Roll-to-roll atomic layer deposition process for flexible electronics applications

Atomic Layer Deposition (ALD) is the technology of choice where very thin and highquality films are required. Its advantage is its ability to deposit dense and pinhole-free coatings in a controllable manner. It has already shown promising results in a range of applications, e.g. diffusion barrier coatings for OLED displays, surface passivation layers for solar panels. Spatial Atomic Layer Deposition (SALD) is a concept that allows a dramatic increase in ALD throughput. During the SALD process, the substrate moves between spatially separated zones filled with the respective precursor gases and reagents in such a manner that the exposure sequence replicates the conventional ALD cycle. The present work describes the development of a high-throughput ALD process. Preliminary process studies were made using an SALD reactor designed especially for this purpose. The basic properties of the ALD process were demonstrated using the wellstudied Al2O3 trimethyl aluminium (TMA)+H2O process. It was shown that the SALD reactor is able to deposit uniform films in true ALD mode. The ALD nature of the process was proven by demonstrating self-limiting behaviour and linear film growth. The process behaviour and properties of synthesized films were in good agreement with previous ALD studies. Issues related to anomalous deposition at low temperatures were addressed as well. The quality of the coatings was demonstrated by applying 20 nm of the Al2O3 on to polymer substrate and measuring its moisture barrier properties. The results of tests confirmed the superior properties of the coatings and their suitability for flexible electronics encapsulation. Successful results led to the development of a pilot scale roll-to-roll coating system. It was demonstrated that the system is able to deposit superior quality films with a water transmission rate of 5x10-6 g/m2day at a web speed of 0.25 m/min. That is equivalent to a production rate of 180 m2/day and can be potentially increased by using wider webs. State-of-art film quality, high production rates and repeatable results make SALD the technology of choice for manufacturing ultra-high barrier coatings for flexible electronics.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.

Effects of internationalization on packaging decisions of manufacturing companies

The world has witnessed a great deal of globalization and a rise in international activities in recent years compared to decades ago. This has contributed to an upsurge in competition among manufacturing firms resulting in the use of different marketing strategies to survive. Packaging is one of the tools that has been used by marketers to make products different and appealing to both local and international customers. The purpose of this research work was to investigate more on packaging as a marketing tool and how internationalization affects the decisions management makes in relation to it. To this effect, a qualitative research was conducted using five manufacturing companies as case studies and data collected through semi-structured interviews and also personal observation. Secondary sources were also used in order to get deeper insight into the case companies under study. The study revealed that there are many advantages that internationalization provides firms. The general revelations made by the firms that were researched did not point to a negative impact of internationalization on their packaging decisions. Internationalization has provided positive improvements on their packaging and made them more competitive. This proves that for packaging decisions to improve better, one key enabler will be exposure to the international environment since it provides a wider array of options for package improvements for firms.

Paper- and membrane-based ion-modulated electronics

Avhandlingen handlar om pappers- och membranbaserad jonmodulerad elektronik. Målet med forskningen har varit att utveckla billig, miljövänlig och brännbar elektronik, som kan användas i vardagliga engångsprodukter. Baskomponenterna som utvecklas och presenteras i avhandlingen är transistorer och kondensatorer. Mer komplicerad logisk kretselektronik demonstreras också med hjälp av dessa komponenter. Substraten som utnyttjas vid framställningen av dessa elektroniska komponenter är papper och membran. Dessa substrat är flexibla, hållbara, billiga, miljövänliga, etc. och därför väl anpassade för befintliga tryckteknologier. Själva baskomponenterna framställs sedan på dessa substrat genom att trycka flera skikt på varandra, där varje enskilt skikt är ett individuellt material. Detta är möjligt eftersom de organiska materialen som används i dessa komponenter är upplösta i ett lösningsmedel och kan därmed tryckas på samma sätt som ett vanligt bläck. Ett tredimensionellt objekt kan på detta sätt framställas. I avhandlingen presenteras flera olika typer av transistorer, men den gemensamma nämnaren bland dessa är att isolatorn är en jonledare. Denna, ganska ovanliga, transistormodellen har den stora fördelen att lågspänningskomponenter kan relativt enkelt framställas. Det som är speciellt med våra transistorer är att vi har använt miljövänliga jonledare. Detta, bl.a., leder till att våra komponenter visar både god prestanda, tillika som de är miljövänliga. I avhandlingen demonstrerar vi även tryckta superkondensatorer, en motsvarighet till laddningsbara batterier, konstruerade på papper med aktiverat kol och miljövänliga jonledare. De mest komplicerade logiska kretsar som demonstreras i denna avhandling är ring-oscillatorer och 1-bits-minnen konstruerade på papper. --------------------------------------------- Väitöskirja käsittelee paperille ja polymeerikalvolle tulostettua ionimoduloitua elektroniikkaa. Tutkimuksen tavoitteena oli kehittää edullista, ympäristöystävällistä ja polttokelpoista elektroniikkaa, jota voidaan käyttää esim. tavanomaisissa kertakäyttötuotteissa. Väitöskirjassa esitellään erilaisia transistoreita ja kondensaattoreita. Näitä elektronisia peruskomponentteja käyttäen demonstroidaan myös monimutkaisempia loogisia piirejä. Komponenttien valmistuksessa alustana käytettiin paperia ja polymeerikalvoa. Valitut alustat ovat joustavia ja kestäviä, ja ovat siksi hyvin yhteensopivia olemassa olevien tulostusmenetelmien kanssa. Peruskomponentit valmistettiin tulostamalla eri materiaaleja päällekkäin. Komponenteissa käytettävät orgaaniset aineet ovat liuenneessa muodossa musteessa, joka voidaan tulostaa samalla periaatteella kuin mikä tahansa normaali muste. Tällä menetelmällä voidaan valmistaa myös kolmiulotteisia tuotteita. Väitöskirjassa esitellään useita erityyppisiä transistoreita, joissa yhdistävänä tekijänä on ionisesti johtava eriste. Tällaista suhteellisen harvinaista transistorityyppiä käyttämällä voidaan mahdollistaa matala-jännitteisten komponenttien yksinkertainen valmistus. Valmistettujen transistoreiden etu on ionisten nesteiden ympäristöystävällisyys. Elektroniset komponentit ovat täten hyviä suorituskyvyltään, mutteivät haitallisia ympäristölle. Väitöskirjassa demonstroidaan myös tulostettujen superkondensaattoreiden, eli ladattavien paristojen vastineiden, valmistus paperille aktiivihiiltä ja ionisia nesteitä käyttäen. Kaikkein monimutkaisimmat loogiset piirit, jotka tässä väitöskirjassa esitellään, ovat rengasoskillaattorit sekä 1-bittinen paperille valmistettu muisti.

Identification of fatty foods with contamination possibilities by plasticizers when stored in PVC film packaging

Poly-(vinyl chloride) (PVC) requires the addition of plasticizers - additives that give flexibility and malleability for its processing into flexible film. The most used ones are: di-(2-ethylhexyl) adipate (DEHA) and di-(2-ethylhexyl) phthalate (DEHP). Toxic effects of DEHP have been observed by several authors. Phthalates are being replaced by alternative substances in PVC flexible products, because of their possible toxicological effects. DEHA is a substitute for phthalates widely used as a plasticizer in PVC materials for involving food. Some authors have shown that the exposure to DEHA also induces toxicity. A cross-sectional study was performed to identify which fatty foods carry the possibility of contamination by DEHP and DEHA. Eighteen different foods with at least 3% (m/m) fat and the possibility of being wrapped in plastic film were determined. This study suggested that all foods were subject to contamination by DEHP and DEHA in those conditions - in decreasing consumption order of 96 to 22% in the convenience sample. New guidelines on the limits of DEHA and DEHP established by the Brazilian legislation, as additives in PVC film for packaging fatty food, are still relevant to ensure human health.

Guava Jam packaging determinant attributes in consumer buying decision

Using packaging and labels to lure consumers and to communicate product benefits directly on the shelf is a competitive advantage factor in the food industry sector. The label is especially effective since besides supplying basic details, such as weight, ingredients, and instructions in compliance with governmental regulations, it attracts consumers' attention and the desire to buy and which often becomes synonymous to the brand name. The objective of this study was to obtain detailed information on consumers' attitudes, opinions, behavior, and concepts regarding guava jam packaging using the focus group technique. The results showed that label color and design, packaging type and information, and brand name and price are determinant attributes in the consumers' decision to buy guava jam.

Influence of packaging and potassium sorbate on the physical, physicochemical and microbiological alterations of guava preserves

The elaboration of preserves through fruit processing is a promising alternative for their conservation. Such processing provides pleasant flavor due to the increase of sweetness and allows good conservation of the product for a prolonged time. Seeking quality and higher durability of fruit preserves, the purpose of this work was to evaluate the interference of potassium sorbate addition, and polypropylene, metallic and cellophane film packaging on the quality of guava (Psidium guajava L.) preserves during storage, through the physical, physiochemical and microbiological characteristics. The physical, physiochemical and microbiological analyses showed that the different types of packaging did not interfere in the stability of the guava preserves until the 5th month of storage - time being the factor that most influences the quality of the preserves when stored under temperature and humidity of 19.6 °C and 76.2%, respectively. The potassium sorbate caused an increase of the soluble solid levels and a decrease of the water activity. Regardless of the treatment, the preserves remained microbiologically stable during storage.

Oxidative stability of cereal bars made with fruit peels and baru nuts packaged in different types of packaging

Food industries have been concerned about managing the waste generated by their production processes in order to minimize environmental impacts and also about the development of formulations with different and innovative ingredients such as fruits from the Brazilian savanna. Seeking to meet the expectations of consumers who desire healthy and practical products, this study aimed to evaluate the oxidative stability and the variations in chemical composition and antioxidant potential of cereal bars made with fruit peels and baru nuts packaged in different types of packaging. The bars formulated were packed in four different types of packaging: laminated without vacuum (LWV), transparent without vacuum (TWV), transparent under vacuum (TV), and laminated under vacuum (LV); they were subsequently analyzed for proximate composition, fatty acid profiles, antioxidant activity, and oxidative capacity. The results showed that the cereal bars made with fruit peel and baru are sources of protein, dietary fiber, and fat, especially unsaturated fatty acids such as oleic and linoleic acids. The cereal bars exhibited oxidative stability up to 120 days of storage, and the type of packaging was not significant for the variables evaluated; therefore, they can be stored in low cost packaging such as transparent packaging without vacuum for a period of 120 days.

Effect of an edible crosslinked coating and two types of packaging on antioxidant capacity of castilla blackberries

In order to increase the shelf life and maintain the quality and stability of the biological compounds with antioxidant activity present in Castilla blackberry fruits, a sodium alginate-based edible crosslinked coating was applied, and the fruits were packed in two different plastic containers and stored under refrigeration (3 ± 1 °C). Total antioxidant capacity and its relationship to physicochemical variables such as pH, Brix, and acidity were evaluated in six treatments: uncoated blackberry stored in a macroperforated container (T1) and thermosealed container (T2), without crosslinked coating in a macroperforated container (T3) and thermosealed container (T4), with crosslinked coating (calcium ions) packed in macroperforated container (T5) and thermosealed container (T6). The results indicated that factors such as gas permeability in the coatings, the packaging used, and physicochemical parameters significantly affected the fruit total antioxidant capacity, with the highest level in T1 (0.22 µgEAA/ml) at the end of the essay, which is related to the lowest levels of pH and direct exposure to air. On the other hand, the lowest value was obtained in T6 (0.16 µgEAA/ml) due to the crosslinked coating, packaging in the thermosealed container, and higher pH value. Variations in acidity, Brix, and pH indicate the presence of degenerative processes in the crosslinked coating treatments, which limited the physicochemical changes.

Effects of different packaging techniques on the microbiological and physicochemical properties of coated pumpkin slices

Abstract In this study the effects of zein film coating along with benzoic acid on the quality of sliced pumpkin samples, which were packaged with different techniques were investigated. The samples were allocated into different groups and were treated with different processes. Following processing, the samples were stored at +4 °C for twenty days. Physicochemical and microbiological analyses were carried out on the samples once every five days during the storage period. According to color analysis, the L* value was observed to have significantly decreased in the processed and packaged samples in comparison with the control group. Besides, a* and b* values increased in all groups. It was determined that zein film alone did not exhibit the expected effectiveness against moisture loss in the samples. According to the results of microbiological analysis, a final decrease at approximately 1.00 log level was determined in total count of mesophilic aerobic bacteria (TMAB) in the group which was vacuum packaged in PVDC with zein coating when compared with the initial TMAB. Furthermore, no molding occurred in zein-coated group on the last day of the storage period, while massive mold growth was noted in the group which was packaged without any pretreatment procedure.