Synthesis of Printable Polyvinyl Alcohol for Aerosol Jet and Inkjet Printing Technology
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micromachines Article Synthesis of Printable Polyvinyl Alcohol for Aerosol Jet and Inkjet Printing Technology Mahmuda Akter Monne 1 , Chandan Qumar Howlader 1, Bhagyashree Mishra 1 and Maggie Yihong Chen 1,2,* 1 Materials Science, Engineering, and Commercialization Program, Texas State University, San Marcos, TX 78666, USA; [email protected] (M.A.M.); [email protected] (C.Q.H.); [email protected] (B.M.) 2 Ingram School of Engineering, Texas State University, San Marcos, TX 78666, USA * Correspondence: [email protected] Abstract: Polyvinyl Alcohol (PVA) is a promising polymer due to its high solubility with water, availability in low molecular weight, having short polymer chain, and cost-effectiveness in processing. Printed technology is gaining popularity to utilize processible solution materials at low/room temperature. This work demonstrates the synthesis of PVA solution for 2.5% w/w, 4.5% w/w, 6.5% w/w, 8.5% w/w and 10.5% w/w aqueous solution was formulated. Then the properties of the ink, such as viscosity, contact angle, surface tension, and printability by inkjet and aerosol jet printing, were investigated. The wettability of the ink was investigated on flexible (Kapton) and non-flexible (Silicon) substrates. Both were identified as suitable substrates for all concentrations of PVA. Additionally, we have shown aerosol jet printing (AJP) and inkjet printing (IJP) can produce multi-layer PVA structures. Finally, we have demonstrated the use of PVA as sacrificial material for micro-electro-mechanical-system (MEMS) device fabrication. The dielectric constant of printed PVA is 168 at 100 kHz, which shows an excellent candidate material for printed or traditional Citation: Monne, M.A.; transistor fabrication. Howlader, C.Q.; Mishra, B.; Chen, M.Y. Synthesis of Printable Polyvinyl Keywords: aerosol jet printing; dielectric; etching; inkjet printing; polyvinyl alcohol (PVA), polymers; Alcohol for Aerosol Jet and Inkjet sacrificial material; micro-electro-mechanical-system (MEMS) Printing Technology. Micromachines 2021, 12, 220. https://doi.org/ doi:10.3390/mi12020220 1. Introduction Academic Editor: Andrea Ehrmann In 1915, Poly(vinyl alcohol) was discovered by F. Klatte from the precursor Poly(vinyl acetate) [1]. After that, the preparation of PVA was firstly described by W. O. Herrmann and Received: 20 January 2021 W. Haehnel in 1924 [2–4]. However, it cannot be prepared with traditional polymerization Accepted: 12 February 2021 Published: 22 February 2021 because its monomer vinyl alcohol is not stable and rearranges readily to acetaldehyde. It is usually manufactured from hydrolysis of polyvinyl acetate, which involves the partial or Publisher’s Note: MDPI stays neutral total replacement of the ester groups of vinyl acetate by hydroxyl groups under defined with regard to jurisdictional claims in conditions. Later, the PVA is precipitated, washed, and finally dried. The PVA properties published maps and institutional affil- depend on the polymer chain’s length or the degree of polymerization and the degree of iations. hydrolysis [5,6]. PVA is an example of a water-soluble semi-crystalline synthetic polymer, and it is also slightly soluble in ethanol. It is important to mention that the higher the degree of hydrolysis and polymerization, the lower the solubility of PVA in cold water. Polyvinyl alcohol is a semi-crystalline, non-toxic, water-soluble, and biodegradable polymer. It is also biocompatible with human tissues and has excellent gas-barrier properties [7]. PVA Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. has many applications, including but not limited to the manufacturing of cleaning and This article is an open access article detergent products, in the food packaging industry, water treatment, textile, agriculture, distributed under the terms and and construction [7–11]. It also has recently attracted an increasing amount of attention conditions of the Creative Commons for pharmaceutical uses (i.e., drug delivery) and in medical applications (e.g., wound Attribution (CC BY) license (https:// dressing, soft contact lenses, and eye drops) [12–15]. PVA films can be produced in either creativecommons.org/licenses/by/ a melt or solution form. Melt processing is compatible only with low hydrolysis or heavily 4.0/). plasticized PVA. At the same time, a PVA film can be deposited from the solution form Micromachines 2021, 12, 220. https://doi.org/10.3390/mi12020220 https://www.mdpi.com/journal/micromachines Micromachines 2021, 12, 220 2 of 15 through drop casting, spin coating, and electrospinning, etc. [16–18]. However, these methods have a few limitations in terms of waste of material. In case of spin coating, it has been reported that about 95% of material is wasted with no design/features/patterning capability [19–21]. Our work reports the synthesis of PVA and the potential of aerosol jet and inkjet printing technologies as a mean to provide a novel platform to produce multi- layer structures. This phenomenon will have a substantial impact on both the material processing and application perspectives. Recent developments in the thin-film deposition sector have focused on cheap, simple, eco-friendly, and energy-saving processes. Printing is a modern fabrication process that fits perfectly within this framework. The significant advantages of printing technology are material utilization efficiency, mask-free and additive patterning, large area capability, compatibility with many substrates, and the low-cost fabrication process [22–27]. Printing technology is used to successfully deposit conductive and non-conductive nanomaterial, polymers, ceramic, 1D/2D materials, dielectric, biological, and pharmaceutical-based materials [28–31]. With the advancement of flexible electronics, low molecular weight and water-soluble elastic polymers as well as high permittivity dielectrics are in demand for MEMS device and flexible transistor fabrication [32–37]. Many polymers like polyvinylpyrrolidone (PVP), polymethylmethacrylate (PMMA), and PVA have been studied for their water solubility, electrical, and dielectric properties [38]. However, PVA is the most studied polymer due to its versatile properties. It is highly water-soluble, has a low cost, and has suitable film-forming properties. The selection of appropriate sacrificial material is a crucial part of the MEMS fabri- cation process. The sacrificial material must be deposited and finally removed without disturbing other layers. Along with developing printed technology, researchers have been working on selecting appropriate sacrificial materials for years. In [39], the use of sacrificial layer technique is discussed to create multilayer metalized structure using SU-8 dielectric. Multilayer suspended structure was successfully fabricated by adopting sputter coating, which is another form of solution processible technique. Additionally, the MEMS fabrication process is less standardized than other microelec- tronics fabrication processes. 3D printed MEMS is a potential candidate among researchers for a selection of less expensive materials and producing new structures for future appli- cations [40]. However, it may be difficult to achieve sufficient resolution only with this technology compared to traditional MEMS fabrication technology [36,37,41]. A fundamen- tal study has been conveyed to fabricate graphene or graphite-based flexible MEMS devices which enables future researchers to fabricate 2D material-based MEMS devices [42,43]. This study aims to present the synthesis of PVA solution for printing technology (aerosol jet and inkjet printing), characterize the solution, and present the application of PVA for MEMS and transistor device fabrication. 2. Experiments Ink Formulation: The PVA solution is synthesized by mixing low molecular weight (<400 kDa) PVA crystal with DI water and heating with a microwave. Different percent- age of w/w PVA solutions were prepared for two printing techniques. Viscosity of the PVA solution was varied by changing the percent of PVA powder. It is observed that 0.5%–4.5% w/w PVA is good for inkjet printing technology and aerosol jet technology with the ultrasonic atomizer. The solution with >4.5% w/w PVA is suitable for aerosol jet printing with the pneumatic atomizer and other printing methods such as screen printing, spray coating, bar coating, blade coating, etc. To prepare a 2% w/w 10ml PVA solution, 10 mL of DI water is mixed with 0.2 g of low molecular weight PVA crystal and heated with a microwave. The microwave’s power setting is kept at 1000 watts, and the solution is microwaved for 180 s until a homogeneous solution is achieved. Later, the homogeneous solution is centrifuged for 30 min at 5000 rpm to eliminate the big and clustered polymer chains. Finally, the solution is filtered using a 0.25–0.45 µm filter before loading it to the Micromachines 2021, 12, x 3 of 16 Micromachinessolution2021 is, 12centrifuged, 220 for 30 min at 5000 rpm to eliminate the big and clustered polymer3 of 15 chains. Finally, the solution is filtered using a 0.25–0.45 µm filter before loading it to the printer reservoir. Figureprinter 1 shows reservoir. the Figure 98%1 hydr showsolyzed the 98% PVA hydrolyzed crystal PVA from crystal Sigma from Aldrich Sigma Aldrich (St. Louis, MO 63178, USA)(St. and Louis, the MO in-lab 63178, USA)prepared and the PVA in-lab solution. prepared PVA solution. (a) (b) Figure 1. (a) The 98%Figure hydrolyzed 1. (a) The 98% PVA hydrolyzed crystal. PVA (b crystal.) In-lab (b) In-labprepared prepared PVA PVA solution. solution. Ink Characterization (Viscosity): Ink was prepared with 5 different concentrations; Ink Characterization2.5% w /(Viscosity)w, 4.5% w/w, 6.5%: Inkw /wasw, 8.5% preparedw/w, and with 10.5% w5/ differentw PVA in DI concentrations; water. An AMETEK 2.5% w/w, 4.5% w/w, Brookfield6.5% w/w, (DV2T) 8.5% (Chandler, w/w, and AZ 85225,10.5% USA) w/w viscometer PVA in isDI used water. to measure An AMETEK the viscosity of each solution. Since the instrument gives multiple measured data for the viscosity Brookfield (DV2T) (Chandler,measurement AZ for 85225, different USA) shear rates, viscometer so standard is deviation used to of measure viscosity is the added viscosity to Table1 .