-methyl groups of syndiotactic-PMMA are ordered and tilted toward the surface normal. For the isotactic-PMMA, the α-methyl groups are less ordered compared to their ester-methyl groups. The backbone methylene groups have a broad angular distribution and are disordered, independent of tacticity and temperature. We have compared the SFG results with theoretical spectra calculated using MD simulations and ab initio calculations. Our analysis shows that the weaker intensity of α-methyl groups in SFG spectra is due to a combination of smaller molecular hyperpolarizability, lower ordering, and lower surface number density. This work highlights the importance of combining SFG spectroscopy with MD simulations and ab initio calculations in understanding polymer surfaces. ■ INTRODUCTIONOne of the simplest and still commonly used technique to characterize surfaces of polymers is the measurement of water contact angle. Although this is a very simple technique to judge the wettability of surfaces, it lacks molecular level sensitivity to identify the chemical composition and molecular structure of surfaces. In addition, the rearrangement of molecules at the surface after exposure to water complicates the interpretation of contact angle results. 1 X-ray photoelectron spectroscopy (XPS), a vacuum-based technique, provides excellent information regarding the elemental composition present at the surfaces. However, to identify different hydrocarbon groups (or bondings) is not trivial and relies on subtle shifts of carbon binding energies in the high-resolution XPS analysis. 2 Attenuated-total-reflectance infrared can be used to pick up molecular fingerprints, but this technique samples a much thicker layer than the surface region that affects wetting, surface energy, and friction. 3 In the past two decades, surface-sensitive infrared−visible sum frequency generation spectroscopy (SFG) has been used to study polymer surfaces, 4−7 polymer/liquid interfaces, 7−11 polymer/metal or metal oxide interfaces, 5,12−15 and polymer/polymer interfaces. 12,16−19 SFG is a second-order nonlinear optical technique, and under electric dipole approximation, the SFG signal is only generated by the ordered molecules at surfaces or interfaces and the contribution from ...

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The chemical composition and molecular structure of polymeric surfaces are important in understanding wetting, adhesion, and friction. Here, we combine interfacesensitive sum frequency generation spectroscopy (SFG), allatom molecular dynamics (MD) simulations, and ab initio calculations to understand the composition and the orientation of chemical groups on poly(methyl methacrylate) (PMMA) surface as a function of tacticity and temperature. The SFG spectral features for isotactic and syndiotactic PMMA surfaces are similar, and the dominant peak in the spectra corresponds to the ester-methyl groups. The SFG spectra for solid and melt states are very similar for both syndiotactic and isotactic PMMA. In comparison, the MD simulation results show that both the ester-methyl and the α-methyl groups of syndiotactic-PMMA are ordered and tilted toward the surface normal. For the isotactic-PMMA, the α-methyl groups are less ordered compared to their ester-methyl groups. The backbone methylene groups have a broad angular distribution and are disordered, independent of tacticity and temperature. We have compared the SFG results with theoretical spectra calculated using MD simulations and ab initio calculations. Our analysis shows that the weaker intensity of α-methyl groups in SFG spectra is due to a combination of smaller molecular hyperpolarizability, lower ordering, and lower surface number density. This work highlights the importance of combining SFG spectroscopy with MD simulations and ab initio calculations in understanding polymer surfaces. ■ INTRODUCTIONOne of the simplest and still commonly used technique to characterize surfaces of polymers is the measurement of water contact angle. Although this is a very simple technique to judge the wettability of surfaces, it lacks molecular level sensitivity to identify the chemical composition and molecular structure of surfaces. In addition, the rearrangement of molecules at the surface after exposure to water complicates the interpretation of contact angle results. 1 X-ray photoelectron spectroscopy (XPS), a vacuum-based technique, provides excellent information regarding the elemental composition present at the surfaces. However, to identify different hydrocarbon groups (or bondings) is not trivial and relies on subtle shifts of carbon binding energies in the high-resolution XPS analysis. 2 Attenuated-total-reflectance infrared can be used to pick up molecular fingerprints, but this technique samples a much thicker layer than the surface region that affects wetting, surface energy, and friction. 3 In the past two decades, surface-sensitive infrared−visible sum frequency generation spectroscopy (SFG) has been used to study polymer surfaces, 4−7 polymer/liquid interfaces, 7−11 polymer/metal or metal oxide interfaces, 5,12−15 and polymer/polymer interfaces. 12,16−19 SFG is a second-order nonlinear optical technique, and under electric dipole approximation, the SFG signal is only generated by the ordered molecules at surfaces or interfaces and the contribution from ...

Structures of amphiphilic molecules at the liquid/solid and solid/solid interfaces are important in understanding lubrication, colloid stabilization, chromatography, and nucleation. Here, we have used interface-sensitive sum frequency generation (SFG) spectroscopy to characterize the interfacial structures of long-chain alcohols above and below the bulk melting temperature (Tm). The melting temperature of the ordered hexadecanol monolayer was measured to be around 30 °C above the bulk Tm, consistent with the transition temperature reported using X-ray reflectivity [ Phys. Rev. Lett. 2011 , 106 , 137801 ]. The disruption of hydrogen bonds between the sapphire and the alcohol hydroxyl groups was directly measured as a function of temperature. The strength of this hydrogen-bonding interaction, which explained the monolayer thermal stability above Tm, was calculated using the Badger-Bauer equation. Below Tm, the ordered self-assembled monolayer influenced the structure of the interfacial crystalline layer, and the transition from the ordered monolayer to the bulk crystalline phases (α rotator phase, β crystalline phase, and γ crystalline phase) resulted in packing frustrations at the interface.

Spent mushroom substrate (SMS) can be used as the component of growing medium for the culture of crop plants. Fresh SMS may have the potential as an alternative to peat to raise horticultural plants. In this study, five container media characterized by the proportions of SMS to commercial peat in 0% (control), 25%, 50%, 75%, and 100% were used to raise pepper (Capsicum annum L.) plants. Initial SMS was found to have low available nitrogen (N) content (<20 mg kg-1) but moderate extractable phosphorus (P) content (900 mg kg-1). In the second month photosynthetic rate was found to decline in the 75% treatment. At harvest in the third month, plants in the 100% treatment nearly died out. The 25% treatment resulted in the highest height (19 cm) and diameter growth (0.3 cm), shoot (0.6 g) and root biomass accumulation (0.13 g), fruit weight (3 g), and shoot carbohydrate content (98 mg g-1), but lowest foliar acid phosphatase activity (30 µg NPP g-1 FW min-1). With the increase of SMS proportion in the substrate, the medium pH and electrical conductance (EC) increased with the decrease of foliar size. The available N and P contents in the substrates showed contrasting relationship with N and P contents in pepper plants. Therefore, fresh SMS cannot be directly used as the substrate for the culture of pepper plants. According to our findings fresh SMS was recommended to be mixed in the proportion of 25% with commercial peat for the culture of horticultural plants.

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Sum frequency generation spectroscopy (SFG) and attenuated-total-reflection IR (ATR-IR) were used to investigate polymer adsorption on solid surfaces in CCl 4 (neutral), CHCl 3 (acidic), and acetone (basic) solvents. Fowkes showed that the adsorbed amount of the polymer from acidic and basic solvents is less than that from a neutral solvent (Ind. Eng. Chem. Prod. Res. Dev. 1978, 17, 3−7). Here, we show that besides the differences in adsorbed amount, chains adsorbed from an acidic solvent adopted a flat conformation with a much smaller ratio of segments of loops and tails to trains compared to those adsorbed from a neutral solvent. Sapphire (Al 2 O 3 ) surfaces were saturated by train segments at 1.3 × 10 −5 volume fraction for both CCl 4 and CHCl 3 solutions, with a large fraction of the surface sites occupied by the PMMA segments, which was different from what was expected based on Fowkes' experiment. In contrast, PMMA segments were not able to replace acetone molecules from the surface in a time period of 2 h. Surface interaction parameters alone were unable to predict the differences in conformation of chains adsorbed from acidic or neutral solvents.