Surface characterization of the hydroxy-terminated poly(∈-caprolactone)/poly(dimethylsiloxane) triblock copolymers by electron spectroscopy for chemical analysis and contact angle measurements

The surface composition and free energy properties of two grades of amphiphilic and semicrystalline triblock copolymers consisting of a poly(dimethylsiloxane) (PDMS) midblock (Mw ≃ 2300) coupled to poly(∈-caprolactone) (PCL) end blocks having differing molecular weights (Mw ≃ 2000, sample P3, and Mw ≃ 3000, sample P2) and homopolymer PCL (Mw ∼ 40 000) were investigated by Fourier transform infrared, spectroscopy, electron spectroscopy for chemical analysis (ESCA), and contact angle measurements using critical surface tension, one-liquid and two-liquid methods. ESCA showed that the molar concentration of PDMS increased from 36.5% in the bulk up to 70.2% in the surface for sample P2 and from 46.3% in the bulk up to 79.2% in the surface for sample P3 in high vacuum. This indicates that the lower surface energy PDMS microdomains were segregated in the surface region to minimize the surface energy of the copolymer. The longer the PCL block, the higher the phase separation. One-liquid contact angle results were evaluated by using van Oss, Good, and Chaudhury's Lifshitz-van der Waals and Lewis acid-base (AB) methodology, and it was determined that the basicity surface tension coefficients (γs-) of the copolymers decreased with the increase of the PDMS content at the surface, a result in agreement with the ESCA results but not proportional to them, indicating that the surfaces of the copolymers are highly mobile and molecular rearrangement takes place upon contacting with a polar testing liquid drop. The strong AB interaction between the basic carboxyl groups of PCL segments with the Lewis acidic groups of the polar liquids restructured the surface molecular composition at the contact area by increasing PCL and decreasing PDMS concentration in polar environments. The two-liquid contact angle method was also applied, and it was determined that γs- decreased inverse proportionally with the increase of PDMS segments. Also, it was realized that the molecular restructuring did not take place in the two-liquid method

Selective adsorption of L1210 leukemia cells/human leukocytes on micropatterned surfaces prepared from polystyrene/polypropylene-polyethylene blends

The objective of this study is to prepare polymeric surfaces which will adsorb L1210 leukemia cells selectively more than that of healthy human leukocytes in order to develop new treatment options for people with leukemia. Chemically heterogeneous and micropatterned surfaces were formed on round glass slides by dip coating with accompanying phase-separation process where only commercial polymers were used. Surface properties were determined by using optical microscopy, 3D profilometry, SEM and measuring contact angles. Polymer, solvent/nonsolvent types, blend composition and temperature were found to be effective in controlling the dimensions of surface microislands. MTT tests were applied for cell viability performance of these surfaces. Polystyrene/polyethylene-polypropylene blend surfaces were found to show considerable positive selectivity to L1210 leukemia cells where L1210/healthy leukocytes adsorption ratio approached to 9-fold in vitro. Effects of wettability, surface free energy, microisland size geometry on the adsorption performances of L1210/leukocytes pairs are discussed. © 2013 Elsevier B.V

Multi-technique analysis of MOCVD-grown lead lanthanum titanate (Pb1-xLax)TiO3 thin films on quartz substrates

Materials Research Society Symposium - Proceedings493493-498MRSP

Osteoselection supported by phase separated polymer blend films

The instability of implants after placement inside the body is one of the main obstacles to clinically succeed in periodontal and orthopedic applications. Adherence of fibroblasts instead of osteoblasts to implant surfaces usually results in formation of scar tissue and loss of the implant. Thus, selective bioadhesivity of osteoblasts is a desired characteristic for implant materials. In this study, we developed osteoselective and biofriendly polymeric thin films fabricated with a simple phase separation method using either homopolymers or various blends of homopolymers and copolymers. As adhesive and proliferative features of cells are highly dependent on the physicochemical properties of the surfaces, substrates with distinct chemical heterogeneity, wettability, and surface topography were developed and assessed for their osteoselective characteristics. Surface characterizations of the fabricated polymer thin films were performed with optical microscopy and SEM, their wettabilities were determined by contact angle measurements, and their surface roughness was measured by profilometry. Long-term adhesion behaviors of cells to polymer thin films were determined by F-actin staining of Saos-2 osteoblasts, and human gingival fibroblasts, HGFs, and their morphologies were observed by SEM imaging. The biocompatibility of the surfaces was also examined through cell viability assay. Our results showed that heterogeneous polypropylene polyethylene/polystyrene surfaces can govern Saos-2 and HGF attachment and organization. Selective adhesion of Saos-2 osteoblasts and inhibited adhesion of HGF cells were achieved on micro-structured and hydrophobic surfaces. This work paves the way for better control of cellular behaviors for adjustment of cell material interactions. © 2014 Wiley Periodicals, Inc

Combined XPS and contact angle studies of ethylene vinyl acetate and polyvinyl acetate blends

In this study, we prepared thin films by blending ethylene vinyl acetate copolymers (EVA) containing 12-33 (wt.%) vinyl acetate (VA) with polyvinyl acetate (PVAc) and high density polyethylene homopolymers. Large area micropatterns having controlled protrusion sizes were obtained by phase-separation especially for the PVAc/EVA-33 blends using dip coating. These surfaces were characterized by XPS and contact angle measurements. A reasonably linear relation was found between the VA content on the surface (wt.%) obtained from XPS analysis and the VA content in bulk especially for PVAc/EVA-33 blend surfaces. PE segments were more enriched on the surface than that of the bulk for pure EVA copolymer surfaces similar to previous reports and VA enrichment was found on the EVA/HDPE blend surfaces due to high molecular weight of HDPE. Water θe decreased with the increase in the VA content on the blend surface due to the polarity of VA. A good agreement was obtained between γs-and atomic oxygen surface concentration with the increase of VA content. The applicability of Cassie-Baxter equation was tested and found that it gave consistent results with the experimental water contact angles for the case where VA content was lower than 55 wt.% in the bulk composition. © 2011 Elsevier B.V. All rights reserved

Topography and wettability characterization of surfaces manufactured by SLM and treated by chemical etching

Selective Laser Melting process represents an interesting opportunity in the biomedical field to fabricate customized implants. However, the surface roughness of components obtained through additive manufacturing is a major limitation and affects the surface wettability. In the present work, chemical etching is adopted to deal with such an issue. To do so, the effects of chemical etching parameters (such as immersion time and composition of the solution) on the surface roughness, weight loss and wettability is analyzed. Different samples (obtained through different printing orientations) are considered. The tests show that the roughness and the wetting of the surfaces are improved thanks to chemical etching. As a major result, the most influencing parameters on surface wetting are two: the roughness and the material properties (which vary with samples depth)