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At least 19 records

Experimental investigation of defect-assisted and intrinsic water vapor permeation through ultrabarrier films

In the development of ultrabarrier films for packaging electronics, the effective water vapor transmission rate is a combination of permeation through pinhole defects and the intrinsic permeation through the actual barrier film. While it is possible to measure the effective permeation rate through barriers, it is important to develop a better understanding of the contribution from defects to the overall effective barrier performance. Here, we demonstrate a method to investigate independently defect-assisted permeation and intrinsic permeation rates by observing the degradation of a calcium layer encapsulated with a hybrid barrier film, that is, prepared using atomic layer deposition (ALD) and plasma enhanced deposition (PECVD). The results are rationalized using an analytical diffusion model to calculate the permeation rate as a function of spatial position within the barrier. It was observed that a barrier film consisting of a PECVD SiN{sub x} layer combined with an ALD Al{sub 2}O{sub 3}/HfO{sub x} nanolaminate resulted in a defect-assisted water vapor transmission rate (WVTR) of 4.84 × 10{sup −5} g/m{sup 2} day and intrinsic WVTR of 1.41 × 10{sup −4} g/m{sup 2} day at 50 °C/85% RH. Due to the low defect density of the tested barrier film, the defect-assisted WVTR was found to be three times lower than the intrinsic WVTR, and an effective (or total) WVTR value was 1.89 × 10{sup −4} g/m{sup 2} day. Thus, improvements of the barrier performance should focus on reducing the number of defects while also improving the intrinsic barrier performance of the hybrid layer.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Radio frequency plasma power dependence of the moisture permeation barrier characteristics of Al{sub 2}O{sub 3} films deposited by remote plasma atomic layer deposition

In the present study, we investigated the gas and moisture permeation barrier properties of Al{sub 2}O{sub 3} films deposited on polyethersulfone films (PES) by capacitively coupled plasma (CCP) type Remote Plasma Atomic Layer Deposition (RPALD) at Radio Frequency (RF) plasma powers ranging from 100 W to 400 W in 100 W increments using Trimethylaluminum [TMA, Al(CH{sub 3}){sub 3}] as the Al source and O{sub 2} plasma as the reactant. To study the gas and moisture permeation barrier properties of 100-nm-thick Al{sub 2}O{sub 3} at various plasma powers, the Water Vapor Transmission Rate (WVTR) was measured using an electrical Ca degradation test. WVTR decreased as plasma power increased with WVTR values for 400 W and 100 W of 2.6 × 10{sup −4} gm{sup −2}day{sup −1} and 1.2 × 10{sup −3} gm{sup −2}day{sup −1}, respectively. The trends for life time, Al-O and O-H bond, density, and stoichiometry were similar to that of WVTR with improvement associated with increasing plasma power. Further, among plasma power ranging from 100 W to 400 W, the highest power of 400 W resulted in the best moisture permeation barrier properties. This result was attributed to differences in volume and amount of ion and radical fluxes, to join the ALD process, generated by O{sub 2} plasma as the plasma power changed during ALD process, which was determined using a plasma diagnosis technique called the Floating Harmonic Method (FHM). Plasma diagnosis by FHM revealed an increase in ion flux with increasing plasma power. With respect to the ALD process, our results indicated that higher plasma power generated increased ion and radical flux compared with lower plasma power. Thus, a higher plasma power provides the best gas and moisture permeation barrier properties.

36 MATERIALS SCIENCE↗

Al{sub 2}O{sub 3} multi-density layer structure as a moisture permeation barrier deposited by radio frequency remote plasma atomic layer deposition

Al{sub 2}O{sub 3} films deposited by remote plasma atomic layer deposition have been used for thin film encapsulation of organic light emitting diode. In this study, a multi-density layer structure consisting of two Al{sub 2}O{sub 3} layers with different densities are deposited with different deposition conditions of O{sub 2} plasma reactant time. This structure improves moisture permeation barrier characteristics, as confirmed by a water vapor transmission rate (WVTR) test. The lowest WVTR of the multi-density layer structure was 4.7 × 10{sup −5} gm{sup −2} day{sup −1}, which is one order of magnitude less than WVTR for the reference single-density Al{sub 2}O{sub 3} layer. This improvement is attributed to the location mismatch of paths for atmospheric gases, such as O{sub 2} and H{sub 2}O, in the film due to different densities in the layers. This mechanism is analyzed by high resolution transmission electron microscopy, elastic recoil detection, and angle resolved X-ray photoelectron spectroscopy. These results confirmed that the multi-density layer structure exhibits very good characteristics as an encapsulation layer via location mismatch of paths for H{sub 2}O and O{sub 2} between the two layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evaluation of the Durability of Flexible Barrier Materials

To enable the production of lightweight photovoltaic modules, it is desired to use thin film absorbers on metal substrates in a flexible package. To do this with a polymer based frontsheet, it is estimated that a water vapor transmission rate (WVTR) less than 10-4 g/m2/day must be achieved and maintained through the expected life of the module. Barrier-frontsheet films have been developed at 3M with very low permeation rates and evaluated for their long term durability with respect to WVTR and optical transmittance. After exposure to 2500 h of 10 UV suns at 105 degrees C, one design was found which experienced negligible loss in optical transmission while maintaining a WVTR well below the required 10-4 g/m2/day. Further accelerated tests were conducted at different stress levels. For some less durable designs we were able to obtain degradation acceleration factors suggesting the highest exposure was equal to between 4.4 and 10 y on a roof.

14 SOLAR ENERGY↗

Effect of Varying Filler Concentration on Zinc Oxide Nanoparticle Embedded Chitosan Films as Potential Food Packaging Material

Prevailing scenario of non-biodegradable food packaging materials worldwide was the motivation for this research. More than half of the packaging materials used today are non-biodegradable and lack one or the other feature that keeps it from being an ideal food packaging material. Based on the current need of food grade packaging materials, the present study illustrates the amelioration of the properties of biodegradable chitosan films with the incorporation of zinc oxide (ZnO) nanoparticles in varying concentration. The ZnO nanoparticles (ZnONPs) used as fillers in the chitosan films were synthesized by supersaturation method. They were characterized using UV–visible spectrophotometry, X-ray diffraction and field emission scanning electron microscopy (FE-SEM). The particles were observed to be around 100–200 nm in size. The chitosan films with varying concentration of ZnONPs were synthesized and characterized using Fourier transform infrared spectroscopy and FE-SEM. The films were studied for their thermal stability, water vapor transmission rate (WVTR) and mechanical properties. The thermal stability, as determined by Thermo Gravimetric Analysis and Differential Scanning Calorimetry increased slightly with increasing percentage of embedded ZnONPs while a substantial decrease in WVTR was observed. Mechanical properties also showed improvements with 77% increment in tensile modulus and 67% increment in tensile strength. The antimicrobial activity of the films was also studied on gram positive bacterium Bacillus subtilis (B. subtilis) and gram negative bacterium Escherichia coli (E. coli) by serial dilution method. A twofold and 1.5-fold increment in the antimicrobial activity was observed for B. subtilis and E. coli, respectively, with increased ZnONPs concentration in the films from 0(w/w) to 2%(w/w). Films thus prepared can prove to be of immense potential in the near future for antimicrobial food packaging applications.

36 MATERIALS SCIENCE↗

Water vapor transmission rate measurement for moisture barriers using infrared imaging

Here, in this work, we demonstrate a spatially resolved imaging methodology for water vapor transmission rate (WVTR) testing that relies on quantified infrared characterization at water absorption bands. This technique is validated using a moisture barrier on a polymer substrate via calibration of the infrared image intensity with moisture content in the polymer substrate from images taken at different times. The method is compared to existing state of the art techniques such as membrane permeation measurement with coulometric phosphorous pentoxide sensor and optical calcium film testing. This fast, non-destructive and in-situ method enables defect visualization and shows the WVTR with a sensitivity limit of 5·10 –5 g/m 2 /day.

47 OTHER INSTRUMENTATION↗

Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants

A strategy is developed to enhance the barrier protection of polyethylene oxide (PEO)-metal–organic framework (MOF) composite films against chemical warfare agent simulants. To achieve enhanced protection, an impermeable high-aspect-ratio filler in the form of Laponite RD (LRD) clay platelets was incorporated into a composite PEO film containing MOF UiO-66-NH 2 . The inclusion of the platelets aids in mitigating permeation of inert hydrocarbons (octane) and toxic chemicals (2-chloroethyl ethyl sulfide, 2-CEES) of dimensions/chemistry similar to prominent vesicant threats while still maintaining high water vapor transport rates (WVTR). By utilizing small-angle neutron scattering, small-angle X-ray scattering, and wide-angle X-ray scattering, the LRD platelet alignment of the films was determined, and the structure of the films was correlated with performance as a barrier material. Performance of the membranes against toxic chemical threats was assessed using permeation testing of octane and 2-CEES, a common simulant for the vesicant mustard gas, and breathability of the membranes was assessed using WVTR measurements. To assess their robustness, chemical exposure (in situ diffuse reflectance infrared Fourier transform spectroscopy) and mechanical (tensile strength) measurements were also performed. It was demonstrated that the barrier performance of the film upon inclusion of the LRD platelets exceeds that of other MOF-polymer composites found in the literature and that this approach establishes a new path for improving permselective materials for chemical protection applications.

36 MATERIALS SCIENCE↗

Transparent Metal–Organic Framework/Polymer Mixed Matrix Membranes as Water Vapor Barriers

Preventing the permeation of reactive molecules into electronic devices or photovoltaic modules is of significant concern to ensure their life span and reliability. Our report is focused on the formation of highly functioning barrier films based on nanocrystals (NCs) of a water-scavenging metal-organic framework (MOF) and a hydrophobic cyclic olefin copolymer (COC) to overcome the current limitations. Water vapor transmission rates (WVTR) of the films reveal a 10-fold enhancement in the WVTR compared to the substrate while maintaining outstanding transparency over most of the visible and solar spectrum, a necessary condition for integration with optoelectronic devices.

36 MATERIALS SCIENCE↗

Enhanced Water Vapor Blocking in Transparent Hybrid Polymer–Nanocrystal Films

Highly transparent and effective encapsulating materials have become increasingly important for photovoltaic (PV) modules to prevent water vapor molecules from permeating PV cells. The composite consists of block copolymer (PS- b -P2VP), comprised of hydrophobic and hydrophilic parts, and hygroscopic nanocrystals (Magnesium Oxide, MgO) incorporated to enhance water vapor blocking by both presenting obstacles for mass transport and also scavenging water molecules. Here, the water vapor transmission rate (WVTR) values were reduced ~3000 times, compared to homopolymer (PS), for both polymer and composite samples. Achieving both high transparency and low WVTR, it is expected that the composite materials can function as an excellent water vapor blocking layer for PV modules.

36 MATERIALS SCIENCE↗

Polyhydroxybutyrate laminated trilayer films with enhanced barrier and mechanical properties for active food packaging

Polysaccharides such as starch and chitosan have been explored for sustainable food packaging films. However, their inherent hydrophilicity and brittleness cause poor water vapor barrier performance and limited mechanical properties. To address these issues, starch was first functionalized with acetoacetate groups and subsequently blended with chitosan. Dynamic cross-linking occurred between the acetoacetate groups and the primary amine groups of chitosan, forming vinylogous urethane linkages that reduced the water solubility of the films while preserving high mechanical strength. With 30 wt% of glycerol as a plasticizer, the resulting films showed a tensile strength of up to 24.68 MPa and an elongation at break of up to 83.96%. To improve the barrier properties, poly(3-hydroxybutyrate) (PHB), plasticized with 5-15 wt% epoxidized vegetable oil, was laminated on top of the chitosan/modified starch films, resulting in a significantly reduced water vapor transmission rate (WVTR) of 66%. Additional components, such as food colors like β-carotene were incorporated into this layer to make UV-protective films. A third layer of PHB without active additives was then coated to further reduce WVTR by 99%. Therefore, this multilayer lamination strategy effectively enhanced the barrier and mechanical properties of the polysaccharide-based packaging films.

Active packaging↗

Integration of molecular-layer-deposited aluminum alkoxide interlayers into inorganic nanolaminate barriers for encapsulation of organic electronics with improved stress resistance

Diffusion barrier stacks for the encapsulation of organic electronics made from inorganic nanolaminates of Al{sub 2}O{sub 3} and TiO{sub 2} with aluminum alkoxide interlayers have been deposited by atomic layer deposition (ALD) and molecular layer deposition (MLD). As a part of the MLD process development, the deposition of aluminum alkoxide with low a density of about 1.7 g/cm{sup 3} was verified. The ALD/MLD diffusion barrier stack is meant to be deposited either on a polymer film, creating a flexible barrier substrate, or on top of a device on glass, creating a thin-film encapsulation. In order to measure the water vapor transmission rate (WVTR) through the barrier, the device is replaced by a calcium layer acting as a water sensor in an electrical calcium test. For the barrier stack applied as thin-film encapsulation on glass substrates, high resolution scanning electron microscopy investigations indicate that the inorganic nanolaminates without MLD interlayers are brittle as they crack easily upon the stress induced by the corroding calcium below. The introduction of up to three MLD interlayers of 12 nm each into the 48 nm barrier film laminate successfully mitigates stress issues and prevents the barrier from cracking. Using the three MLD interlayer configurations on glass, WVTRs of as low as 10{sup −5} g/m{sup 2}/d are measured at 38 °C and 32% relative humidity. On polymer barrier substrates, the calcium is evaporated onto the barrier stack and encapsulated with a cavity glass. In this configuration, the corroding calcium has space for expansion and gas release without affecting the underlying barrier film. In consequence, a WVTR of about 3 × 10{sup −3} g/m{sup 2}/d is measured for all samples independently of the number of MLD interlayers. In conclusion, a stabilization and preservation of the ALD barrier film against mechanical stress is achieved by the introduction of MLD interlayers into the inorganic nanolaminate.

36 MATERIALS SCIENCE↗

Moisture ingress in commercial steel drums: Water content determination, diffusion modelling and predicted permeation rates

Commercial steel drums underpin the global economy, playing a pivotal role in the storage and transportation of critical materials. Transported and stored materials, such as food, chemical and nuclear waste, can be sensitive to ambient conditions, particularly moisture that can enhance negative effects such as corrosion and material degradation. Although international standards and regulations are in place for the qualification of steel drums, there are no current testing requirements, established limits or boundaries for the permeation of moisture into the drums during transportation or storage. This work aims to provide insights into the moisture ingress over time into properly sealed steel drums and provides estimated moisture ingress rates over time through extrapolation. Water vapour transmission rate (WVTR) measurements through the gasket material at 10–40°C were 0.11–2.1 g/m 2 /day resulting in a permeation activation energy of 30.2 kJ/mol. Water sorption measurements and Karl Fischer titration (KFT) on ethylene propylene diene monomer (EPDM) gasket material revealed a decrease in equilibrium moisture saturation with increasing temperature. KFT measurements also revealed the presence of moisture within the adhesive and drum wall after exposure to ambient conditions. KFT and Fourier transform infrared spectroscopy (FTIR) show that moisture will desorb from the EPDM and drum wall after exposure to desiccating conditions, although a minimal amount of moisture will remain present. When sealed to the manufacturer's recommendations, the steel drums are effective in minimizing moisture ingress. In conclusion, in sealed empty drums, moisture ingress rates for 19-L drums were 0.4–1.5 mg/day at 25°C 15% relative humidity (RH) and increased to 7.1–8.8 mg/day at 40°C 90% RH, and moisture ingress rates for 210-L drums were 2.5 and 3.5 mg/day at field deployment conditions of 15.5°C 51.5% RH and 23°C 40% RH, respectively.

42 ENGINEERING↗

Enabling Long Term, Shelf‐Stable Perovskite Solar Cells: Alumina Barriers to Protect Perovskite Devices from Moisture and Oxygen

Current encapsulation architectures for thin-film metal halide perovskite do not adequately eliminate all ambient stressors. Here, we develop low transmission rate barrier layers using atomic layer deposited (ALD) aluminum oxide grown directly on the completed photovoltaic (PV) device stack to provide an additional seal, prior to full packaging. We investigate the effect of deposition temperature and oxidant chemistries on the barrier growth for protection of perovskite photovoltaic devices. We characterize the layers individually, then integrate into devices to detail the tradeoff between protection and deposition compatibility. To enhance compatibility and impermeability, we present an approach using water as the aluminum oxidant during nucleation and switching from water to ozone for the remainder of the growth. At 50 nm, the barrier results in a water vapor transmission rate (WVTR) of 4.5·10 −4 g/m 2 /day, and 1,000-hour device stability under 45°C with 85% relative humidity without further packaging. This barrier provides sufficient protection to enable minimal degradation of the perovskite solar cells while completely submerged in water for 140 minutes. Additionally, we characterize the oxygen transmission rate (OTR) to be 0.49 cm 3 /m 2 /day at 23°C and 0% relative humidity, which is 1.5 orders of magnitude improvement over the OTR of the current encapsulation.

14 SOLAR ENERGY↗

Pressure-assisted thermal sterilization of avocado puree in high barrier polymeric packaging

The aim of this study was to examine the influence of pressure-assisted thermal sterilization (PATS) on properties of polymeric packaging and packaged avocado puree. High pressure of 600 MPa and initial vessel temperature of 90 °C were used over 5 min processing time. We used two high barrier film pouches: Film A-(PE/PA6//EVOH//PA6/PE) and film B-(AlO x -coated PET//AlO x -coated PET//PA//CPP). Oxygen transmission rates (OTR) changed from 0.16 ± 0.07 to 3.24 ± 0.52 cm 3 /m 2 .day for film A after processing while OTRs were not detected for film B. Water vapor transmission rates (WVTR) changed from 3.72 ± 0.06 to 4.97 ± 0.14 g/m 2 .day for film A and 0.11 ± 0.02 to 0.62 ± 0.0.6 g/m 2 .day for film B. The dissolved oxygen in packaged avocado puree reduced from 21% to 3% after PATS for both films. Reduced oxygen level in packaged avocado may help extend its shelf life. Dielectric properties and X-ray diffraction helped explain PATS induced changes in film barrier properties. The total chlorophyll, greenness, and lightness decreased significantly (p < 0.05) after PATS. The thiobarbituric acid activity reduced after PATS. PATS showed potential to produced shelf-stable avocado puree; however, shelf-life studies are needed to further develop PATS process.

42 ENGINEERING↗

Minimizing Oxygen Permeability in Chitin/Cellulose Nanomaterial Coatings by Tuning Chitin Deacetylation

The demand for packaging materials with low gas permeabilities is increasing, but commonly used petroleum-derived single-use plastics are not renewable, biodegradable, or easy to recycle. Nanomaterials composed of chitin and cellulose, which are abundant in nature, have high crystallinities and low oxygen permeabilities (OP), providing a viable alternative. In this work, we explore how deacetylation conditions of crab shell chitin can be used to tune the charge and size of resulting chitin nanowhiskers (ChNWs) and the resulting OP of layered film structures. Three deacetylation factors, the concentration of sodium hydroxide (%NaOH), temperature (T), and reaction time, were explored using a three-factor three-level Taguchi design with an orthogonal array. Furthermore, the resulting ChNW suspensions were sequentially spray-coated with suspensions of cellulose nanocrystals (CNCs) onto cellulose acetate (CA) films to form a multilayer structure. We show that ChNWs prepared under more aggressive deacetylation conditions inside the original orthogonal array (higher %NaOH, T, and time) had shorter lengths but the surface charge was significantly influenced only by more aggressive deacetylation outside of the original design conditions. With only ~10% decrease in the ultimate tensile strength and no significant loss in failure strain, the ChNW-CNC coating resulted in ~20% decrease in WVTR in comparison to uncoated CA films. The optimization of process conditions resulted in CA-ChNW-CNC films with a 91-99% decrease in OP (132-16.7 cm 3 ∙μm/m 2 /day/kPa versus 1553 cm3∙μm/m2/day/kPa for uncoated CA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Note: Inhibiting bottleneck corrosion in electrical calcium tests for ultra-barrier measurements

A major failure mechanism is identified in electrical calcium corrosion tests for quality assessment of high-end application moisture barriers. Accelerated calcium corrosion is found at the calcium/electrode junction, leading to an electrical bottleneck. This causes test failure not related to overall calcium loss. The likely cause is a difference in electrochemical potential between the aluminum electrodes and the calcium sensor, resulting in a corrosion element. As a solution, a thin, full-area copper layer is introduced below the calcium, shifting the corrosion element to the calcium/copper junction and inhibiting bottleneck degradation. Using the copper layer improves the level of sensitivity for the water vapor transmission rate (WVTR) by over one order of magnitude. Thin-film encapsulated samples with 20 nm of atomic layer deposited alumina barriers this way exhibit WVTRs of 6 × 10{sup −5} g(H{sub 2}O)/m{sup 2}/d at 38 °C, 90% relative humidity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photocured epoxy/graphene nanocomposites with enhanced water vapor barrier properties

A transparent, water vapor barrier film made of an epoxy resin and graphene oxide (GO) was synthesized by photopolymerization process. The epoxy/GO film with just 0.05 wt% GO gives a 93% WVTR reduction with respect to the pristine polymer, reaching barrier properties better than other polymer composites containing higher amounts of graphene. The excellent water vapor barrier is attributed to the good dispersion of GO in the polymer matrix. Moreover, GO significantly enhances the toughness and the damping capacity of the epoxy resins. The hybrid film can have potential applications in anticorrosive coatings, electronic devices, pharmaceuticals and food packaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flexible Ultra Moisture Barrier Film for Thin-Film Photovoltaic Applications

Flexible Thin-film photovoltaic (TFPV) is a low cost alternative to incumbent c-Si PV products as it requires less volume of costly semiconductor materials and it can potentially reduce installation cost. Among the TFPV options, copper indium gallium diselenide (CIGS) has the highest efficiency and is believed to be one of the most attractive candidates to achieve PV cost reduction. However, CIGS cells are very moisture sensitive and require module water vapor transmission rate (WVTR) of less than 1x10 -4 gram of water per square meter per day (g-H 2 O/m 2 /day). Successful development and commercialization of flexible transparent ultra moisture barrier film is the key to enable flexible CIGS TFPV products, and thus enable ultimate PV cost reduction.

14 SOLAR ENERGY↗