Emerging Technologies and Materials for High-Resolution 3D Printing of Microfluidic Chips.

In recent years, 3D printing has had a huge impact on the field of biotechnology: from 3D-printed pharmaceuticals to tissue engineering and microfluidic chips. Microfluidic chips are of particular interest and importance for the field of biotechnology, since they allow for the analysis and screening of a wide range of biomolecules - including single cells, proteins, and DNA. The fabrication of microfluidic chips has historically been time-consuming, however, and is typically limited to 2.5 dimensional structures and a restricted palette of well-known materials. Due to the high surface-to-volume ratios in microfluidic chips, the nature of the chip material is of paramount importance to the final system behavior. With the emergence of 3D printing, however, a wide range of microfluidic systems are now being printed for the first time in a manner that facilitates flexibility while minimizing time and cost. Nevertheless, resolution and material choices still remain challenges and in the focus of current research, aiming for (1) 3D printing with high resolutions in the range of tens of micrometers and (2) a wider range of available materials for these high-resolution prints. The first part of this chapter highlights recent emerging technologies in the field of high-resolution printing via stereolithography (SL) and 2-photon polymerization (2PP) and seeks to identify particularly interesting emerging technologies which could have a major impact on the field in the near future. The second part of this chapter highlights current developments in the field of materials that are used for these high-resolution 3D printing technologies.

Facile fabrication of micro-/nanostructured, superhydrophobic membranes with adjustable porosity by 3D printing.

Porous membranes with special wetting properties have attracted great interest due to their various functions and wide applications, including water filtration, selective oil/water separation and oil skimming. Special wetting properties such as superhydrophobicity can be achieved by controlling the surface chemistry as well as the surface topography of a substrate. Three-dimensional (3D) printing is a promising method for the fast and easy generation of various structures. The most common method for 3D printing of superhydrophobic materials is a two-step fabrication process: 3D printing of user-defined topographies, such as surface structures or bulk porosity, followed by a chemical post-processing with low-surface energy chemicals such as fluorinated silanes. Another common method is using a hydrophobic polymer ink to print intricate surface structures. However, the resolution of most common printers is not sufficient to produce nano-/microstructured textures, moreover, the resulting delicate surface micro- or nanostructures are very prone to abrasion. Herein, we report a simple approach for 3D printing of superhydrophobic micro-/nanoporous membranes in a single step, combining the required topography and chemistry. The bulk porosity of this material, which we term "Fluoropor", makes it insensitive to abrasion. To achieve this, a photocurable fluorinated resin is mixed with a porogen mixture and 3D printed using a stereolithography (SLA) printing process. This way, micro-/nanoporous membranes with superhydrophobic properties with static contact angles of 164° are fabricated. The pore size of the membranes can be adjusted from 30 nm to 300 nm by only changing the porogen ratio in the mixture. We show the applicability of the printed membranes for oil/water separation and the formation of Salvinia layers which are of great interest for drag reduction in maritime transportation and fouling prevention.

High Resolution Patterning of an Organic-Inorganic Photoresin for the Fabrication of Platinum Microstructures.

Platinum (Pt) is an interesting material for many applications due to its high chemical resilience, outstanding catalytic activity, high electrical conductivity, and high melting point. However, microstructuring and especially 3D microstructuring of platinum is a complex process, based on expensive and specialized equipment often suffering from very slow processing speeds. In this work, organic-inorganic photoresins, which can be structured using direct optical lithography as well as two-photon lithography (TPL) with submicrometer resolution and high-throughput is presented. The printed structures are subsequently converted to high-purity platinum using thermal debinding of the binder and reduction of the salt. With this technique, complex 3D structures with a 3D resolution of 300 nm were fabricated. At a layer thickness of 35 nm, the patterns reach a high conductivity of 67% compared to bulk platinum. Microheaters, thermocouple sensors as well as a Lab-on-a-Chip system are presented as exemplary applications. This technology will enable a broad range of application from electronics, sensing and heating elements to 3D photonics and metamaterials.

High-throughput injection molding of transparent fused silica glass.

Glass is one of the most relevant high-performance materials that has the benefit of a favorable environmental footprint compared with that of other commodity materials. Despite the advantageous properties of glasses, polymers are often favored because they can be processed using scalable industrial replication techniques like injection molding (IM). Glasses are generally processed through melting, which is both energy intensive and technologically challenging. We present a process for glassworks using high-throughput IM of an amorphous silicon dioxide nanocomposite that combines established process technologies and low-energy sintering. We produce highly transparent glass using classical IM and sintering, allowing for a potentially substantial reduction in energy consumption. Our strategy merges polymer and glass processing, with substantial implications for glass utilization.

Two-Photon Polymerization of Nanocomposites for the Fabrication of Transparent Fused Silica Glass Microstructures.

Fused silica glass is the material of choice for many high-performance components in optics due to its high optical transparency combined with its high thermal, chemical, and mechanical stability. Especially, the generation of fused silica microstructures is of high interest for microoptical and biomedical applications. Direct laser writing (DLW) is a suitable technique for generating such devices, as it enables nearly arbitrary structuring down to the sub-micrometer level. In this work, true 3D structuring of transparent fused silica glass using DLW with tens of micrometer resolution and a surface roughness of Ra  ≈ 6 nm is demonstrated. The process uses a two-photon curable silica nanocomposite resin that can be structured by DLW, with the printout being convertible to transparent fused silica glass via thermal debinding and sintering. This technology will enable a plethora of applications from next-generation optics and photonics to microfluidic and biomedical applications with resolutions on the scale of tens of micrometers.

Fused Deposition Modeling of Microfluidic Chips in Polymethylmethacrylate.

Polymethylmethacrylate (PMMA) is one of the most important thermoplastic materials and is a widely used material in microfluidics. However, PMMA is usually structured using industrial scale replication processes, such as hot embossing or injection molding, not compatible with rapid prototyping. In this work, we demonstrate that microfluidic chips made from PMMA can be 3D printed using fused deposition modeling (FDM). We demonstrate that using FDM microfluidic chips with a minimum channel cross-section of ~300 µm can be printed and a variety of different channel geometries and mixer structures are shown. The optical transparency of the chips is shown to be significantly enhanced by printing onto commercial PMMA substrates. The use of such commercial PMMA substrates also enables the integration of PMMA microstructures into the printed chips, by first generating a microstructure on the PMMA substrates, and subsequently printing the PMMA chip around the microstructure. We further demonstrate that protein patterns can be generated within previously printed microfluidic chips by employing a method of photobleaching. The FDM printing of microfluidic chips in PMMA allows the use of one of microfluidics' most used industrial materials on the laboratory scale and thus significantly simplifies the transfer from results gained in the lab to an industrial product.

A Nontoxic Battery with 3D-Printed Housing for On-Demand Operation of Microcontrollers in Microfluidic Sensors.

Microcontrollers have a low energy consumption and are convenient tools for the operation and readout of small lab-on-a-chip devices. The operation of microcontrollers for data collection and analysis is key for measurements and statistics in field experiments. However, for portable lab-on-a-chip or point-of-care systems in low-resource settings, the availability of energy sources is a bottleneck. Here, we present a simple, nontoxic aluminum/air redox battery with a 3D-printed housing for on-demand operation of a sensor using a microcontroller for data collection. The battery is stored in a dry state and can be manufactured conveniently using off-the-shelf components and a simple 3D printer. It can be quickly assembled and operates a microcontroller for at least one hour in continuous operation mode. We demonstrate its performance by collecting data from a capacitive sensor capable of determining the conductivity of liquid samples. Such sensors can be used for, e.g., determining the water quality or phase formation in liquid mixtures. The sensor performance in determining different conductivities of nonconductive and conductive liquids in droplets is demonstrated.

Liquid Glass for Photovoltaics: Multifunctional Front Cover Glass for Solar Modules.

Advanced optical concepts, making use of tailored microstructured front cover glasses, promise to reduce the losses encountered with encapsulated solar modules. However, implementing optical concepts into the conventional architecture of encapsulated solar modules and simultaneously maintaining high durability represent a severe technological challenge. The liquid glass technique offers a route to meet this challenge by enabling the implementation of these optical concepts directly into the durable front cover glass of solar modules. In this work, we demonstrate for the first time two showcases of texturing fused silica front cover glass, using the facile liquid glass technique: (I) multifunctional microcone textures that reduce front-side reflection losses by ∼80% compared to a planar reference, which correlates to an increase in short-circuit current density of encapsulated planar monocrystalline silicon heterojunction solar cells by 2.9 mA cm-2, and exhibit strong hydrophilic behavior facilitating self-cleaning and (II) embedded freeform surface cloaks that redirect incident light away from the metallic contact grids of the solar cell and demonstrate a cloaking efficiency of ∼88%.

Analytical Solution of the Time-Dependent Microfluidic Poiseuille Flow in Rectangular Channel Cross-Sections and its Numerical Implementation in Microsoft Excel.

We recently demonstrated that the Navier-Stokes equation for pressure-driven laminar (Poiseuille) flow can be solved in any channel cross-section using a finite difference scheme implemented in a spreadsheet analysis tool such as Microsoft Excel. We also showed that implementing different boundary conditions (slip, no-slip) is straight-forward. The results obtained in such calculations only deviated by a few percent from the (exact) analytical solution. In this paper we demonstrate that these approaches extend to cases where time-dependency is of importance, e.g., during initiation or after removal of the driving pressure. As will be shown, the developed spread-sheet can be used conveniently for almost any cross-section for which analytical solutions are close-to-impossible to obtain. We believe that providing researchers with convenient tools to derive solutions to complex flow problems in a fast and intuitive way will significantly enhance the understanding of the flow conditions as well as mass and heat transfer kinetics in microfluidic systems.

Fabrication of arbitrary three-dimensional suspended hollow microstructures in transparent fused silica glass.

Fused silica glass is the preferred material for applications which require long-term chemical and mechanical stability as well as excellent optical properties. The manufacturing of complex hollow microstructures within transparent fused silica glass is of particular interest for, among others, the miniaturization of chemical synthesis towards more versatile, configurable and environmentally friendly flow-through chemistry as well as high-quality optical waveguides or capillaries. However, microstructuring of such complex three-dimensional structures in glass has proven evasive due to its high thermal and chemical stability as well as mechanical hardness. Here we present an approach for the generation of hollow microstructures in fused silica glass with high precision and freedom of three-dimensional designs. The process combines the concept of sacrificial template replication with a room-temperature molding process for fused silica glass. The fabricated glass chips are versatile tools for, among other, the advance of miniaturization in chemical synthesis on chip.

High-Performance Materials for 3D Printing in Chemical Synthesis Applications.

3D printing has emerged as an enabling technology for miniaturization. High-precision printing techniques such as stereolithography are capable of printing microreactors and lab-on-a-chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D-printed chips are highly sought for bringing chemistry up-to-date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D-printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.

Study of Biofilm Growth on Slippery Liquid-Infused Porous Surfaces Made from Fluoropor.

Undesired growth of biofilms represents a fundamental problem for all surfaces in long-term contact with aqueous media. Mature biofilms resist most biocide treatments and often are a pathogenic threat. One way to prevent biofilm growth on surfaces is by using slippery liquid-infused porous surfaces (SLIPS). SLIPS consist of a porous substrate which is infused with a lubricant immiscible with the aqueous medium in which the bacteria are suspended. Because of the lubricant, bacteria cannot attach to the substrate surface and thus formation of the biofilm is prevented. For this purpose, we manufactured substrates with different porosity and surface roughness values via UV-initiated free-radical polymerization in Fluoropor. Fluoropor is a class of highly fluorinated bulk-porous polymers with tunable porosity, which we recently introduced. We investigated the growth of the biofilm on the substrates, showing that a reduced surface roughness is beneficial for the reduction of biofilm growth. Samples of low roughness effectively reduced Pseudomonas aeruginosa biofilm growth for 7 days in a flow chamber experiment. The low-roughness samples also become transparent when infused with the lubricant, making such surfaces ideal for real-time observation of biofilm growth by optical examination.

Highly Fluorinated Methacrylates for Optical 3D Printing of Microfluidic Devices.

Highly fluorinated perfluoropolyether (PFPE) methacrylates are of great interest for transparent and chemically resistant microfluidic chips. However, so far only a few examples of material formulations for three-dimensional (3D) printing of these polymers have been demonstrated. In this paper we show that microfluidic chips can be printed using these highly fluorinated polymers by 3D stereolithography printing. We developed photocurable resin formulations that can be printed in commercial benchtop stereolithography printers. We demonstrate that the developed formulations can be printed with minimal cross-sectional area of 600 µm for monolithic embedded microfluidic channels and 200 µm for open structures. The printed and polymerized PFPE methacrylates show a good transmittance above 70% at wavelengths between 520⁻900 nm and a high chemical resistance when being exposed to organic solvents. Microfluidic mixers were printed to demonstrate the great variability of different designs that can be printed using stereolithography.

Glassomer-Processing Fused Silica Glass Like a Polymer.

Fused silica glass is one of the most important high-performance materials for scientific research, industry, and society. However due to its high chemical and thermal resistance as well as high hardness, fused silica glass is notoriously difficult to structure. This work introduces Glassomer, a solid nanocomposite, which can be structured using polymer molding and subtractive technologies at submicrometer resolution. After polymer processing Glassomer is turned into optical grade fused silica glass during a final heat treatment. The resulting glass has the same optical transparency as commercial fused silica and a smooth surface with a roughness of a few nanometers. This work makes high-performance fused silica glass components accessible to high-throughput fabrication technologies and will enable numerous optical, photonic and medical applications in science and industry.

Transparent, abrasion-insensitive superhydrophobic coatings for real-world applications.

Superhydrophobic surfaces and surface coatings are of high interest for many applications in everyday life including non-wetting and low-friction coatings as well as functional clothing. Manufacturing of these surfaces is intricate since superhydrophobicity requires structuring of surfaces on a nano- to microscale. This delicate surface structuring makes most superhydrophobic surfaces very sensitive to abrasion and renders them impractical for real-life applications. In this paper we present a transparent fluorinated polymer foam that is synthesized by a simple one-step photoinitiated radical polymerization. We term this material "Fluoropor". It possesses an inherent nano-/microstructure throughout the whole bulk material and is thus insensitive to abrasion as its superhydrophobic properties are not merely due to a thin-layer surface-effect. Due to its foam-like structure with pore sizes below the wavelength of visible light Fluoropor appears optically transparent. We determined contact angles, surface energy, wear resistance and Vickers hardness to highlight Fluoropor's applicability for real-word applications.

Three-dimensional printing of transparent fused silica glass.

Glass is one of the most important high-performance materials used for scientific research, in industry and in society, mainly owing to its unmatched optical transparency, outstanding mechanical, chemical and thermal resistance as well as its thermal and electrical insulating properties. However, glasses and especially high-purity glasses such as fused silica glass are notoriously difficult to shape, requiring high-temperature melting and casting processes for macroscopic objects or hazardous chemicals for microscopic features. These drawbacks have made glasses inaccessible to modern manufacturing technologies such as three-dimensional printing (3D printing). Using a casting nanocomposite, here we create transparent fused silica glass components using stereolithography 3D printers at resolutions of a few tens of micrometres. The process uses a photocurable silica nanocomposite that is 3D printed and converted to high-quality fused silica glass via heat treatment. The printed fused silica glass is non-porous, with the optical transparency of commercial fused silica glass, and has a smooth surface with a roughness of a few nanometres. By doping with metal salts, coloured glasses can be created. This work widens the choice of materials for 3D printing, enabling the creation of arbitrary macro- and microstructures in fused silica glass for many applications in both industry and academia.

Numerics made easy: solving the Navier-Stokes equation for arbitrary channel cross-sections using Microsoft Excel.

The fluid mechanics of microfluidics is distinctively simpler than the fluid mechanics of macroscopic systems. In macroscopic systems effects such as non-laminar flow, convection, gravity etc. need to be accounted for all of which can usually be neglected in microfluidic systems. Still, there exists only a very limited selection of channel cross-sections for which the Navier-Stokes equation for pressure-driven Poiseuille flow can be solved analytically. From these equations, velocity profiles as well as flow rates can be calculated. However, whenever a cross-section is not highly symmetric (rectangular, elliptical or circular) the Navier-Stokes equation can usually not be solved analytically. In all of these cases, numerical methods are required. However, in many instances it is not necessary to turn to complex numerical solver packages for deriving, e.g., the velocity profile of a more complex microfluidic channel cross-section. In this paper, a simple spreadsheet analysis tool (here: Microsoft Excel) will be used to implement a simple numerical scheme which allows solving the Navier-Stokes equation for arbitrary channel cross-sections.

Liquid Glass: A Facile Soft Replication Method for Structuring Glass.

Liquid glass is a photocurable amorphous silica nanocomposite that can be structured using soft replication molds and turned into glass via thermal debinding and sintering. Simple polymer bonding techniques allow the fabrication of complex microsystems in glass like microfluidic chips. Liquid glass is a step toward prototyping of glass microstructures at low cost without requiring cleanroom facilities or hazardous chemicals.

Tacky cyclic olefin copolymer: a biocompatible bonding technique for the fabrication of microfluidic channels in COC.

Cyclic olefin copolymer (COC) is widely used in microfluidics due to its UV-transparency, its biocompatibility and high chemical resistance. Here we present a fast and cost-effective solvent bonding technique, which allows for the efficient bonding of protein-patterned COC structures. The bonding process is carried out at room temperature and takes less than three minutes. Enzyme activity is retained upon bonding and microstructure deformation does not occur.

Polysiloxane layers created by sol-gel and photochemistry: ideal surfaces for rapid, low-cost and high-strength bonding of epoxy components to polydimethylsiloxane.

In this article we introduce and compare three techniques for low-cost and rapid bonding of stereolithographically structured epoxy components to polydimethylsiloxane (PDMS). In short, we first create a polysiloxane layer on the epoxy surface via silane surface coupling and polymerization. Afterwards, the modified epoxy surface can be bonded to a PDMS component at room temperature using a handheld corona discharger, which is a commonly used low-cost technique for bonding two PDMS components. Using these methods bonds of desirable strength can be generated within half an hour. Depending on the epoxy resin, we found it necessary to modify the silanization procedure. Therefore, we provide a total of three different silanization techniques that allow bonding of a wide variety of stereolithographically structurable epoxy resins. The first technique is a UV-light induced silanization process which couples a silane that contains an epoxy-ring ((3-glycidoxypropyl)trimethoxysilane (GPTMS)). For surfaces that cannot be modified with this silane we use dimethoxydimethylsilane (DMDMS). This silane can either be coupled to the surface by a sol-gel process or UV-light induced polymerisation. The sol-gel process which is a heat induced surface modification technique results in high bond strengths. Because of the heat which triggers the sol-gel process, this technique is limited to epoxy polymers with high glass transition temperatures. For the majority of stereolithographically structured epoxy resins which typically have glass transition temperatures of around 60 °C the light-induced bonding technique is preferable. For all three techniques we performed DIN EN-conform tensile testing demonstrating maximum bond strengths of up to 350 kPa which is comparable with bond strengths reported for PDMS-to-PDMS bonds. For all bond methods, long-term stability as well as hydrolytic stability was assessed.