Effect of Low-Pressure Nitrogen DC Plasma Treatment on the Surface Properties of Biaxially Oriented Polypropylene, Poly (Methyl Methacrylate) and Polyvinyl Chloride Films

In this study, commercial biaxially oriented polypropylene （BOPP）, polyvinyl chlo- ride （PVC） and poly （methyl methacrylate） （PMMA） films were treated with nitrogen plasma over different exposure times in a Pyrex tube surrounded by a DC variable magnetic field. The chemi- cal changes that appeared on the surface of the samples were investigated using Fourier transform infrared （FT4R） spectroscopy and attenuated total reflectance Fourier transform infrared （ATR- FTIR） spectroscopy after treatment for 2 min, 4 min and 6 rain in a nitrogen plasma chamber. Effects of the plasma treatment on the surface topographies and contact angles of the untreated and plasma treated films were also analyzed by atomic force microscopy （AFM） and a contact angle measuring system. The results show that the plasma treated films become more hydrophilic with an enhanced wettability due to the formation of some new polar groups on the surface of the treated films. Moreover, at higher exposure times, the total surface energy in all treated films increased while a reduction in contact angle occurred. The behavior of surface roughness in each sample was completely different at higher exposure times.

Surface Characterization and Tribology Behavior of PMMA Processed by Excimer Laser

Polyoxymethylene methacrylate (PMMA) is widely used in ophthalmic biomaterials. Misuse of PMMA in extreme environments is likely to damage the ocular surface and intraocular structures. The surface characterization and tribological behavior of PMMA processed using an excimer laser were investigated in this study by contrasting diferent lubrication conditions and friction cycles. The results show that the roughness of the material surface increases with laser processing, which changes its physical structure. Under lubrication, the laser-treated PMMA exhibits better hydrophilicity, especially during the use of eye drops. No obvious relationship exists between the laser-processing time and friction behavior. However, the laser treatment may contribute to the formation of friction and wear mechanisms of PMMA materials. Laser-treated PMMA in saline solution exhibits better abrasive resistance by showing a lower wear rate than that in eye drops, although it has a higher friction coefcient. In this study, the diferent friction stages in laser-treated PMMA were clarifed under two lubrication conditions. The wear rates of the laser-treated PMMA were found to decrease with the number of cycles, and the friction coefcient has a similar variation tendency. The wear behavior of the laser-treated PMMA is dominated by the main abrasive wear and secondary transferred flm formation. This study provides a theoretical basis for the development and application of ophthalmic biomaterials in complex environments by examining the material surface interface behavior and wear mechanism after laser processing using PMMA as the research matrix.

Low-Temperature Plasma Induced Grafting of 2-Methacryloyloxyethyl Phosphorylcholine onto Poly(tetrafluoroethylene) Films

Modification of poly(tetrafluoroethylene)(PTFE) films with 2-methacryloyloxyethyl phosphorylcholine(MPC) was performed by low-temperature plasma treatment and grafting polymerization.Surface properties of PTFE were characterized by attenuated total reflectance Fourier transform infrared(ATR-FTIR) spectra,X-ray photoelectron spectroscopy(XPS) ,and static contact angle.The results show that MPC has been grafted onto PTFE film surface successfully.Contact angle for the modified PTFE films in the water decreased from 108°to 58.25°,while surface energy increased from 17.52 mN/m to 45.47 mN/m.The effects of plasma treatment time,monomer concentration and grafting time on degree of grafting were determined.In the meanwhile,blood compatibility of the PTFE films was studied by checking thrombogenic time of blood plasma.

SELF-ASSEMBLED MICRO-DOMAINS ON THE UPPERMOST SURFACE OF FLUORINATED POLY(CARBONATE URETHANE)S WITH FLUORINATED SIDE CHAIN ATTACHED ON HARD SEGMENTS

The surface phase separated structure of polyurethanes is always desired due to the advantage of better biocompatibility, compared with the homogeneous one. The key issue is how to control and characterize the surface morphology. In this work, we report the uppermost surface morphology of fluorinated poly(carbonate urethane)s with fluorinated side chains attached to hard segments as studied by AFM, XPS and contact angle measurement. A self-assembled micro-domain with the fluorinated side chain standing up on the uppermost surface has been proposed for polyurethane with higher fluorinated content, based on the result obtained.

ELECTROSPRAYING/ELECTROSPINNING OF POLY(γ-STEARYL-LGLUTAMATE):FORMATION OF SURFACES WITH SUPERHYDROPHOBICITY

Electrospraying/electrospinning of poly(γ-stearyl-L-glutamate) (PSLG) was investigated on a series solutions with different concentrations in chloroform.Field emission scanning electron microscopy (FESEM) and attenuated Iotal reflectance Fourier transform infrared spectroscopy (FT-IR/ATR) were used to characterize the morphology and structure of the electrosprayed/electrospun polypeptide mats.It was found that electrospraying of PSLG with concentrations lower than 16 wt% afforded beads,while microfibers cou...

SURFACE OF GELATIN MODIFIED POLY(L-LACTIC ACID)FILM

In this paper, the surface structure of poly(L-lactic acid) (PLLA) film modified with gelatin was investigated. ThePLLA film specimens were treated directly with aqueous alkali solution to provide their surfaces with carboxyl groups, sothat these functional groups could become the reactive sites for gelatin immobilization. The functional groups of the PLLAfilms were identified by ATR-FTIR spectra and XPS spectra, the changes in surface morphology were observed by usingenvironmental scanning electron microscopy (ESEM), and the hydrophilicity of modified PLLA films was examined bywater contact angle measurement. Experimental results showed that the gelatin was immobilized with water-solublecarbodiimide (EDC) onto the PLLA film's surfaces, and the gelatin content on the polymer surface was related to carboxylicgroup formed in the controlled hydrolysis process. Rough surfaces caused by hydrolysis will predominantly favor the adhesion and growth of cell; and the hydrophilicity of these surfaces after the modification procedure is enhanced.

Surface Modification of Polycarbonate Urethane by Covalent Linkage of Heparin with a PEG Spacer

Heparin was grafted onto polycarbonate urethane (PCU) surface via a three-step procedure utilizing α, ωdiamino-poly(ethylene glycol) (APEG, M n =2 000) as a spacer. In the first step, isocyanate functional groups were introduced onto PCU surface by the treatment of hexamethylene diisocyanate (HDI) in the presence of di-n-butyltin dilaurate (DBTDL) as a catalyst. In the second step, APEG was linked to the PCU surface to obtain the APEG conjugated PCU surface (PCU-APEG). In the third step, heparin was covalently coupled with PCU-APEG in the presence of N-hydroxysuccinimide (NHS) and 1-ethyl-3-(3-dimethylamidopropyl) carbodiimide (EDAC). The amount of heparin (1.639 μg/cm 2 ) covalently immobilized on the PCU-APEG surface was determined by the toluidine blue method. The modified surface was characterized by water contact angle, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The hemocompatibility was preliminarily studied by platelet adhesion test. The results indicated that heparin was successfully grafted onto the PCU surface, and meanwhile the hydrophilicity and hemocompatibility of the modified PCU surface were improved significantly compared with the blank PCU surface.

Surface-modified Biphasic Calcium Phosphate/Poly (L-lactide) Biocomposite

Biphasic calcium phosphate （BCP） powders were prepared by hydrolyzation proc-ess and surface-modified by directly grafted L-lactide （LLA） onto the surface of BCP through a chemical linkage. The grafting ratio of organic groups was 9 wt%. After surface modification, the surface of BCP powders was covered by the lamella-shaped crystal. Poly （L-lactide） was mixed with BCP to form the BCP/PLLA biocomposite. Modified BCP （mBCP） particles could be uniformly dis-persed in PLLA matrix. The compressive strength of the mBCP/PLLA composite is 115 MPa, 28% higher than that of unmodified-BCP/PLLA composite. The improved mechanical strength is attributed to the enhanced adhesion between the inorganic BCP filler and the organic PLLA matrix.

Surface Characterization and in Vitro Blood Compatibility of Poly (Ethylene Terephthalate) Immobilized with Hirudin

Poly （ethylene terephthalate）（dacron, PET） films were exposed under argon plasma glow discharge with different glows and induced polymerization of acrylic acid（AA） in order to in- troduce carboxylic acid group onto PET （PET-AA） assisted by ultraviolet radiation（UV）. Hirudin- immobilized PET （PET-HRD） films were prepared by the grafting of PET-AA, followed by chem- ical reaction with hirudin. The surface structure of the treated PET was determined by X-ray photoelectron spectroscopy （XPS）. The wettability, surface free energy, and interface free energy of the films were investigated by contact angle measurement. The blood compatibility of the films was assessed by platelet-adhesion test and fibrinogen conformational change measurements to eval- uate the viability of the materials in biomedical engineering. Measurement by scanning electron microscopy （SEM） revealed that the amounts of adhered, aggregated and morphologically changed platelets were reduced on the hirudin-immobilized PET films. Enzyme-linked-immunoassay mea- surements that disclosed fibrinogen conformational changes showed results consistent with the platelets＇ behavior.

HYDROPHILIC MODIFICATION OF PPESK POROUS MEMBRANES VIA AQUEOUS SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

Hydrophilic surface modification of poly(phthalazinone ether sulfone ketone)(PPESK) porous membranes was achieved via surface-initiated atom transfer radical polymerization(ATRP) in aqueous medium.Prior to ATRP.chloromethyl groups were introduced onto PPESK main chains by chloromethylation.Chloromethvlated PPESK(CMPPESK) was fabricated into porous membrane through phase inversion technique.Hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate)(P(PEGMA)) brushes were grafted from CMPPESK membrane ...

In vitro Blood Compatibility of Polyethylene Terephthalate with Covalently Bounded Hirudin on Surface

Polyethylene terephthalate （PET,Dacron） was modified by surface immobilization of hirudin with glutaraldehyde（GA） as coupling reagent to improve the blood compatibility.Hirudin-immobilized PETs were characterized by X-ray photoelectron spectroscopy （XPS） and contact angle measurements.The blood compatibility of the PETs was evaluated by platelet adhesion evaluation and fibrinogen conformational change measurements in vitro.The results showed the decrease of platelet adhesion and activation on hirudin-immobilized PET with increasing of glutaraldehyde concentration.Fibrinogen experiment showed that fibrinogen adherence and conformational changes of PET-HRD were less than those of untreated PET,which made the materials difficult to form thrombus.The proper reason of blood compatibility improvement was low interface tension between hirudin-immobilized PETs and blood,as well as blood proteins,and low ratio of dispersive/polar component of the surface energy（γsd/γsp） and high hydrophilicity.

Surface Modification of Poly Vinyl Chloride (PVC) Using Low Pressure Argon and Oxygen Plasma

In this study, commercial poly vinyl chloride （PVC） films were treated by oxygen and argon plasmas in a cylindrical glass tube which was surrounded by a DC variable magnetic field, with different sample positions in the plasma reactor and also different exposure durations. Effects of the plasma treatment on the hydrophilic properties of the films were studied by mea- suring the water drop contact angle on the surface of the samples. The surface topography of the untreated and plasma treated films was analyzed and compared by atomic force microscopy （AFM）. The optical characteristic changes in treated samples were investigated using reflective spectrophotometry. Also, the chemical changes which appeared on the surface of the samples were investigated using Fourier transform infrared spectroscopy （FTIR）. The results show that the plasma treated PVC becomes more hydrophilic with an enhanced wettability. A sharp de- crease in the water contact angle may also be a consequence of the surface texturization. The aging effect on wettability of the samples was also investigated. The results show that the effect of oxygen plasma on the surface properties of the samples is more pronounced compared with that of argon plasma.

APPLICATION OF SURFACE GRAFTED POLY N-ISOPROPYL ACRYLAMIDE BY RADIATION TECHNOLOGY FOR PROTEIN SOLUTION CONCENTRATION

Poly N-isopropyl acrylamide (abbreviated as PNIPA) as a kind of thermally sensitive hydrogel is utilized to concentrate Bovin Serum Albumin (BSA) solution. In order to decrease its surface adsorption to BSA in aqueous solution, surface layer grafting of the gels by radiation technology was carried out. The results showed that hydroxyl propyl methacrylate (HPMA) grained gel exhibited a low level of BSA adsorption and still kept the original thermally sensitive properties of PNIPA hydrogels.

XPS STUDIES ON SURFACE MODIFIED POLY [1-(TRIMETHYLSILYL)-1-PROPYNE] MEMBRANES Ⅱ SURFACE MODIFICATION BY BROMINE VAPOR

Surface modification of poly [1-(trimethylsilyl)-1-propyne] (PTMSP) membranes bybromine vapor has been studied. It is shown that Br/C atomic ratio at the surfaces increased withthe time of bromination until about 60 min, then it reached a plateau. The results of XPS and IRstudies indicated that the addition of bromine to double bonds and the replacement of H on CH_3 bybromine had taken place so that a new peak at 286.0 eV (C--Br)in C_(1s) spectra and some newbands, e. g. at 1220 and 580cm^(-1) in IR spectra were formed. The fact,t Po_2, permeability ofoxygen, decreased and α_(O_2/N_2), separation factor of oxygen relative to nitrogen, increased withbromination time, shows that surface modification of PTMSP by bromine may be an efficient approach to prepare PTMSP membranes used for practical gas separations.

A Comparative Assessment of the Surface Roughness of Thermoplastic Denture Base Resins Following Adjustment and Re-Polishing

Purpose: This study assessed the roughness of two injection-molded, thermoplastic materials used for denture bases compared with a polyamide material and compression molded Polymethylmethacrylate (PMMA) after the adjustment and re-polishing with either a laboratory protocol or a chair side protocol. Methods: Forty specimens, each of PMMA, Valplast, DuraFlex, Dura Cetal were fabricated and finished according to individual manufactures’ instructions. These materials were adjusted with tungsten carbide (TC) burs to mimic gross adjustments, and then re-polished either on a lathe or bonded silicon carbide (B-SC). Following instrumentation, the specimens were assessed using contact profilometry and scanning electron microscopy. Two-factor ANOVA was used to determine significant differences in mean surface roughness (Ra and Rmax), with included factors being material type and re-polishing regimen. Results: Mean Ra values ranged from 0.26 (DuraFlex control) to 1.82 (Valplast adjusted with TC burs). Mean Rmax values ranged from 1.88 (Dura Flex control) to 13.76 (Valplast adjusted with TC burs). Two-factor ANOVA revealed that interaction of both factors was significant (p Ra and Rmax. There was a statistically significant increase in both Ra (p Rmax (p < 0.05) for all material types following the gross adjustment. With the exception of DuraFlex, re-polishing of samples that were previously adjusted with TC burs, on the dental lathe produced surfaces that were comparable to control samples. Conclusion: Adjustment of DuraFlex should be kept to a minimum since the adjustment produced the significant surface detriment that could not be corrected with either of the polishing regimens.

The Metal/Electroactive Polymer Interface Studied by Surface Resistance

The experimental arrangement in this investigation was one in which a poly(o-aminophenol) (POAP) film was supported on a thin gold film electrode whose thickness is of the order of the mean free path of conduction electrons of gold. This arrangement allows one to apply the surface resistance technique to study the electrochemical processes occurring at the metal film surface coated with the polymer film. The dependence of the resistance change of the thin gold film electrode on the external electrolyte composition for polymer thickness lower than 0.25 mC.cm-2, was attributed to a competition, at the gold film surface, between the redox process of the polymer and adsorption of different ion species contained in the electrolyte. This competition reflects a discontinuous character of polymer thickness lower than 0.25 mC.cm-2 at the metal polymer interface. The resistance response of the metal film becomes independent of both the external electrolyte composition and polymer thickness for polymer thickness higher than 0.8 mC.cm-2. Then, POAP thicknesses higher than 0.8 mC.cm-2 seem to be compact enough at the metal polymer interface to prevent the interaction of the species contained in the supporting electrolyte with the gold film surface. The increase of the gold film resistance in going from the reduced to the oxidized state for POAP thicknesses higher than 0.8 mC.cm-2 was attributed to the redox conversion of poly(o-aminophenol) from amine to imine groups. This resistance increase was explained as a transition from specular to diffuse scattering of conduction electrons of gold at the gold poly(o-aminophenol) interface due to a less compact distribution of oxidised sites of POAP as compared with that of the reduced ones. An attenuation of the resistance response of the gold film was observed when the POAP films were deactivated either by contact with a ferric cation solution or prolonged potential cycling. The deactivation of the polymer film was attributed to the creation of inactive gaps within the redox sites configuration of POAP. The surface resistance technique allows one to detect different redox sites configurations of POAP on the gold film, according to the method used to deactivate the polymer films. In this work, it is demonstrated that the surface resistance technique can be employed to study not only the ability of a POAP film to inhibit the interaction of different species in solution with a metal surface but also the deactivation of the polymer film.

A Study of Surface Modification of Poly(lactic-co-glycolic) Acid Using Argon Ion Irradiation

The effect of Argon ion irradiation to the surface properties of poly(lactic-co-glycolic) acid (PLGA) was studied. A beam of 170 keV Argon ions was implanted at different fluencies (1 × 1012, 1 × 1013, 1 × 1014, and 1 × 1015 ions/cm2). X-ray photoelectron spectroscopy (XPS) was used to analyze the evolution of the bonding microstructure of PLGA due to irradiation. Surface morphology was monitored using atomic force microscopy (AFM). AFM analysis shows that film roughness increased to maximum at the dose of 1 × 1014 ions/cm2 where the formations of hillocks were also detected. Hydrophilicity of PLGA is important for their applications in biomedicine such as bioscaffolds. Hydrophilicity was monitored using water contact angle measurements for both unmodified and ion-modified PLGA. It was observed that hydrophilicity of PLGA changes with the ion irradiation. This demonstrates that ion irradiation can be an alternative approach to control hydrophilicity of PLGA. PLGA scaffolds modified with ion irradiation could therefore be more suitable for the biomedical applications.

PHASE SEPARATION BEHAVIOR OF ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMER INDUCED BY SURFACES OF VARIOUS POLYMERS

This paper reports the phase separation behavior of ABS films cast on the surfaces of homopelymers or random copolymers.It is found that phase separation of ABS films was induced by the surfaces of the substrate polymers.The relationship between the miscibility of the sub- strate polymers and the phase separation behavior of ABS films was also examined.

Study of radiation-induced grafting of acrylic acid-sodium styrene sulfonate onto poly (tetrafluoroethylene-co-hexafluoropropylene) film

Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were immersed in aqueous solution of acrylic acid (AA) and sodium styrene sulfonate (SSS), then irradiated by Co γ-rays at 25℃. The effects of reaction 60 time,absorbed dose, dose-rate, inhibitor and monomer concentration on the grafting yield were studied. Grafting yields of both AA and SSS onto FEP, respectively, increase with irradiation dose, but some saturation will appear at high dose and monomer concentration. The grafting yield increases with reaction time and then levels off. The graft- ing of SSS onto FEP is more difficult than the grafting of AA. The analysis of grafted membranes using DSC and FT-IR have been done.

CHARACTERIZATION OF AMPHIPHILIC AND MICROPHASE SEPARATED GRAFT COPOLYMERS Ⅱ SURFACE CHARACTERIZATION AND IN VITRO BLOOD-COMPATIBILITY ASSESSMENT OF POLYSTYRENE-GRAFT-ω-STEARYLPOLY (ETHYLENE OXIDE)

This paper reported the research results concerning the surface characterization ofpolystyrene-graft-w-stearyl poly(ethylene oxide) (PS-g-SPEO) by means of XPS,contactangle measurement and TEM, and its in vitro blood compatibility assessment by measuringthe plasma recalcification time (RT) and partial thromboplastin time (PTT). The XPSresults demonstrated that the surface and bulk composition of the PS-g-SPEO graftcopolymers differ remarkably from each other,and that SPEO component was constantlyenriched at the copolymer/air interface. Contact angle studies indicated that the surfacewater wettability can be adjusted effectively by changing the composition of the copolymer.PS-g-SPEO graft copolymers can undergo microphase separation as clearly illustrated byTEM photographs. The relationship between the surface properties of PS-g-SPEO graftcopolymer and its blood compatibility was also discussed.