Name: forming micro-and nano-plastics from agricultural plastic films for employment in fundamental research studies
Uploaded: 2022-07-27T14:15:00
Description: Watch this Scientific Journal Video about Forming Micro-and Nano-Plastics from Agricultural Plastic Films for Employment in Fundamental Research Studies at JoVE.com

This research was funded by the Herbert College of Agriculture, the Biosystems Engineering and Soil Department, and the Science Alliance at the University of Tennessee, Knoxville. Furthermore, the authors gratefully acknowledge the financial support provided through the USDA Grant 2020-67019-31167 for this research. The initial feedstocks for preparing MNPs of PBAT-based biodegradable mulch film were kindly provided by BioBag Americas, Inc. (Dunevin, FL, USA), and&#160;PBAT pellets by Mobius, LLC (Lenoir City, TN).

1. Processing of MPs from plastic pellets through cryogenic pretreatment and milling
NOTE: This methodology is based on a procedure described elsewhere, employing a PBAT film composed of the same material used for this presented study29.
<ol>
	<li>Weigh polymer pellet samples of ~1 g and transfer into a 50 mL glass jar.</li>
	<li>Place the &#34;rectangular delivery&#34; tube with a 20 mesh (840 &#181;m) sieve in the slot in front of the rotary cutting...

This method describes an effective process initially described in a previous publication29, to prepare MNPs sourced from pellets and mulch films for environmental studies. The size reduction process involved cryogenic cooling (for film only), dry milling, and wet grinding stages, to manufacture model MNPs. We have applied this method to prepare MNPs from a wide range of polymeric feedstocks, including low-density polyethylene (LDPE), polybutyrate adipate-co-terephthalate (PBAT), and polylactic aci...

In recent decades, the rapidly increasing global production of plastics and improper disposal and lack of recycling for plastic waste has led to environmental pollution that has impacted marine and terrestrial ecosystems1,2,3. Plastic materials are essential for contemporary agriculture, particularly to cultivate vegetables, small fruit, and other specialty crops. Their usage as mulch films, high and low tunnel coverings, drip tape, and other applications aim to enhance crop yield and quality, lower production costs, and promote sustainable farming methods4,5. However, the expanding employment of &#34;plasticulture&#34; has raised concerns about the formation, distribution, and retention of plastic pieces in agricultural environments. After a continuous fragmentation process caused by embrittlement through environmental degradation during service life, larger plastic fragments form micro- and nanoplastics (MNPs), which persist in soil or migrate to adjacent waterways via water runoff and wind6,7,8. Environmental factors such as ultraviolet (UV) radiation through sunlight, mechanical forces of water, and biological factors trigger plastic embrittlement of environmentally dispersed plastics, resulting in the breakdown of larger plastic fragments into macro- or meso-plastic particles9,10. Further defragmentation forms microplastics (MPs) and nanoplastics (NPs), reflecting particles of average size (nominal diameter; dp) of 1-5000 &#181;m and 1-1000 nm, respectively11. However, the upper dp limit for NPs (i.e., a lower limit for MPs) is not universally agreed upon and&#160;in several papers, this is listed as 100 nm12.
MNPs from plastic waste pose an emerging global threat to soil health and ecosystem services. Adsorption of heavy metals from freshwater by MPs led to an 800-fold higher concentration of heavy metals compared to the surrounding environment13. Furthermore, MPs in aquatic ecosystems pose multiple stressors and contaminants by altering light penetration, causing oxygen depletion, and causing adhesion to various biota, including penetration and accumulation in aquatic organisms14.
Recent studies suggest that MNPs can impact soil geochemistry and biota, including microbial communities and plants15,16,17. Furthermore, NPs threaten the food web17,18,19,20. Since MNPs readily undergo vertical and horizontal transport in soil, they can carry absorbed contaminants such as pesticides, plasticizers, and microorganisms through the soil into groundwater or aquatic ecosystems such as rivers and streams21,22,23,24. Conventional agricultural plastics such as mulch films are made from polyethylene, which must be removed from the field after usage and disposed of in landfills. However, incomplete removal leads to substantial plastic debris accumulation in soils9,25,26. Alternatively, soil-biodegradable plastic mulches (BDMs) are designed to be tilled into the soil after use, where they will degrade over time. However, BDMs persist temporarily in soil and gradually degrade and fragment into MPs and NPs9,27.
Many current environmental ecotoxicological and fate studies employ idealized and non-representative MPs and NPs model materials. The most commonly used surrogate MNPs are monodisperse polystyrene micro- or nanospheres, which do not reflect the actual MNPs residing in the environment12,28. Consequently, the selection of unrepresentative MPs and NPs may result in inaccurate measurements and results. Based on the lack of appropriate model &#924;NPs for terrestrial environmental studies, the authors were motivated to prepare such models from agricultural plastics. We previously reported on the formation of MNPs from BDMs and polyethylene pellets through mechanical milling and grinding of plastic pellets and film materials and the dimensional and molecular characteristics of MNPs29. The current paper provides a more detailed protocol for preparing MNPs that can be applied more broadly to all agricultural plastics, such as mulch films or their pelletized feedstocks (Figure 1). Here, to serve as an example, we chose a mulch film and spherical pellets of the biodegradable polymer polybutylene adipate terephthalate (PBAT) to represent agricultural plastics.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Aluminum dish, 150 mL&#160;</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>08-732-103</td>
			<td>Drying of collected NPs</td>
		</tr>
		<tr>
			<td>Aluminum dish, 500 mL</td>
			<td>VWR International, Radnor, PA, USA</td>
			<td>25433-018</td>
			<td>Collecting NPs after wet-grinding</td>
		</tr>
		<tr>
			<td>Centrifuge</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>Centrific 228</td>
			<td>Container for centrifugation</td>
		</tr>
		<tr>
			<td>Delivery tube, #20, 840 &#181;m</td>
			<td>Thomas Scientific, Swedesboro, NJ, USA</td>
			<td>3383M30</td>
			<td>Sieving of the first fraction during milling</td>
		</tr>
		<tr>
			<td>Delivery tube, #60, 250 &#181;m</td>
			<td>Thomas Scientific, Swedesboro, NJ, USA</td>
			<td>3383M45</td>
			<td>Sieving of the second fraction (3x)&#160; during milling</td>
		</tr>
		<tr>
			<td>Thermomixer,&#160; 5350 Mixer</td>
			<td>Eppendorf North America, Enfield, CT, USA</td>
			<td>05-400-200</td>
			<td>Analysis of sieving experiments</td>
		</tr>
		<tr>
			<td>FT-IR Spectrum Two, spectrometer with attenuated total reflectance (ATR)</td>
			<td>Perkin Elmer, Waltham, MA, USA</td>
			<td>L1050228&#160;</td>
			<td>Measuring FTIR spectra</td>
		</tr>
		<tr>
			<td>Glass beaker, 1000 mL</td>
			<td>DWK Life Sciences, Milville, NJ, USA</td>
			<td>02-555-113</td>
			<td>Stirring of MPs-water slurry before grinding</td>
		</tr>
		<tr>
			<td>Glass front plate</td>
			<td>Thomas Scientific, Swedesboro, NJ, USA</td>
			<td>3383N55&#160;</td>
			<td>Front cover plaste for Wiley Mini Mill</td>
		</tr>
		<tr>
			<td>Glass jar, 50 mL</td>
			<td>Uline, Pleasant Prairie, WI, USA</td>
			<td>S-15846P</td>
			<td>Collective MPs after milling</td>
		</tr>
		<tr>
			<td>Glove Box, neoprene</td>
			<td>Bel-Art-SP Scienceware, Wayne, NJ, USA</td>
			<td>BEL-H500290000</td>
			<td>22-Inch, Size 10</td>
		</tr>
		<tr>
			<td>Zetasizer Nano ZS 90 size analyzer</td>
			<td>Malvern Panalytical, Worcestershire, UK&#160;</td>
			<td>Zetasizer Nano ZS</td>
			<td>Measuring nanoplastics dispersed in DI-water</td>
		</tr>
		<tr>
			<td>Microscope camera</td>
			<td>Nikon, Tokyo,&#160;108-6290, Japan</td>
			<td>Nikon Digital Sight 10</td>
			<td>Combined with Olympus microscope to receive digital images</td>
		</tr>
		<tr>
			<td>Microscope</td>
			<td>Olympus, Shinjuku, Tokyo, Japan</td>
			<td>Model SZ 61</td>
			<td>Imaging of MPs</td>
		</tr>
		<tr>
			<td>Nitrogen jar, low form dewar flasks</td>
			<td>Cole-Palmer, Vernon Hills, IL, USA</td>
			<td>UX-03771-23</td>
			<td>Storage of liquid nitrogen during cryogenic cooling</td>
		</tr>
		<tr>
			<td>Accurate Blend 200, 12-speed blender</td>
			<td>Oster, Boca Raton, FL, USA</td>
			<td>6684</td>
			<td>Initiating the size reduction of cryogenically treated plastic film</td>
		</tr>
		<tr>
			<td>PBAT film, - BioAgri&#8482; (Mater-Bi&#174;)</td>
			<td>BioBag Americas, Inc, Dunedin, FL, USA</td>
			<td>0.7 mm thick</td>
			<td>Feedstock to form MPs and NPs, agricultural mulch film</td>
		</tr>
		<tr>
			<td>PBAT pellets</td>
			<td>Mobius, LLC, Lenoir City, TN, USA</td>
			<td>Diameter 3 mm</td>
			<td>Feedstock to form microplastics (MPs) and nanoplastics (NPs) trough milling and grinding</td>
		</tr>
		<tr>
			<td>Plastic centrifuge tubes, 50 mL</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>06-443-18</td>
			<td>Centrifugation of slurry after wet-grinding</td>
		</tr>
		<tr>
			<td>Plastic jar, 1000 mL, pre-cleaned, straight sided</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>05-719-733</td>
			<td>Collection of NPs during and after wet grinding</td>
		</tr>
		<tr>
			<td>Polygon stir bars, diameter&#248;=8 mm, length=50.8 mm&#160;&#160;</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>14-512-127</td>
			<td>Stirring of MPs slurry prior to wet-grinding</td>
		</tr>
		<tr>
			<td>Scissors, titanium bonded</td>
			<td>Westcott, Shelton, CT, USA</td>
			<td>13901</td>
			<td>Cutting of initial PBAT film feedstocks</td>
		</tr>
		<tr>
			<td>Square glass cell with square aperture and cap, 12 mm O.D.</td>
			<td>Malvern Panalytical, Worcestershire, UK&#160;</td>
			<td>PCS1115</td>
			<td>Measuring of NPs particle size</td>
		</tr>
		<tr>
			<td>Stainless steel bottom, 3 inch, pan</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>8401</td>
			<td>For sieving after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel sieve, 3 inch, No. 140 (106 &#181;m)</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>1308</td>
			<td>For sieving after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel sieve, 3 inch, No. 20 (850 &#181;m)</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>1296</td>
			<td>Sieving of MPs after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel sieve, 3 inch, No. 325 (45 &#181;m)</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>1313</td>
			<td>Sieving of MPs after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel sieve, 3 inch, No. 60 (250 &#181;m)</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>1303</td>
			<td>Sieving of MPs after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel top cover, 3 inch</td>
			<td>Hogentogler &#38; Co. Inc, Columbia, MD, USA</td>
			<td>8406</td>
			<td>Sieving of MPs after Wiley-milling</td>
		</tr>
		<tr>
			<td>Stainless steel tweezers</td>
			<td>Global Industrial, Port Washington, NY, USA</td>
			<td>T9FB2264892</td>
			<td>Transferring of&#160; frozen film particles from jar into blender</td>
		</tr>
		<tr>
			<td>Vacuum oven, model 281A</td>
			<td>Fisher Scientific, Waltham, MA, USA</td>
			<td>13-262-50</td>
			<td>Vacuum oven to dry NPs after wet-grinding</td>
		</tr>
		<tr>
			<td>Friction grinding machine, Supermass Colloider</td>
			<td>Masuko Sangyo, Tokyo, Japan</td>
			<td>MKCA6-2J</td>
			<td>Grinding machine to form NPs from MPs</td>
		</tr>
		<tr>
			<td>Wet-grinding stone, grit size: 297 &#956;m -420 &#956;m</td>
			<td>Masuko Sangyo, Tokyo, Japan</td>
			<td>MKE6-46DD</td>
			<td>Grinding stone to form NPs from MPs</td>
		</tr>
		<tr>
			<td>Wiley Mini Mill, rotary cutting mill</td>
			<td>Thomas Scientific, Swedesboro, NJ, USA</td>
			<td>NC1346618</td>
			<td>Size reduction of pellets and film into MPs and NPs</td>
		</tr>
		<tr>
			<td>Software</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>FTIR-Spectroscopy software</td>
			<td>Perkin Elmer, Waltham, MA, USA</td>
			<td>Spectrum 10&#160;</td>
			<td>Collection of spectra from the initial plastic, MPs and NPs</td>
		</tr>
		<tr>
			<td>Image J, image processing program</td>
			<td>National Institutes of Health, Bethesda, MD, USA</td>
			<td>Version 1.53n</td>
			<td>Analysis of digital images received from microscopy&#160;</td>
		</tr>
		<tr>
			<td>Microscope software, ds-fi1 software</td>
			<td>Malvern Panalytical , Malvern, UK</td>
			<td>Firmware DS-U1 Ver3.10</td>
			<td>Recording of digital images</td>
		</tr>
		<tr>
			<td>Microsoft, Windows, &#160;Excel 365, spreadsheet software</td>
			<td>Microsoft, Redmond, WA, USA</td>
			<td>Office 365</td>
			<td>Calculating the average particle size and creating FTIR spectra images</td>
		</tr>
		<tr>
			<td>JMP software, statistical software</td>
			<td>SAS Institute Inc., Cary, NC, 1989-2021</td>
			<td>Version 15</td>
			<td>Statistical analysis of particle size and perform best fit of data set</td>
		</tr>
		<tr>
			<td>Unscrambler software</td>
			<td>Camo Analytics, Oslo, Norway</td>
			<td>Version 9.2</td>
			<td>Normalizing and converting FTIR spectra into .csv fromat</td>
		</tr>
	</tbody>
</table>

forming micro-and nano-plastics from agricultural plastic films for employment in fundamental research studies

Microplastics (MPs) and nanoplastics (NPs) dispersed in agricultural ecosystems can pose a severe threat to biota in soil and nearby waterways. In addition, chemicals such as pesticides adsorbed by NPs can harm soil organisms and potentially enter the food chain. In this context, agriculturally utilized plastics such as plastic mulch films contribute significantly to plastic pollution in agricultural ecosystems. However, most fundamental studies of fate and ecotoxicity employ idealized and poorly representative MP materials, such as polystyrene microspheres.
Therefore, as described herein, we developed a lab-scale multi-step procedure to mechanically form representative MPs and NPs for such studies. The plastic material was prepared from commercially available plastic mulch films of polybutyrate adipate-co-terephthalate (PBAT) that were embrittled through either cryogenic treatment (CRYO) or environmental weathering (W), and from untreated PBAT pellets. The plastic materials were then treated by mechanical milling to form MPs with a size of 46-840 &#181;m, mimicking the abrasion of plastic fragments by wind and mechanical machinery. The MPs were then sieved into several size fractions to enable further analysis. Finally, the 106 &#181;m sieve fraction was subjected to wet grinding to generate NPs of 20-900 nm, a process that mimics the slow size reduction process for terrestrial MPs. The dimensions and the shape for MPs were determined through image analysis of stereomicrographs, and dynamic light scattering (DLS) was employed to assess particle size for NPs. MPs and NPs formed through this process possessed irregular shapes, which is in line with the geometric properties of MPs recovered from agricultural fields. Overall, this size reduction method proved efficient for forming MPs and NPs composed of biodegradable plastics such as polybutylene adipate-co-terephthalate (PBAT), representing mulch materials used for agricultural specialty crop production.

To validate the experimental procedure method and analysis, MPs and NPs were formed from pellets and film materials and compared by size and shape using microscopic images. The method described in Figure 1 efficiently formed MPs and NPs from biodegradable plastic pellets and films; this was achieved through cryogenic cooling, milling, and wet-grinding and characterization. The former step was unnecessary for environmentally weathered films because weathering induced embrittlement (Astner et ...

Watch this Scientific Journal Video about Forming Micro-and Nano-Plastics from Agricultural Plastic Films for Employment in Fundamental Research Studies at JoVE.com

Forming Micro-and Nano-Plastics from Agricultural Plastic Films for Employment in Fundamental Research Studies

We show the formation and dimensional characterization of micro- and nanoplastics (MPs and NPs, respectively) using a stepwise process of mechanical milling, grinding, and imaging analysis.

Microplastics (MPs) and nanoplastics (NPs) dispersed in agricultural ecosystems can pose a severe threat to biota in soil and nearby waterways. In ...

Anton Astner:This protocol describes the preparation of engineered micro and nanoplastics sourced from a wide range of polymer feed stocks, such as pellets and films representing authentic model materials. This method efficiently forms micro nanoplastics through a simple mechanical procedure involving cryogenic milling, seething and wet grinding that can serve a surrogate materials for environmental studies. To begin retrieve foam from roll and cut P B A T foam into strips with a paper cutter pre soak fragments in deionized water for 10 minutes and transfer the foam material into a cryogenic container.Slowly add 200 milliliters of liquid nitrogen to a cryogenic container transfer pres soaked foam fragments or pellets carefully into the cryogenic container with steel tweezers. Next, transfer frozen foam fragments or pellets into a blender and process for 10 seconds. Add 400 milliliters of DI water and blend the foam water slurry for five minutes.Transfer slur into a buchner funnel with a filter and apply vacuum for one hour. Then transfer the sample with the funnel into a vacuum oven. Dry at 30 degrees Celsius for at least 48 hours.Weigh polymer film or pellet samples and transfer into a 50 milliliter glass jar. Place the rectangular delivery tube with a 20 mesh seed in the slot in front of the rotary cutting milk and raise the delivery tube until it hits the stock pin. Position the glass plate over the milling chambers face and secure it with the adjustable clamp.Next place a 50 milliliter glass jar under the mill outlet. Position the sliding side arm support on the mill slightly off center on the front glass and tighten with the neural bolt. Insert the hopper funnel on top of the mill into the opening of the upper milling chamber.Plug a line cord into a power outlet and press the cord switch to start the mill operation. Feed the sample slowly and add the next batch of film or pellet fragments after the audible noise reduces. After processing the film or pellet fragments press the cord switch to stop the mill operation for approximately 20 minutes to cool down.Clean the cutting chamber with a spatula and bristle brush And collect particles in the glass jar. Remove the 20 mesh 840 micrometer delivery tube and replace it with the 60 mesh delivery tube. Upon completion of the first batch reintroduce the collected material into the mill hopper.Follow the same procedure for the 60 mash milling fraction. Recover the remaining particles in the chamber and add them to the collected main fraction. Prepare a slurry of microplastics.Start by taking di water into a glass beaker and insert a stirring bar. Introduce eight grams of the collected 250 micrometer plastic fraction. Place the glass beaker on a stirring plate and stir magnetically for 24 hours at 400 rotations per minute.To soak the particles in water transfer the particles into a plastic container. Fill in additional two one liter plastic containers with di water, which will be used to rinse off endearing particles on the grinder's hopper. During the grinding process.Place stones with a 46 green size in the wet friction grinder and fasten the center nut. Hand tight with a 17 millimeter wrench add the hopper on top and fasten the four bolts with the five millimeter Allen wrench. Place a one liter plastic collection jar under the outlet of the collider.Place a second empty one liter bucket next to the outlet which will be used for exchanging while processing. Switch the power on and carefully adjust the gauge clearance by turning the adjustment wheel clockwise, corresponding to a positive 0.10 micrometer shift from the zero position until hearing the grinding stones touch. Next, adjust the flexible measurement ring to zero and turn the wheel counterclockwise immediately.By default, the speed is adjusted to 1500 revolutions per minute. Turn the adjustment wheel clockwise until the stones touch and gently fill the water nanoplastic slurry into the hopper. Decrease the gap continually to a clearance gauge of negative 2.0 corresponding to a negative 0.20 micrometer shift from the zero position after the slurry was introduced.Collect the slurry by exchanging the collection buckets. Once the filling level and the bucket exceeds 0.5 liters collect and reintroduce the particles into the grinder between 30 to to 60 times higher. Passes result in smaller particle size.Wash endearing particles on the hopper with the prepared DI water bottle to allow suitable slurry mixing while processing. Recover the slurry and stir for four hours at 400 rotations per minute at 25 degrees Celsius to allow it to mix well let the slurry stand for 48 hours to stabilize. The numerical analysis revealed the bimodal particle size distribution for nanoplastics produced from both feed stocks.The main particle populations for nanoplastics from P B A T pallets were at approximately 79 and 530 nanometers, and corresponding number density frequency values were at 25 and 5%respectively. On the other hand, nanoplastics derived from P B A T foams possessed size maxima at approximately 50 and 106 nanometers with corresponding number density frequency values of 11 and 10%respectively. FTIR R results for P B A T Nanoplastics indicate a distinct decrease in absorbance values between 980 and 1200 centimeter inverse reflecting the starch component leaching during wet grinding.Consistent with previous study observations Anton Astner:For microplastic formation from plastic film and pellets cryogenic pretreatment induces embrittlement to the plastics. It mimics the impact of environmental weathering but not perfectly, which allows accelerated defragmentation. The cryo milling procedure combined with the wet grinding process allows the processing of numerous differently plastic feed stocks to form authentical micro nanoplastics used in environmental studies studies.

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Research

JoVE Journal

Engineering

Micropunching Lithography for Generating Micro- and Submicron-patterns on Polymer Substrates

Conducting polymers have attracted great attention since the discovery of high conductivity in doped polyacetylene in 19771. They offer the advantages of low weight, easy tailoring of properties and a wide spectrum of applications2,3. Due to sensitivity of conducting polymers to environmental conditions (e.g., air, oxygen, moisture, high temperature and chemical solutions), lithographic techniques present significant technical challenges when working with these materials4. For example, current photolithographic methods, such as ultra-violet (UV), are unsuitable for patterning the conducting polymers due to the involvement of wet and/or dry etching processes in these methods. In addition, current micro/nanosystems mainly have a planar form5,6. One layer of structures is built on the top surfaces of another layer of fabricated features. Multiple layers of these structures are stacked together to form numerous devices on a common substrate. The sidewall surfaces of the microstructures have not been used in constructing devices. On the other hand, sidewall patterns could be used, for example, to build 3-D circuits, modify fluidic channels and direct horizontal growth of nanowires and nanotubes.
A macropunching method has been applied in the manufacturing industry to create macropatterns in a sheet metal for over a hundred years. Motivated by this approach, we have developed a micropunching lithography method (MPL) to overcome the obstacles of patterning conducting polymers and generating sidewall patterns. Like the macropunching method, the MPL also includes two operations (Fig. 1): (i) cutting; and (ii) drawing. The "cutting" operation was applied to pattern three conducting polymers4, polypyrrole (PPy), Poly(3,4-ethylenedioxythiophen)-poly(4-styrenesulphonate) (PEDOT) and polyaniline (PANI). It was also employed to create Al microstructures7. The fabricated microstructures of conducting polymers have been used as humidity8, chemical8, and glucose sensors9. Combined microstructures of Al and conducting polymers have been employed to fabricate capacitors and various heterojunctions9,10,11. The "cutting" operation was also applied to generate submicron-patterns, such as 100- and 500-nm-wide PPy lines as well as 100-nm-wide Au wires. The "drawing" operation was employed for two applications: (i) produce Au sidewall patterns on high density polyethylene (HDPE) channels which could be used for building 3D microsystems12,13,14, and (ii) fabricate polydimethylsiloxane (PDMS) micropillars on HDPE substrates to increase the contact angle of the channel15.

A micropunching lithography approach is developed to generate micro- and submicron-patterns on top, sidewall and bottom surfaces of polymer substrates. It overcomes the obstacles of patterning conducting polymers and generating sidewall patterns. This method allows rapid fabrication of multiple features and is free of aggressive chemistry.

Conducting polymers have attracted great attention since the discovery of high conductivity in doped polyacetylene in 19771. They offer the advantages of ...

Formation of Thick Dense Yttrium Iron Garnet Films Using Aerosol Deposition

Aerosol deposition (AD) is a thick-film deposition process that can produce layers up to several hundred micrometers thick with densities greater than 95% of the bulk. The primary advantage of AD is that the deposition takes place entirely at ambient temperature; thereby enabling film growth in material systems with disparate melting temperatures. This report describes in detail the processing steps for preparing the powder and for performing AD using the custom-built system. Representative characterization results are presented from scanning electron microscopy, profilometry, and ferromagnetic resonance for films grown in this system. As a representative overview of the capabilities of the system, focus is given to a sample produced following the described protocol and system setup. Results indicate that this system can successfully deposit 11 &#181;m thick yttrium iron garnet films that are &#160;&#62; 90% of the bulk density during a single 5 min deposition run. A discussion of methods to afford better control of the aerosol and particle selection for improved thickness and roughness variations in the film is provided.

This report describes the use of a custom-built system to perform aerosol deposition of thick films of yttrium iron garnet onto sapphire substrates at RT. The deposited films are characterized using scanning electron microscopy, profilometry, and ferromagnetic resonance to give a representative overview of the capabilities of the technique.

Aerosol deposition (AD) is a thick-film deposition process that can produce layers up to several hundred micrometers thick with densities greater than 95% ...

Characterization of Nanocrystal Size Distribution using Raman Spectroscopy with a Multi-particle Phonon Confinement Model

Analysis of the size distribution of nanocrystals is a critical requirement for the processing and optimization of their size-dependent properties. The common techniques used for the size analysis are transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence spectroscopy (PL). These techniques, however, are not suitable for analyzing the nanocrystal size distribution in a fast, non-destructive and a reliable manner at the same time. Our aim in this work is to demonstrate that size distribution of semiconductor nanocrystals that are subject to size-dependent phonon confinement effects, can be quantitatively estimated in a non-destructive, fast and reliable manner using Raman spectroscopy. Moreover, mixed size distributions can be separately probed, and their respective volumetric ratios can be estimated using this technique. In order to analyze the size distribution, we have formulized an analytical expression of one-particle PCM and projected it onto a generic distribution function that will represent the size distribution of analyzed nanocrystal. As a model experiment, we have analyzed the size distribution of free-standing silicon nanocrystals (Si-NCs) with multi-modal size distributions. The estimated size distributions are in excellent agreement with TEM and PL results, revealing the reliability of our model.

We demonstrate how to determine the size distribution of semiconductor nanocrystals in a quantitative manner using Raman spectroscopy employing an analytically defined multi-particle phonon confinement model. Results obtained are in excellent agreement with the other size analysis techniques like transmission electron microscopy and photoluminescence spectroscopy.

Analysis of the size distribution of nanocrystals is a critical requirement for the processing and optimization of their size-dependent properties. The ...

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobalt metals.

Because of the importance and extensive use of palladium, gold and cobalt metals in high-technology equipment, their recovery and recycling constitute an important industrial challenge. The metal recovery system described herein is a simple, low-cost means for the effective detection, removal, and recovery of these metals from the urban mine.

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in ...

Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films

Solution-based electrospray film deposition, which is compatible with continuous, roll-to-roll processing, is applied to chalcogenide glasses. Two chalcogenide compositions are demonstrated: Ge23Sb7S70 and As40S60, which have both been studied extensively for planar mid-infrared (mid-IR) microphotonic devices. In this approach, uniform thickness films are fabricated through the use of computer numerical controlled (CNC) motion. Chalcogenide glass (ChG) is written over the substrate by a single nozzle along a serpentine path. Films were subjected to a series of heat treatments between 100 &#176;C and 200 &#176;C under vacuum to drive off residual solvent and densify the films. Based on transmission Fourier transform infrared (FTIR) spectroscopy and surface roughness measurements, both compositions were found to be suitable for the fabrication of planar devices operating in the mid-IR region. Residual solvent removal was found to be much quicker for the As40S60 film as compared to Ge23Sb7S70. Based on the advantages of electrospray, direct printing of a gradient refractive index (GRIN) mid-IR transparent coating is envisioned, given the difference in refractive index of the two compositions in this study.

Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films

A method of uniform thickness solution-derived chalcogenide glass film deposition is demonstrated using computer numerical controlled motion of a single-nozzle electrospray.

Solution-based electrospray film deposition, which is compatible with continuous, roll-to-roll processing, is applied to chalcogenide glasses. Two ...

Measuring Spray Droplet Size from Agricultural Nozzles Using Laser Diffraction

When making an application of any crop protection material such as an herbicide or pesticide, the applicator uses a variety of skills and information to make an application so that the material reaches the target site (i.e., plant). Information critical in this process is the droplet size that a particular spray nozzle, spray pressure, and spray solution combination generates, as droplet size greatly influences product efficacy and how the spray moves through the environment. Researchers and product manufacturers commonly use laser diffraction equipment to measure the spray droplet size in laboratory wind tunnels. The work presented here describes methods used in making spray droplet size measurements with laser diffraction equipment for both ground and aerial application scenarios that can be used to ensure inter- and intra-laboratory precision while minimizing sampling bias associated with laser diffraction systems. Maintaining critical measurement distances and concurrent airflow throughout the testing process is key to this precision. Real time data quality analysis is also critical to preventing excess variation in the data or extraneous inclusion of erroneous data. Some limitations of this method include atypical spray nozzles, spray solutions or application conditions that result in spray streams that do not fully atomize within the measurement distances discussed. Successful adaption of this method can provide a highly efficient method for evaluation of the performance of agrochemical spray application nozzles under a variety of operational settings. Also discussed are potential experimental design considerations that can be included to enhance functionality of the data collected.

We present protocols to be used in the measurement of spray droplet size from agricultural nozzles used in both aerial and ground based agrochemical applications. These methods presented were developed to provide consistent and repeatable droplet size data both inter- and intra-laboratory, when using laser diffraction systems.

When making an application of any crop protection material such as an herbicide or pesticide, the applicator uses a variety of skills and information to ...

Fabrication of Polymer Microspheres for Optical Resonator and Laser Applications

This paper describes three methods of preparing fluorescent microspheres comprising &#960;-conjugated or non-conjugated polymers: vapor diffusion, interface precipitation, and mini-emulsion. In all methods, well-defined, micrometer-sized spheres are obtained from a self-assembling process in solution. The vapor diffusion method can result in spheres with the highest sphericity and surface smoothness, yet the types of the polymers able to form these spheres are limited. On the other hand, in the mini-emulsion method, microspheres can be made from various types of polymers, even from highly crystalline polymers with coplanar, &#960;-conjugated backbones. The photoluminescent (PL) properties from single isolated microspheres are unusual: the PL is confined inside the spheres, propagates at the circumference of the spheres via the total internal reflection at the polymer/air interface, and self-interferes to show sharp and periodic resonant PL lines. These resonating modes are so-called "whispering gallery modes" (WGMs). This work demonstrates how to measure WGM PL from single isolated spheres using the micro-photoluminescence (&#181;-PL) technique. In this technique, a focused laser beam irradiates a single microsphere, and the luminescence is detected by a spectrometer. A micromanipulation technique is then used to connect the microspheres one by one and to demonstrate the intersphere PL propagation and color conversion from coupled microspheres upon excitation at the perimeter of one sphere and detection of PL from the other microsphere. These techniques, &#181;-PL and micromanipulation, are useful for experiments on micro-optic application using polymer materials.

Protocols for the synthesis of microspheres from polymers, the manipulation of microspheres, and micro-photoluminescence measurements are presented.

This paper describes three methods of preparing fluorescent microspheres comprising &#960;-conjugated or non-conjugated polymers: vapor diffusion, ...

Measurements of Soil Carbon by Neutron-Gamma Analysis in Static and Scanning Modes

The herein described application of the inelastic neutron scattering (INS) method for soil carbon analysis is based on the registration and analysis of gamma rays created when neutrons interact with soil elements. The main parts of the INS system are a pulsed neutron generator, NaI(Tl) gamma detectors, split electronics to separate gamma spectra due to INS and thermo-neutron capture (TNC) processes, and software for gamma spectra acquisition and data processing. This method has several advantages over other methods in that it is a non-destructive in situ method that measures the average carbon content in large soil volumes, is negligibly impacted by local sharp changes in soil carbon, and can be used in stationary or scanning modes. The result of the INS method is the carbon content from a site with a footprint of ~2.5 - 3 m2 in the stationary regime, or the average carbon content of the traversed area in the scanning regime. The measurement range of the current INS system is &#62;1.5 carbon weight % (standard deviation &#177; 0.3 w%) in the upper 10 cm soil layer for a 1 hmeasurement.

Here, we present the protocol for in situ measurement of soil carbon using the neutron-gamma technique for single point measurements (static mode) or field averages (scanning mode). We also describe system construction and elaborate data treatment procedures.

The herein described application of the inelastic neutron scattering (INS) method for soil carbon analysis is based on the registration and analysis of ...

Fabrication of Ultra-thin Color Films with Highly Absorbing Media Using Oblique Angle Deposition

Ultra-thin film structures have been studied extensively for use as optical coatings, but performance and fabrication challenges remain.&#160; We present an advanced method for fabricating ultra-thin color films with improved characteristics. The proposed process addresses several fabrication issues, including large area processing. Specifically, the protocol describes a process for fabricating ultra-thin color films using an electron beam evaporator for oblique angle deposition of germanium (Ge) and gold (Au) on silicon (Si) substrates.&#160; Film porosity produced by the oblique angle deposition induces color changes in the ultra-thin film. The degree of color change depends on factors such as deposition angle and film thickness. Fabricated samples of the ultra-thin color films showed improved color tunability and color purity. In addition, the measured reflectance of the fabricated samples was converted into chromatic values and analyzed in terms of color. Our ultra-thin film fabricating method is expected to be used for various ultra-thin film applications such as flexible color electrodes, thin film solar cells, and optical filters. Also, the process developed here for analyzing the color of the fabricated samples is broadly useful for studying various color structures.

We present a detailed method for fabricating ultra-thin color films with improved characteristics for optical coatings. The oblique angle deposition technique using an electron beam evaporator allows improved color tunability and purity. Fabricated films of Ge and Au on Si substrates were analyzed by reflectance measurements and color information conversion.

Ultra-thin film structures have been studied extensively for use as optical coatings, but performance and fabrication challenges remain.&#160; We present ...

Preparation of Large-area Vertical 2D Crystal Hetero-structures Through the Sulfurization of Transition Metal Films for Device Fabrication

We have demonstrated that through the sulfurization of transition metal films such as molybdenum (Mo) and tungsten (W), large-area and uniform transition metal dichalcogenides (TMDs) MoS2 and WS2 can be prepared on sapphire substrates. By controlling the metal film thicknesses, good layer number controllability, down to a single layer of TMDs, can be obtained using this growth technique. Based on the results obtained from the Mo film sulfurized under the sulfur deficient condition, there are two mechanisms of (a) planar MoS2 growth and (b) Mo oxide segregation observed during the sulfurization procedure. When the background sulfur is sufficient, planar TMD growth is the dominant growth mechanism, which will result in a uniform MoS2 film after the sulfurization procedure. If the background sulfur is deficient, Mo oxide segregation will be the dominant growth mechanism at the initial stage of the sulfurization procedure. In this case, the sample with Mo oxide clusters covered with few-layer MoS2 will be obtained. After sequential Mo deposition/sulfurization and W deposition/sulfurization procedures, vertical WS2/MoS2 hetero-structures are established using this growth technique. Raman peaks corresponding to WS2 and MoS2, respectively, and the identical layer number of the hetero-structure with the summation of individual 2D materials have confirmed the successful establishment of the vertical 2D crystal hetero-structure. After transferring the WS2/MoS2 film onto a SiO2/Si substrate with pre-patterned source/drain electrodes, a bottom-gate transistor is fabricated. Compared with the transistor with only MoS2 channels, the higher drain currents of the device with the WS2/MoS2 hetero-structure have exhibited that with the introduction of 2D crystal hetero-structures, superior device performance can be obtained. The results have revealed the potential of this growth technique for the practical application of 2D crystals.

Through the sulfurization of pre-deposited transition metals, large-area and vertical 2D crystal hetero-structures can be fabricated. The film transferring and device fabrication procedures are also demonstrated in this report.

We have demonstrated that through the sulfurization of transition metal films such as molybdenum (Mo) and tungsten (W), large-area and uniform transition ...