Response Surface Optimisation of Polydimethylsiloxane (PDMS) on Borosilicate Glass and Stainless Steel (SS316) to Increase Hydrophobicity

Particle deposition on the surface of a drying chamber is the main drawback in the spray drying process, reducing product recovery and affecting the quality of the product. In view of this, the potential application of chemical surface modification to produce a hydrophobic surface that reduces the powder adhesion (biofouling) on the wall of the drying chamber is investigated in this study. A hydrophobic polydimethylsiloxane (PDMS) solution was used in the vertical dipping method at room temperature to determine the optimum coating parameters on borosilicate glass and stainless steel substrates, which were used to mimic the wall surface of the drying chamber, to achieve highly hydrophobic surfaces. A single-factor experiment was used to define the range of the PDMS concentration and treatment duration using the Response Surface Methodology (RSM). The Central Composite Rotatable Design (CCRD) was used to study the effects of the concentration of the PDMS solution (X₁, %) and the treatment duration (X₂, h) on the contact angle of the substrates (°), which reflected the hydrophobicity of the surface. A three-dimensional response surface was constructed to examine the influence of the PDMS concentration and treatment duration on contact angle readings, which serve as an indicator of the surface’s hydrophobic characteristics. Based on the optimisation study, the PDMS coating for the borosilicate glass achieved an optimum contact angle of 99.33° through the combination of a PDMS concentration of X₁ = 1% (w/v) and treatment time of X₂ = 4.94 h, while the PDMS coating for the stainless steel substrate achieved an optimum contact angle of 98.31° with a PDMS concentration of X₁ = 1% (w/v) and treatment time of X₂ = 1 h. Additionally, the infrared spectra identified several new peaks that appeared on the PDMS-treated surfaces, which represented the presence of Si-O-Si, Si-CH₃, CH₂, and CH₃ functional groups for the substrates coated with PDMS. Furthermore, the surface morphology analysis using the Field Emission Scanning Electron Microscopy (FESEM) showed the presence of significant roughness and a uniform nanostructure on the surface of the PDMS-treated substrates, which indicates the reduction in wettability and the potential effect of unwanted biofouling on the spray drying chamber. The application of PDMS and PTFE on the optimally coated substrates successfully reduced the amount of full cream milk particles that adhered to the surface. The low surface energy of the treated surface (19–27 mJ/m²) and the slightly higher surface tension of the full cream milk (54–59 mJ/m²) resulted in a high contact angle (102–103°) and reduced the adhesion work on the treated substrates (41–46 mJ/m²) as compared to the native substrates.     

Cell and protein compatibility of parylene-C surfaces

Parylene-C, which is traditionally used to coat implantable devices, has emerged as a promising material to generate miniaturized devices due to its unique mechanical properties and inertness. In this paper we compared the surface properties and cell and protein compatibility of parylene-C relative to other commonly used BioMEMS materials. We evaluated the surface hydrophobicity and roughness of parylene-C and compared these results to those of tissue culture-treated polystyrene, poly(dimethylsiloxane) (PDMS), and glass. We also treated parylene-C and PDMS with air plasma, and coated the surfaces with fibronectin to demonstrate that biochemical treatments modify the surface properties of parylene-C. Although plasma treatment caused both parylene-C and PDMS to become hydrophilic, only parylene-C substrates retained their hydrophilic properties over time. Furthermore, parylene-C substrates display a higher degree of nanoscale surface roughness (>20 nm) than the other substrates. We also examined the level of BSA and IgG protein adsorption on various surfaces and found that surface plasma treatment decreased the degree of protein adsorption on both PDMS and parylene-C substrates. After testing the degree of cell adhesion and spreading of two mammalian cell types, NIH-3T3 fibroblasts and AML-12 hepatocytes, we found that the adhesion of both cell types to surface-treated parylene-C variants were comparable to standard tissue culture substrates, such as polystyrene. Overall, these results indicate that parylene-C, along with its surface-treated variants, could potentially be a useful material for fabricating cell-based microdevices.     

Spatially controlled cell adhesion via micropatterned surface modification of poly(dimethylsiloxane)

Spatial control of cell growth on surfaces can be achieved by the selective deposition of molecules that influence cell adhesion. The fabrication of such substrates often relies upon photolithography and requires complex surface chemistry to anchor adhesive and inhibitory molecules. The production of simple, cost-effective substrates for cell patterning would benefit numerous areas of bioanalytical research including tissue engineering and biosensor development. Poly(dimethylsiloxane) (PDMS) is routinely used as a biomedical implant material and as a substrate for microfluidic device fabrication; however, the low surface energy and hydrophobic nature of PDMS inhibits its bioactivity. We present a method for the surface modification of PDMS to promote localized cell adhesion and proliferation. Thin metal films are deposited onto PDMS through a physical mask in the presence of a gaseous plasma. This treatment generates topographical and chemical modifications of the polymer surface. Removal of the deposited metal exposes roughened PDMS regions enriched with hydrophilic oxygen-containing species. The morphology and chemical composition of the patterned substrates were assessed by optical and atomic force microscopies as well as X-ray photoelectron spectroscopy. We observed a direct correlation between the surface modification of PDMS and the micropatterned adhesion of fibroblast cells. This simple protocol generates inexpensive, single-component substrates capable of directing cell attachment and growth.     

Oxygen plasma-treatment effects on Si transfer

Oxygen plasma-treatment is commonly used to increase the hydrophilicity of poly(dimethylsiloxane) (PDMS) stamps used for microcontact printing (muCP) aqueous-based inks. Review of the literature reveals that a wide range of plasma parameters are currently employed to modify stamp surfaces. However, little is known about the effect of these parameters (e.g., power, chamber pressure, duration) on the undesirable transfer of low-molecular-weight silicon-containing fragments from the stamps that commonly occurs during muCP. To study the effect of oxygen plasma-treatment on Si transfer, unpatterned PDMS stamps were treated with oxygen plasma under various conditions and used to stamp deionized water on plasma-activated poly(methyl methacrylate) (PMMA) substrates. Once stamped, the PMMA substrates were analyzed with X-ray photoelectron spectroscopy (XPS) to quantify and characterize silicon present on the substrate surface. In addition, used PDMS stamps were analyzed with scanning electron microscopy (SEM) to observe topographical changes that occur during oxygen plasma-treatment. XPS results show that all plasma treatments studied significantly reduced the amount of Si transfer from the treated stamps during muCP as compared to untreated PDMS stamps and that the source of transfer is residual PDMS fragments not removed by oxygen plasma. SEM results show that, although the treated stamps undergo a variety of topographical changes, no correlation exists between stamp topography and extent of Si transfer from the stamps.     

On the surface modification of microchannels for microcapillary electrophoresis chips

This paper presents systematic investigation of the microchannel surface properties in microCE chips. Three popular materials for microCE chips, polydimethylsiloxane (PDMS), quartz, and glass, are used. The zeta potentials of these microchannels are calculated by measuring the EOF velocity to evaluate the surface properties after surface modification. The hydrophobic PDMS is usually plasma-treated for microCE applications. In this study, a new method using a high-throughput atmospheric plasma generator is adopted to treat the PDMS surface under atmospheric conditions. In this approach, the cost and time for surface treatment can be significantly reduced compared with the conventional vacuum plasma generator method. Experimental results indicate that new functional groups could be formed on the PDMS surface after treatment, resulting in a change in the surface property. The time-dependent surface property of the plasma-treated PDMS is then measured in terms of the zeta potential. Results show that the surface property will reach a stable condition after 1 h of plasma treatment. For glass CE chips, two new methods for changing the microchannel surface properties are developed. Instead of using complicated and time-consuming chemical silanization procedures for CE channel surface modification, two simple and reliable methods utilizing organic-based spin-on-glass and water-soluble acrylic resin are reported. The proposed method provides a fast batch process for controlling the surface properties of glass-based CE channels. The proposed methods are evaluated using PhiX-174 DNA maker separation. The experimental data show that the surface property is modified and separation efficiency greatly improved. In addition, the long-term stability of both coatings is verified in this study. The methods proposed in this study show potential as an excellent solution for glass-based microCE chip surface modification.     

Poly(dimethylsiloxane) contamination in microcontact printing and its influence on patterning oligonucleotides

It is well-established that, during microcontact printing (muCP) using poly(dimethylsiloxane) (PDMS)-based stamps, some unexpected siloxane fragments can be transferred from the stamp to the surface of the sample. This so-called contamination effect coexists with the delivery of the molecules constituting the ink and by this way influences the printing process. The real impact of this contamination for the muCP technique is still partially unknown. In this work, we investigate the kinetics of this contamination process through the surface characterization of both the sample and the stamp after imprinting. The way both the curing conditions of the PDMS material and the contact time influence the degree of contamination of the surface is investigated on silicon and glass substrates. We propose a cleaning process of the stamp during several hours which eliminates any trace of contamination during printing. We show that hydrophobicity recovery of PDMS surfaces after hydrophilic treatment using oxygen plasma is considerably slowed down when the PDMS material is cleaned using our procedure. Finally, by comparing cleaned and uncleaned PDMS stamps, we show the influence of contamination on the quality of muCP using fluorescent DNA molecules as an ink. Surprisingly, we observe that the amount of DNA molecules transferred during muCP is higher for the uncleaned stamp, highlighting the positive impact of the presence of low molecular weight siloxane fragments on the muCP process. This result is attributed to the better adsorption of oligonucleotides on the stamp surface in presence of these contaminating molecules.     

A novel metal-protected plasma treatment for the robust bonding of polydimethylsiloxane

We describe a method for the irreversible bonding of PDMS-based microfluidic components by exploiting the first reported "shelfable" plasma treatment of PDMS. Simultaneous plasma activation and protection of PDMS surfaces are achieved via RF magnetron sputtering of thin aluminium films in the presence of an argon plasma. In this process, Ar plasma exposure generates a hydrophilic, silanol-enriched polymer surface amenable to irreversible bonding to glass, PDMS or silicon substrates, while the aluminium film functions as a capping layer to preserve the surface functionality over several weeks of storage in ambient conditions. Prior to bonding, this protective aluminium layer is removed by immersion in an aqueous etchant, exposing the adhesive surface. Employing this technology, PDMS-glass and PDMS-PDMS microfluidic devices were fabricated and the adhesive strength was quantified by tensile and leakage testing. Bonding success rates in excess of 80% were demonstrated for both PDMS-glass and PDMS-PDMS assemblies sealed 24 h and 7 days following initial polymer surface activation. PDMS-glass microdevices performed optimally, displaying maximum adhesive strengths on the order of 5 MPa and burst flow rates of approximately 1 mL min(-1) (channel dimensions: l = 25 mm; w = 300 microm; h = 20 microm). These data demonstrate a significant improvement in performance over previously reported bonding technologies, resulting in the production of more robust, longer-lasting microfluidic systems that can withstand higher pressures and flow rates.     

Microwave plasma treatment of polymer surface for irreversible sealing of microfluidic devices

Microwave plasma was generated in a glass bottle containing 2-3 Torr of oxygen for plasma treatment of a polymer surface. A "kitchen microwave oven" and a dedicated microwave digestion oven were used as the power source. Poly(dimethylsiloxane)(PDMS) slabs treated by a 30 W plasma for 30-60 s sealed irreversibly to form microfluidic devices that can sustain solution flow of an applied pressure of 42 psi without leaking. Experimental set up and conditions for the production of a homogeneous plasma to activate the PDMS surface for irreversible sealing are described in detail. The surface of a microwave plasma-treated PDMS slab was characterized using atomic force microscopy (AFM) and attenuated total reflection-Fourier Transform infrared spectroscopy (ATR-FTIR). The plasma-treated surface bears silica characteristics.     

Light stamping lithography: microcontact printing without inks

We report a new patterning method, called light-stamping lithography (LSL), that uses UV-induced adhesion of poly(dimethylsiloxane) (PDMS). LSL is based on the direct transfer of the contact surface of the PDMS stamp to a substrate via a UV (254 nm)-induced surface bonding between the stamp and the substrate. This procedure can be adopted in automated printing machines that generate patterns with a wide range of feature sizes on diverse substrates. To demonstrate its usefulness, the LSL method was applied to prepare several PDMS patterns on a variety of substrates. The PDMS patterns were then used as templates for selective deposition of TiO2 thin film using atomic layer deposition as well as resists for selective wet etching.     

Surface characterization using chemical force microscopy and the flow performance of modified polydimethylsiloxane for microfluidic device applications

The widespread interest in micro total analysis systems has resulted in efforts to develop devices in cheaper polymer materials such as polydimethylsiloxane (PDMS) as an alternative to expensive glass and silicon devices. We describe the oxidation of the PDMS surface to form ionizable groups using a discharge from a Tesla coil and subsequent chemical modification to augment electroosmotic flow (EOF) within the microfluidic devices. The flow performance of oxidized, amine-modified and unmodified PDMS materials has been determined and directly compared to conventional glass devices. Exact PDMS replicas of glass substrates were prepared using a novel two step micromolding protocol. Chemical force microscopy has been utilized to monitor and measure the efficacy of surface modification yielding information about the acid/base properties of the modified and unmodified surfaces. Results with different substrate materials correlates well with expected flow modifications as a result of surface modification. Oxidized PDMS devices were found to support faster EOF (twice that of native PDMS) similar to glass while those derivatized with 3-aminopropyl triethoxysilane (APTES) showed slower flow rates compared to native PDMS substrates as a result of masking surface charge. Results demonstrate that the surface of PDMS microdevices can be manipulated to control EOF characteristics using a facile surface derivatization methodology allowing surfaces to be tailored for specific microfluidic applications and characterized with chemical force microscopy.     

Photolithographic surface micromachining of polydimethylsiloxane (PDMS)

A major technical hurdle in microfluidics is the difficulty in achieving high fidelity lithographic patterning on polydimethylsiloxane (PDMS). Here, we report a simple yet highly precise and repeatable PDMS surface micromachining method using direct photolithography followed by reactive ion etching (RIE). Our method to achieve surface patterning of PDMS applied an O(2) plasma treatment to PDMS to activate its surface to overcome the challenge of poor photoresist adhesion on PDMS for photolithography. Our photolithographic PDMS surface micromachining technique is compatible with conventional soft lithography techniques and other silicon-based surface and bulk micromachining methods. To illustrate the general application of our method, we demonstrated fabrication of large microfiltration membranes and free-standing beam structures in PDMS.     

Plasma stencilling methods for cell patterning

In this paper we describe plasma stencilling techniques for patterning 10 mammalian cell lines on hydrophobic and cell repellent poly(dimethylsiloxane) (PDMS), methylated glass and bacterial grade polystyrene surfaces. An air plasma produced with a Tesla generator operating at atmospheric pressure was used with microengineered stencils for patterned surface oxidation, selectively transforming the surface to a hydrophilic state to enable cell adhesion and growth. Plasma stencilling obviates the need for directly patterning cell adhesion molecules. Instead, during cell culture, adhesion proteins from the media assemble in a bioactive form on the hydrophilic regions. Critically, the removal of protein patterning prior to cell culture provides the option to also use PDMS–PDMS plasma bonding to incorporate cell patterns within microfluidic systems. Linear patterns were generated using PDMS microchannel stencils, and polyimide stencils with through holes were used for the production of cellular arrays. For the production of smaller cellular arrays, a novel microcapillary-based dielectric barrier discharge system was developed. A numerical method to characterise the cell patterns is also introduced and was used to demonstrate that plasma stencilling is highly effective, with complete patterns confined during long term cell culture (>10 days). In summary, plasma stencilling is simple, rapid, inexpensive, reproducible and a potentially universal cell line patterning capability.

Rapid microfabrication of solvent-resistant biocompatible microfluidic devices

This paper presents a rapid, simple, and low-cost fabrication method to prepare solvent resistant and biocompatible microfluidic devices with three-dimensional geometries. The devices were fabricated in thiolene and replicated from PDMS master with high molding fidelity. Good chemical compatibility for organic solvents allows volatile chemicals in synthesis and analysis applications. The surface can be processed to be hydrophobic or hydrophilic for water-in-oil and oil-in-water emulsions. Monodisperse organic solvent droplet generation is demonstrated to be reproducible in thiolene microchannels without swelling. The thiolene surface prevents cell adhesion but normal cell growth and adhesion on glass substrates is not affected by the adjacent thiolene patterns.     

Changes in silicon elastomeric surface properties under stretching induced by three surface treatments

Poly(dimethylsiloxane) (PDMS) substrates are used in many applications where the substrates need to be elongated and various treatments are used to regulate their surface properties. In this article, we compare the effect of three of such treatments, namely, UV irradiation, water plasma, and plasma polymerization, both from a molecular and from a macroscopic point of view. We focus our attention in particular on the behavior of the treated surfaces under mechanical stretching. UV irradiation induces the substitution of methyl groups by hydroxyl and acid groups, water plasma leads to a silicate-like layer, and plasma polymerization causes the formation of an organic thin film with a major content of anhydride and acid groups. Stretching induces cracks on the surface both for silicate-like layers and for plasma polymer thin coatings. This is not the case for the UV irradiated PDMS substrates. We then analyzed the chemical composition of these cracks. In the case of water plasma, the cracks reveal native PDMS. In the case of plasma polymerization, the cracks reveal modified PDMS. The contact angles of plasma polymer and UV treated surfaces vary only very slightly under stretching, whereas large variations are observed for water plasma treatments. The small variation in the contact angle values observed on the plasma polymer thin film under stretching even when cracks appear on the surface are explained by the specific chemistry of the PDMS in the cracks. We find that it is very different from native PDMS and that its structure is somewhere between Si(O2) and Si(O3). This is, to our knowledge, the first study where different surface treatments of PDMS are compared for films under stretching.     

Effects of flame treatment on the interfacial energy of polyethylene assessed by contact mechanics

The effects of flame treatment of low-density polyethylene (LDPE) on the work of adhesion (W) and energy release rate (G) were assessed by a custom-built adhesion testing device (ATD). The contact area and the vertical displacement between planar LDPE films and PDMS lenses (untreated and UV/ozone treated) were varied as a function of the applied load, P. The adhesion and pull-off forces between the extracted PDMS lenses and the LDPE films were studied as a function of the duration of the flame treatment expressed in treatment numbers. A fracture mechanics approach was used to relate the applied load and the radius of the contact area to the energy release rate (G). The difference between the energy release rate and the thermodynamic work of adhesion, defined as the adhesion hysteresis (G - W), increased systematically with increasing treatment numbers for both lens types. In addition, the adhesion hysteresis appeared to be dependent on the contact time. Finally, the origin of the adhesion hysteresis was discussed. It was concluded that bonding by surface functional groups may be the dominating mechanisms for the changes in the observed hysteresis.     

Surface analysis of plasma‐treated polydimethylsiloxane by x‐ray photoelectron spectroscopy and surface voltage decay

Surface states of polydimethylsiloxane (PDMS) treated by plasma were investigated by x‐ray photoelectron spectroscopy and surface voltage decay. X‐ray photoelectron spectroscopy confirmed the formation of a silica‐like (SiO_x, x = 3–4) oxidative surface layer. This layer increased in thickness with increasing exposure duration of plasma. Plasma exposure lowers the surface resistivity from 1.78 × 10¹⁴ to 1.09 × 10¹³ Ω □^?1 with increasing plasma treatment time. By measuring the decay time constant of surface voltage, the calculated surface resistivity was compared with the value measured directly by a voltage–current method; good agreement between the two methods was obtained. It was observed that plasma treatment led to a decrease in the thermal activation energy of the surface conduction from 31.0 kJ mol^?1 for an untreated specimen to 21.8 kJ mol^?1 for a plasma‐treated specimen for 1 h. Our results allow the examination of effects of plasma on the electrical properties of PDMS. Copyright © 2003 John Wiley & Sons, Ltd.     

Surface modification of titanium with thermally treated polydimethylsiloxane coating and the effect on resin to titanium adhesion

In this study, titanium surface modification by a thermal treatment using a polydimethylsiloxane (PDMS) coating was investigated. The surfaces of four titanium samples were surface treated by polishing, sandblasting, and coating with a PDMS with a thermal treatment at 800 and 1100 °C. The titanium surfaces were characterized by X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy. The effect of the surface treatments on adhesion of resin to titanium was assessed by shear adhesion strength test. XPS analysis showed that there was a change of elemental composition of titanium surfaces after surface treatment. Binding energy shifts for Si2p and O1s were observed after sandblasting and thermally treated PDMS. Therefore, chemical states of Si and O were changed. Atomic force microscopy analysis revealed that the surface topography of the Ti samples was different, and surface roughness was increased after sandblasting and thermal treatment of PDMS coating. Shear adhesion strength test results showed that the adhesion between resin and titanium is affected by the treatment temperature of PDMS coating. The highest adhesion is obtained at 1100 °C (14.7 ± 1.57 MPa). Copyright © 2014 John Wiley & Sons, Ltd.     

Coatings of polyethylene glycol for suppressing adhesion between solid microspheres and flat surfaces

This article describes the development and the examination of surface coatings that suppress the adhesion between glass surfaces and polymer microspheres. Superparamagnetic doping allowed for exerting magnetic forces on the microbeads. The carboxyl functionalization of the polymer provided the means for coating the beads with polyethylene glycol (PEG) with different molecular weight. Under gravitational force, the microbeads settled on glass surfaces with similar polymer coatings. We examined the efficacy of removing the beads from the glass surfaces by applying a pulling force of ~1.2 pN. The percent beads remaining on the surface after applying the pulling force for approximately 5 s served as an indication of the adhesion propensity. Coating of PEG with molecular weight ranging between 3 and 10 kDa was essential for suppressing the adhesion. For the particular substrates, surface chemistry and aqueous media we used, coatings of 5 kDa manifested optimal suppression of adhesion: that is, only 3% of the microbeads remained on the surface after applying the pulling magnetic force. When either the glass or the beads were not PEGylated, the adhesion between them was substantial. Addition of a noncharged surfactant, TWEEN, above its critical micelle concentrations (CMCs) suppressed the adhesion between noncoated substrates. The extent of this surfactant-induced improvement of the adhesion suppression, however, did not exceed the quality of preventing the adhesion that we attained by PEGylating both substrates. In addition, the use of surfactants did not significantly improve the suppression of bead-surface adhesion when both substrates were PEGylated. These findings suggest that such surfactant additives tend to be redundant and that covalently grafted coatings of PEGs with selected chain lengths provide sufficient suppression of nonspecific interfacial interactions.     

Modification of the glass surface property in PDMS-glass hybrid microfluidic devices

This paper presents a simple method to change the hydrophilic nature of the glass surface in a poly(dimethylsiloxane) (PDMS)-glass hybrid microfluidic device to hydrophobic by an extra-heating step during the fabrication process. Glass substrates bonded to a native or oxygen plasma-treated PDMS chip having microchambers (12.5 mm diameter, 110 μm height) were heated at 200°C for 3 h, and then the hydrophobicity of the glass surfaces on the substrate was evaluated by measuring the contact angle of water. By the extra-heating process, the glass surfaces became hydrophobic, and its contact angle was around 109°, which is nearly the same as native PDMS surfaces. To demonstrate the usefulness of this surface modification method, a PDMS-glass hybrid microfluidic device equipped with microcapillary vent structures for pneumatic manipulation of droplets was fabricated. The feasibility of the microcapillary vent structures on the device with the hydrophobic glass surfaces are confirmed in practical use through leakage tests of the vent structures and liquid handling for the electrophoretic separation of DNA molecules.     

Analysis of Dynamic and Thermodynamic Adsorption of Nanoparticles on Solid Surfaces by Dark‐Field Light Scattering Measurements

We have constructed a dark‐field light scattering microscope using a very low‐cost digital camera to investigate the adsorption of gold nanoparticles (AuNPs) on four different substrates at various pH values. The substrates used are glass, polycarbonate (PC), poly(dimethylsiloxane) (PDMS), and poly(methyl methacrylate) (PMMA). The coverage of AuNPs on hydrophobic substrates such as PDMS is greater than that on hydrophilic substrates like glass. The adsorption and aggregation of AuNPs on a particular substrate increased upon decreasing the pH (from 9.0 to 4.0). A greater coverage percentage of AuNPs, but less aggregation, occurs on glass treated with poly(diallyldimethylammonium) (PDDA) than on bare glass. The scattering intensity increases upon increasing the number of layers of adsorbed AuNPs on glass that was treated sequentially with AuNPs and PDDA. When compared to UV‐Vis absorption, dark‐field microscope provides greater sensitivity and qualitative surface information.