Blade and rod coating of low solid dispersions

Työn aiheena oli tehdä ohut barrierkalvo terä- tai sauvapäällystys menetelmällä. Erilaisissa elintarvikepakkauksissa käytetään hyviä barrier-ominaisuuksia omaavia ohuita päällysteitä. Elintarvikepakkauksen tehtävä on suojata pakattua tuotetta ympäristöltä, mahdollistaa helppo kuljetus ja säilytys sekä antaa tarvittavat tiedot tuotteesta tuotteen käsittelijöille ja loppukäyttäjille. Diplomityön teoriaosuudessa keskityttiin barrierpäällystykseen, eri päällystysmenetelmiin, niiden erityisvaatimuksiin ja ominaisuuksiin. Teoriaosuudessa käsiteltiin myös vaadittavia barrier-ominaisuuksia ja haasteita niiden saavuttamisessa. Kirjallisuuden perusteella haasteiksi nousivat helposti muodostuvat mikroreiät. Kokeellinen osa jakautui kahteen osakokonaisuuteen: laboratoriokokeisiin ja pilot-koeajoon. Laboratoriokokeita tehtiin ennen pilot-ajoa, jotta pilot-koeajoon voitiin valita parhaat päällystereseptit. Pilot-koeajonäytteiden päällystemäärät osoittautuivat liian pieniksi ja siksi laboratoriossa tehtiin jatkotutkimuksia riittävän päällystemäärän saavuttamiseksi. Tämän työnperusteella pohjakartongin ominaisuuksilla, erityisesti karheudella, on merkittävä vaikutus päällystyksen onnistumisessa ja yksinkertaisilla resepteillä ja päällystysmenetelmillä ei saada tarpeeksi laadukasta kalvoa.

Toimitusketjun hallinnan erityispiirteet elintarvikepakkausalalla: lainsäädännön ja keskeisten standardien rooli

Tutkimuksen tavoitteena on kuvata elintarvikepakkausalan keskeisen lainsäädännön ja laadunhallintastandardien vaikutusta elintarvikepakkausalan toimitusketjujen hallinnassa. Tutkielmassa sovelletaan kvalitatiivista analyysitapaa ja tutkimus aineistona on kirjallinen materiaali sekä teemahaastattelu.Tutkielman teoreettinen viitekehys rakentuu toimitusketjun hallinnan ympärille. Tutkielmassa kartoitetaan elintarvikepakkausvalmistajiin sovellettavan kontaktimateriaalilainsäädännön ja ISO 9001 laadunhallintastandardin keskeiset vaatimukset, ja tarkastellaan niiden roolia elintarvikepakkausalan toimitusketjun hallinnan välineenä. Tutkimuksen johtopäätöksenä voidaan todeta, että vaikka sekä kontaktimateriaalilainsäädäntö että vapaaehtoiset laadunhallintastandardit tukevat elintarvikepakkausalan toimitusketjujen hallintaa, on niiden vaikuttavuus ja toimitusketjun koordinaation ja integraation kehittäminen pitkälti riippuvainen siitä, kuinka sitoutuneita toimitusketjuun kuuluvat yritykset ovat kehittämään toimi-tusketjun liiketoimintaprosesseja ja johtamiskäytäntöjä.

Development and characterization of thin printed films for gas sensing applications

The monitoring and control of hydrogen sulfide (H2S) level is of great interest for a wide range of application areas including food quality control, defense and antiterrorist applications and air quality monitoring e.g. in mines. H2S is a very poisonous and flammable gas. Exposure to low concentrations of H2S can result in eye irritation, a sore throat and cough, shortness of breath, and fluid retention in the lungs. These symptoms usually disappear in a few weeks. Long-term, low-level exposure may result in fatigue, loss of appetite, headache, irritability, poor memory, and dizziness. Higher concentrations of 700 - 800 ppm tend to be fatal. H2S has a characteristic smell of rotten egg. However, because of temporary paralysis of olfactory nerves, the smelling capability at concentrations higher than 100 ppm is severely compromised. In addition, volatile H2S is one of the main products during the spoilage of poultry meat in anaerobic conditions. Currently, no commercial H2S sensor is available which can operate under anaerobic conditions and can be easily integrated in the food packaging. This thesis presents a step-wise progress in the development of printed H2S gas sensors. Efforts were made in the formulation, characterization and optimization of functional printable inks and coating pastes based on composites of a polymer and a metal salt as well as a composite of a metal salt and an organic acid. Different processing techniques including inkjet printing, flexographic printing, screen printing and spray coating were utilized in the fabrication of H2S sensors. The dispersions were characterized by measuring turbidity, surface tension, viscosity and particle size. The sensing films were characterized using X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and an electrical multimeter. Thin and thick printed or coated films were developed for gas sensing applications with the aim of monitoring the H2S concentrations in real life applications. Initially, a H2S gas sensor based on a composite of polyaniline and metal salt was developed. Both aqueous and solvent-based dispersions were developed and characterized. These dispersions were then utilized in the fabrication of roll-to-roll printed H2S gas sensors. However, the humidity background, long term instability and comparatively lower detection limit made these sensors less favourable for real practical applications. To overcome these problems, copper acetate based sensors were developed for H2S gas sensing. Stable inks with excellent printability were developed by tuning the surface tension, viscosity and particle size. This enabled the formation of inkjet-printed high quality copper acetate films with excellent sensitivity towards H2S. Furthermore, these sensors showed negligible humidity effects and improved selectivity, response time, lower limit of detection and coefficient of variation. The lower limit of detection of copper acetate based sensors was further improved to sub-ppm level by incorporation of catalytic gold nano-particles and subsequent plasma treatment of the sensing film. These sensors were further integrated in an inexpensive wirelessly readable RLC-circuit (where R is resistor, L is inductor and C is capacitor). The performance of these sensors towards biogenic H2S produced during the spoilage of poultry meat in the modified atmosphere package was also demonstrated in this thesis. This serves as a proof of concept that these sensors can be utilized in real life applications.

Functionalisation of spruce O-acetyl-galactoglucomannans for barrier and composite applications

The increasing use of energy, food, and materials by the growing population in the world is leading to the situation where alternative solutions from renewable carbon resources are sought after. The growing use of plastics depends on the raw-oil production while oil refining are politically governed and required for the polymer manufacturing is not sustainable in terms of carbon footprint. The amount of packaging is also increasing. Packaging is not only utilising cardboard and paper, but also plastics. The synthetic petroleum-derived plastics and inner-coatings in food packaging can be substituted with polymeric material from the renewable resources. The trees in Finnish forests constitute a huge resource, which ought to be utilised more effectively than it is today. One underutilised component of the forests is the wood-derived hemicelluloses, although Spruce Oacetyl-galactoglucomannans (GGMs) have previously shown high potential for material applications and can be recovered in large scale. Hemicelluloses are hydrophilic in their native state, which restrains the use of them for food packaging as non-dry item. To cope with this challenge, we intended to make GGMs more hydrophobic or amphiphilic by chemical grafting and consequently with the focus of using them for barrier applications. Methods of esterification with anhydrides and cationic etherification with a trimethyl ammonium moiety were established. A method of controlled synthesis to obtain the desired properties by the means of altering temperature, reaction time, the quantity of the reagent, and even the solvent for purification of the products was developed. Numerous analytical tools, such as NMR, FTIR, SEC-MALLS/RI, MALDI-TOF-MS, RP-HPLC and polyelectrolyte titration were used to evaluate the products from different perspectives and to acquire parallel proofs of their chemical structure. Modified GGMs with different degree of substitution and the correlating level of hydrophobicity was applied as coatings on cartonboard and on nanofibrillated cellulose-GGM films to exhibit barrier functionality. The water dispersibility in processing was maintained with GGM esters with low DS. The use of chemically functionalised GGM was evaluated for the use as barriers against water, oxygen and grease for the food packaging purposes. The results show undoubtedly that GGM derivatives exhibit high potential to function as a barrier material in food packaging.

Effect of incorporation of nutraceutical capsule waste of safflower oil in the mechanical characteristics of corn starch films

Abstract Biodegradable films blends made of safflower oil nutraceutical capsules waste corn starch (20:4, 30:4, 40:4 and 50:4) were prepared. The objective of this study was to evaluate the influence of addition of different concentrations of safflower oil nutraceutical capsule waste in the mechanical properties (tensile strength, elongation at break, Young’s modulus) and thickness of corn starch films. A decrease in tensile strength and Young’s modulus and an increase in elongation at break were observed with the increase in the content of the nutraceutical capsule waste. The results showed that the blends of safflower oil capsules waste-corn starch films demonstrated promising characteristics to form biodegradable films with different mechanical characteristics.

Factors Affecting Runnability of Press Forming Equipment

The growth of the food packaging industry has raised more interest in bio-based fibre packing. The use of petroleum based packages is unfriendly to the environment while bio-based is a sustainable option for food packing. In this Master Thesis the aim was to discover how the press forming machineries runnability is affected by parameters of the press and how it also affects formability of paperboard trays. Familiarisation of the working operation parameters was done with the KAMA ST 75 flat-bed die cutting machine and the VP3-70 mould press. Some small test runs of moulding trays where done to get acquainted to the adjustment parameters of the machines. Literature study was done on how paperboards physical properties react to the forces applied during press forming. The study of what kind of defects to the paperboard tray might occur during forming process and the causes for these defects. Also how the parameters of the press forming machine affects formability of the tray. Maintenance procedures was done to the press forming machine to enhance the reliably of production process. Tool alignment measurement was done to determine proper alignment. Laboratory test of the physical properties of the test material was done to find any connection to how the test material performs in press forming. An evaluation criterion was made to evaluate the dimensions and defects of the tray. From the test result a conclusion can be drawn on how the parameters of the press forming process affect the paperboard material. Based on the results the adjustment the parameters of moulding machines to the mechanical properties of paperboard it is possible to produce high quality fibre passed trays for the food packaging industry.

Leak-proof Heat Sealing of Press-Formed Paperboard Trays

Three-dimensional (3D) forming of paperboard and heat sealing of lidding films to trays manufactured by the press forming process are investigated in this thesis. The aim of the work was to investigate and recognize the factors affecting the quality of heat sealing and the leak resistance (tightness) of press-formed, polymer-coated paperboard trays heatsealed with a multi-layer polymer based lidding film. One target was to achieve a solution that can be used in food packaging using modified atmosphere packaging (MAP). The main challenge in acquiring adequate tightness properties for the use of MAP is creases in the sealing area of the paperboard trays which can act as capillary tubes and prevent leak-proof sealing. Several experiments were made to investigate the effect of different factors and process parameters in the forming and sealing processes. Also different methods of analysis, such as microscopic analysis and 3D-profilometry were used to investigate the structure of the creases in the sealing area, and to analyse the surface characteristics of the tray flange of the formed trays to define quality that can be sealed with satisfactory tightness for the use of MAP. The main factors and parameters that had an effect on the result of leak-proof sealing and must be adjusted accordingly were the tray geometry and dimensions, blank holding force in press forming, surface roughness of the sealing area, the geometry and depth of the creases, and the sealing pressure. The results show that the quality of press-formed, polymer-coated paperboard trays and multi-layer polymer lidding films can be satisfactory for the use of modified atmosphere packaging in food solutions. Suitable tools, materials, and process parameters have to be selected and used during the tray manufacturing process and lid sealing process, however. Utilizing these solutions and results makes it possible for a package that is made mostly from renewable and recyclable sources to be a considerable alternative for packages made completely from oil based polymers, and to achieve a greater market share for fibre-based solutions in food packaging using MAP.

Studies on new processing aids and other compounding ingredients in special purpose rubbers

In the first part of the study we probed the effectiveness of rice bran oil as a multipurpose compounding ingredient for nitrile (NBR) and chloroprene (CR) rubbers. This oil has already been successfully employed in the compounding of NR and SBR in this laboratory.In this context we thought it worthwhile to try this oil in the polar rubbers viz, NBR and CR also. The principle of like dissolves like as applicable to solvents is equally applicable while selecting a plasticiser, elastomer combination. Because of the compatibility considerations polar plasticisers are preferred for polar rubbers like NBR and CR. Although plasticisation is a physical phenomenon and no chemical reaction is involved, the chemical structure of plasticisers determines how much physical attraction there is between the rubber and the plasticiser. In this context it is interesting to note that the various fatty acids present in rice bran oil have a long paraffinic chain, characteristic of waxes, with an acid group at the end of the molecule. The paraffinic end of the molecule contributes lubricating effects and limits compatibility whereas the acid end group contributes some polarity and is also chemically reactive. Because of absorption of acid group on the surface of pigments, these acids will have active pigment wetting characteristics also. These factors justifies the role of rice bran oil as a co-activator and lubricating agent for NBR and CR. In fact in our study we successfully replaced stearic acid as co-activator and aromatic oillDOP as processing aid for CR and NBR with rice bran oil.This part of the study has got special significance in the fact that rubber industry now heavily depends on petroleum industry for process oils. The conventional process oils like aromatic, naphthenic and paraffinic oils are increasingly becoming costlier, as its resources in nature are fast depleting. Moreover aromatic process oils are reported to be carcinogenic because of the presence of higher levels of polycyclic aromatic compounds in these oils.As a result of these factors, a great amount research is going on world over for newer processing aids which are cost effective, nontoxic and performanance wise at par with the conventional ones used in the rubber industry. Trials with vegetable oils in this direction is worth trying.Antioxidants are usually added to the rubber compound to minimise ageing effects from heat, light, oxygen etc. As rice bran oil contains significant amount of tocopherols and oryzanol which are natural antioxidants, we replaced a phenolic antioxidant like styrenated phenol (SP) from the compound recipe of both the rubbers with RBO and ascertained whether this oil could function in the role of antioxidant as well.Preparation and use of epoxidised rice bran oil as plasticiser has already been reported.The crude rice bran oil having an iodine value of 92 was epoxidised in this laboratory using peracetic acid in presence of sulphuric acid as catalyst. The epoxy content of the epoxidised oil was determined volumetrically by treating a known weight of the oil with excess HCI and back titrating the residual HCI with standard alkali solution. The epoxidised oil having an epoxy content of 3.4% was tried in the compounding of NBR and CR as processing aids. And results of these investigations are also included in this chapter. In the second part of the study we tried how RBO/ERBO could perform when used as a processing aid in place of aromatic oil in the compounding of black filled NRCR blends. Elastomers cannot have all the properties required for a particular applications, so it is common practice in rubber industry to blend two elastomers to have desired property for the resulting blend.In this RBO/ERBO was tried as a processing aid for plasticisation, dispersion of fillers, and vulcanisation of black filled NR-CR blends.Aromatic oil was used as a control. The results of our study indicate that these oils could function as a processing aid and when added together with carbon black function as a cure accelerator also.PVC is compatible with nitrile rubber in all proportions, provided NBR has an acrylonitrile content of 25 to 40%. Lower or higher ACN content in NBR makes it incompatible with PVC.PVC is usually blended with NBR at high temperatures. In order to reduce torque during mixing, additional amounts of plasticisers like DOP are added. The plasticiser should be compatible both with PVC and NBR so as to get a homogeneous blend. Epoxidised soyaben oil is reported to have been used in the compounding of PVC as it can perfonn both as an efficient plasticiser and heat stabilizer.At present DOP constitute the largest consumed plasticiser in the PVC compounding. The migration of this plasticiser from food packaging materials made of PVC poses great health hazards as this is harmful to human body. In such a scenario we also thought it worthwhile to see whether DOP could be replaced by rice bran oil in the compounding of NBR-PVC blends Different blends of NBR-PVC were prepared with RBO and were vulcanized using sulphur and conventional accelerators. The various physical and mechanical properties of the vulcanisates were evaluated and compared with those prepared with DOP as the control plasticiser. Epoxidised rice bran oil was also tried as plasticiser for the preparation of NBR-PVC blends. A comparison of the processability and cure characteristics of the different blends prepared with DOP and ERBO showed that ERBO based blends have better processability and lower cure time values. However the elastographic maximum torque values are higher for the DOP based blends. Almost all of the physical properties evaluated are found to be slightly better for the DOP based blends over the ERBO based ones. However a notable feature of the ERBO based blends is the better percentage retention of elongation at break values after ageing over the DOP based blends. The results of these studies using rice bran oil and its epoxidised variety indicated that they could be used as efficient plasticisers in place of DOP and justifies their role as novel, nontoxic, and cheap plasticisers for NBR-PVC blends.

Characterization of safe nanostructured polymeric materials

The addition of small quantities of nanoparticles to conventional and sustainable thermoplastics leads to property enhancements with considerable potential in many areas of applications including food packaging 1, lightweight composites and high performance materials 2. In the case of sustainable polymers 3, the addition of nanoparticles may well sufficiently enhance properties such that the portfolio of possible applications is greatly increased. Most engineered nanoparticles are highly stable and these exist as nanoparticles prior to compounding with the polymer resin. They remain as nanoparticles during the active use of the packaging material as well as in the subsequent waste and recycling streams. It is also possible to construct the nanoparticles within the polymer films during processing from organic compounds selected to present minimal or no potential health hazards 4. In both cases the characterisation of the resultant nanostructured polymers presents a number of challenges. Foremost amongst these are the coupled challenges of the nanoscale of the particles and the low fraction present in the polymer matrix. Very low fractions of nanoparticles are only effective if the dispersion of the particles is good. This continues to be an issue in the process engineering but of course bad dispersion is much easier to see than good dispersion. In this presentation we show the merits of a combined scattering (neutron and x-ray) and microscopy (SEM, TEM, AFM) approach. We explore this methodology using rod like, plate like and spheroidal particles including metallic particles, plate-like and rod-like clay dispersions and nanoscale particles based on carbon such as nanotubes and graphene flakes. We will draw on a range of material systems, many explored in partnership with other members of Napolynet. The value of adding nanoscale particles is that the scale matches the scale of the structure in the polymer matrix. Although this can lead to difficulties in separating the effects in scattering experiments, the result in morphological studies means that both the nanoparticles and the polymer morphology are revealed.

Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 mu m carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 degrees C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE. (C) 2011 Elsevier B.V. All rights reserved.

Konstruktion och design av två glassförpackningar i kartongkvaliteten Frövi Light

This degree project was made in cooperation with AssiDomän Frövi and Charlotte Andersson and the main objectivehas been to create to ice cream pacbges from 250 gsm Frövi Light board. The paekages are intended to be easilyresealable while decreasing in size together with the ice cream. The project also describes the food packaging labelsand symbols currently present in the European common market.Both capsules utilize a separate lid for resealing. One of the paekages (Capsuie A) is indended to be cut along withthe ice cream and thereby decrease in size. The other one (Capsuie B) uses a series of flaps for contracting and expandingwhich enab1es adjusting of the size without cutting the package up.The design for Capsuie A is created both as a series of flavours with a super-hero theme intended for children andwith a colfee flavour for a maturer audience. For Capsule B, a design was created for a sorbet.

Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Optically transparent membrane based on bacterial cellulose/ polycaprolactone

Optically transparent membranes from bacterial cellulose (BC)/polycaprolactone (PCL) have been prepared by impregnation of PCL acetone solution into dried BC membranes. UV-Vis measurements showed an increase on transparency in BC/PCL membrane when compared with pristine BC. The good transparency of the BC/PCL can be related to the presence of BC nanofibers associated with deposit of PCL nano-sized spherulites which are smaller than the wavelength of visible light and practically free of light scattering. XRD results show that cellulose type I structure is preserved inside the BC/PCL membrane, while the mechanical properties suggested indicated that PCL acts as a plasticizer for the BC membrane. The novel BC/PCL membrane could be used for preparation of fully biocompatible flexible display and biodegradable food packaging.

Nanocompósitos com atividade antioxidante de amido de milho/isolado proteico de soro de leite/ óleo essencial de alecrim obtidos por extrusão termoplástica

In order to improve the quality and safety of food, the active packaging emerges as a new technology based on the release of composites beneficial to food products. Thus, biodegradable films incorporated with active substances have the function of acting as a barrier to external elements, protecting the product and increasing its shelf life. They are formulated from proteins, polysaccharides, lipids or from the combination of these compounds. However, there is a need to improve the performance properties of these packages. Nanotechnologies, then, emerges with the study of many nanoparticles as additives to modify the performance of biodegradable polymers. With this, we aimed at developing and active antioxidant film of corn starch blenders and whey protein isolate with rosemary essential oil or microcapsules of rosemary essential oil reinforced with sodium montmorillonite (MMTNa + ) nanoparticles by extrusion. The films were developed and characterized in a first stage for the selection of the best polymeric blender using the following analyses: water vapor permeability (WVP), machanical properties; optical, thermogravimetry (TG), differential scanning calorimetry (DSC), x-ray diffraction (XRD) and scanning electron microscopy (SEM). In the second stage, montmorillonite clay nanoparticles and rosemary essential oil were added as reinforcement to evaluate its antioxidant effect. In a third stage, we studied the addition of microcapsules of rosemary essential oil (MR) as a form of protecting the active agent and its antioxidant potential in the films. The results indicate that the development of p olymeric blender with 30% of corn starch substitution is the most indicated for future work. The addition of rosemary essential oil or microcapsule of rosemary essential oil allowed for the obtaining of nanocomposites with antioxidant potential for application in food packages.

Desenvolvimento e validação de método analítico para determinação de caprolactama em simulantes de alimentos: estudo de migração e efeito da irradiação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)