Recycled material produced during three months from packing polyethylene foils coming from three suppliers was analysed together with one recycled material under complaint from the point of melt flow index (MFI), composition and mechanical properties. The addition of linear low density polyethylene (LLDPE) into the recycled material was studied as well. It was measured melt flow index (MFI), Differential scanning calorimetry (DSC) together with Thermogravimetry methods were used to determine composition. Selected materials were pressed to obtain films with the thickness of 1 mm to determine tensile properties. Recycled materials contained 40–65% LLDPE, small amount of polypropylene as well as chalk. The content of LDPE and LLDPE varied within one supplier and thus mechanical properties did. The results showed the difference in quality of PE films separation among all suppliers. The problems with workability of material under complaint were caused by the material composition – the amount of LLDPE predominated. The addition of LLDPE into the recycled material in the range of 5–20 % increased MFI by 13-78%. Mechanical properties of blends rich in LLDPE were similar to those of clear LLDPE. The presence of LDPE influenced more markedly only the strength to break. The blends of LDPE and LLDPE were evaluated as immiscible but with high affinity of the components with increasing contend of LLDPE. No material was chemically degraded. The methods commonly performed in manufacture, especially MFI, are not able to differentiate LDPE form LLDPE – recommended is DSC.

Motiviert durch die in der Literatur bisher unvollständige Beschreibung der Relaxation hochgeladener Ionen vor Festkörperoberflächen, besonders in Bezug auf den Eintrag potenzieller Energie in Oberflächen und der Aufstellung einer vollständigen Energiebilanz, werden in dieser Arbeit komplementäre Studien präsentiert, die sowohl die Ermittlung des Anteils der deponierten potenziellen Energie als auch die Ermittlung der emittierten potenziellen Energie ermöglichen. Zum Einen wird zur Bestimmung des eingetragenen Anteils der potenziellen Energie eine kalorimetrische Messanordnung verwendet, zum Anderen gelingt die Bestimmung der emittierten potenziellen Energie mittels doppeldifferenzieller Elektronenspektroskopie. Für vertiefende Studien werden Materialien unterschiedlicher elektronischer Strukturen (Cu, n-Si, p-Si und SiO2 ) verwendet. Im Falle der Kalorimetrie wird festgestellt, dass die eingetragene potenzielle Energie linear mit der inneren potenziellen Energie der Ionen wächst. Dabei bleibt das Verhältnis zwischen der eingetragenen potenziellen Energie und der inneren potenziellen Energie nahezu konstant bei etwa (80 ± 10) %. Der Vergleich von Cu, n-Si und p-Si zeigt im Rahmen der Messfehler keine signifikanten Unterschiede in diesem Verhältnis. Es liegen jedoch deutlich unter jenem von SiO2. Die Elektronenspektroskopie liefert ein dazu komplementäres Ergebnis. Für Cu und Si konnte ebenfalls eine lineare Abhängigkeit zwischen emittierter Energie und innerer potenzieller Energie festgestellt werden. Das Verhältnis wurde hierfür bis zum Ladungszustand bis Ar7+ zu etwa (10 ± 5) % unabhängig vom Ladungszustand bestimmt. Im Gegensatz dazu liefert SiO2 eine nahezu verschwindende Elektronenausbeute. Für Ar8+ und Ar9+ steigt die Elektronenausbeute wegen der Beiträge der LMM-Augerelektronen für alle untersuchten Materialien leicht an. Der Anteil der emittierten Energie eines Ar9+ -Ions wird für Cu und Si zu etwa 20 % und für SiO2 zu etwa 10 % angegeben. Diese Ergebnisse sind in guter Übereinstimmung mit den Kalorimetrieexperimenten und erfüllen die Energiebilanz. Zusätzlich werden die experimentellen Ergebnisse mit einer Computersimulation modelliert, welche auf dem erweiterten dynamischen klassischen Barrierenmodell basiert. Aus diesen Rechnungen kann zudem jener Anteil der deponierten potenziellen Energie erhalten werden, welcher durch Bildladungsbeschleunigung vor der Oberfläche in kinetische Energie umgewandelt wurde. / Motivated by the incomplete scientific description of the relaxation of highly charged ions in front of solid surfaces and their energy balance, this thesis describes an advanced complementary study of determining deposited fractions and re-emitted fractions of the potential energy of highly charged ions. On one side, a calorimetric measurement setup is used to determine the retained potential energy and on the other side, energy resolved electron spectroscopy is used for measuring the re-emitted energy due to secondary electron emission. In order to study the mechanism of energy retention in detail, materials with different electronic structures are investigated: Cu, n-Si, p-Si and SiO2 . In the case of calorimetry, a linear relationship between the deposited potential energy and the inner potential energy of the ions was determined. The total potential energy which stays in the solid remains almost constant at about (80 ± 10) %. Comparing the results of the Cu, n-Si and p-Si targets, no significant difference could be shown. Therefore we conclude that the difference in energy deposition between copper, n-doped Si and p-doped Si is below 10 %, which is significantly lower than using SiO2 targets. For this purpose, electron spectroscopy provides a complementary result. For Cu and Si surfaces, an almost linear increase of the re-emitted energy with increasing potential energy of the ion up to Ar7+ was also observed. The ratio of the re-emitted energy is about (10 ± 5) % of the total potential energy of the incoming ion, almost independent of the ion charge state. In contrast, an almost vanishing electron emission was observed for SiO2 and for charge states below q=7. For Ar8+ and Ar9+, the electron emission increased due to the contribution of the projectile LMM Auger electrons and the re-emitted energy amounts up to 20 % for Cu and Si and around 10 % for SiO2 .These results are in good agreement with the calorimetric values. In addition, the experimental results are compared with computer simulations based on the extended dynamical over-the-barrier model. From these calculations, the ratio of deposited potential energy that is transformed into kinetic energy before deposition due to the image charge acceleration can be maintained.

Additives, incorporated in film coating formulations, and their process parameters are generally selected using a trial-and-error approach. However, coating problems and defects, especially those associated with aqueous coating systems, indicate the necessity of embracing a quality-by-design approach to identify the optimum coating parameters. In this study, the feasibility of using thermal and rheological measurements to help evaluate and design novel coating formulations has been investigated. Hydroxypropyl methylcellulose acetate succinate (HPMCAS), an enteric coating polymer, was used as the film forming polymer. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and Parallel Plate Shear Rheometery (PPSR) were used to evaluate the effect of different plasticisers on the performance of HPMCAS. The results illustrate that, for identical formulations, the DSC and DMA methods yielded up to 40% differences in glass transition temperature (Tg) values. Moreover, Tg measured using loss modulus signals were always 20-30 oC less than those measured using tan delta results in DMA testing. Absolute and relative Tg values can significantly vary depending on the geometry of the samples, clamp size, temperature ramping rate and the frequency of the oscillations. Complex viscosity data for different formulations demonstrated a variable shear thinning behaviour and a Tg independent ranking. It is, therefore, insufficient to rely purely on Tg values to determine the relative performance of additives. In addition, complex viscosity results, obtained using both the DMA and PPSR techniques at similar temperatures, are shown to be comparable. The results from both techniques were therefore used to produce continuous master curves for the HPMCAS formulations. Additionally, step strain tests showed that HPMCAS chains do not fully III disentangle after 105 seconds as predicted by the Maxwell model. Finally, in situ aqueous-based coating experiments proved that mixtures of triethyl acetyl citrate and acetylated monoglyceride (TEAC/AMG), even without cooling of the suspension, do not cause blocking of the spray nozzle whereas triethyl citrate (TEC) based formulae did. TEAC (alone or in a combination with AMG) exhibits superior wettability to HPMCAS than TEC/AMG formulations and can be used to enhance the efficiency and film quality of the dry coating process.

Control and analysis of protein aggregation is an increasing challenge to biopharmaceutical research and development. Therefore it is important to understand the interactions, causes and analysis of particles in order to control protein aggregation to enable successful biopharmaceutical formulations. This work investigates the role of different non-ionic surfactants on protein conformational stability, as assessed by HSDSC, and on protein size stability as assessed by Dynamic Light Scattering (DLS), HIAC and MFI. BSA and IgG2 were used as model proteins. Thermal unfolding experiments indicated a very weak surfactant-immunoglobulin IgG2 interaction, compared to much stronger interactions for the BSA surfactant systems. The DLS results showed that BSA and IgG2 with different surfactants and concentration produced different levels of particle size growth. The heat treatment and aging of samples in the presence of Tween 20, Tween 80, Brij 35 and Pluronic F-68 surfactants led to an increase in the populations of larger particles for BSA samples, whereas IgG2 systems did not notably aggregate under storage conditions MFI was shown to be more sensitive than HIAC technique for measuring sub-visible particles in protein surfactant systems. Heat treatment and storage stress showed a significant effect on BSA and IgG2 protein sub-visible particle size stability. This work has demonstrated that both proteins with different Tween 20, Tween 80, Brij 35 and Pluronic F-68 concentrations, have different level of conformational and size stability. Also aging samples and heating stress bears the potential to generate particles, but this depends on surfactant type. Poor predictive correlations between the analytical methods were determined.

В настоящей работе объектом исследования является магнитомягкий аморфный сплав системы Fe-Si-Nb-Cu-Mo-B из группы материалов Finemet. Образец выполнен в виде ленты толщиной 20…30 мкм методом быстрой закалки (спиннингованием). Для определения температурных интервалов фазовых и структурных превращений в исходно аморфном сплаве были использованы методы калориметрии, дилатометрии, терморентгеновского фазового анализа. При скоростях нагрева 0,3…0,5 o/сек установлен температурный диапазон существования данного сплава в нанокристаллическом состоянии. / The research object in that work is magnetically soft amorphous Fe-Si-Nb-Cu-Mo-B alloy. That and same alloy systems was named as Finemet material. The sample is an amorphous ribbon, which has thickness of 20…30 μm, it was producing by melt spinning method. The samples were studied using methods of calorimetry, dilatometry and non-ambient x-ray diffraction analysis. The alloy was heat treated. Data about thermal effects, changes in geometric dimensions, changes in the phase composition, and about critical points are obtained. Interval of nanocrystallic state existence for heating rate 0.3…0.5 o/sec was determined.

No description available.

Plastskräp har blivit ett global problem på grund av nedskräpning och otillräcklig avfallshantering. Användning av biologiskt nedbrytbart material kan underlätta problemet, även om det inte är en universallösning. Produkter gjorda av biologiskt nedbrytbart material skall ändå till avfallshantering eftersom nedbrytningen kan vara långvarig och variera mycket beroende av omgivningen. Därmed är användningen av biologiskt nedbrytbart material endast berättigat då det är svårt att samla in materialet eller avskilja det från organiskt material. Studiens mål var att undersöka biologiskt nedbrytbara material som kan användas i produkter som fungerar under många olika driftsförhållanden och inte kan återställas efter användning. I den litterära delen av denna studie definieras nedbrytning genom egenskaper och förhållanden som påverkar nedbrytningsprocessen. Nedbrytning av polyestrar och cellulosa och de standardprocessarna som används i nedbrytningsexperimenten betraktades. Standardprocesserna för nedbrytning studerades för att få en klarare inblick i den eftertraktade nedbrytningsgraden och de standardiserade förhållandena för nedbrytningen i olika miljöer. En sammanfattning av olika nedbrytningsexperiment och analysmetoder är också inkluderade för att försäkra att experimenten som utfördes är både giltiga och jämförbara med andra forskningsresultat inom fältet. I detta forskningsprojekt utfördes nedbrytningsexperiment i färskvatten- och hemkompostmiljöer. Målet med projektet var att bedöma ifall materialen kunde brytas ned i ett brett spektrum av miljöer, ifall de var mindre skadliga för naturen än konventionella material som används av dagens industri och för att uppskatta nedbrytningstakten. Nedbrytningstiden var 140 dagar och experimentet utfördes med 10 olika material: betecknade som A-J. Materialen analyserades 8 gånger under nedbrytningsperioden förutom materialen I och J som analyserades en gång efter 140 dagar. Materialen analyserades mekaniskt, strukturellt och termiskt med hjälp av dragprovning, FTIR och DSC. Provernas viktförändring bestämdes också. Nedbrytning observerades visuellt från provernas yta och genom mekaniska prover. Materialen som placerades i hemkomposten visade klara tecken på nedbrytning då färgen hade förändrats och förstärkningsfibrerna hade blivit synliga. Materialen som placerats i hemkompostmiljö visade också klara tecken på tillväxt av mikroorganismer och biomassa som uppstått på ytan av materialen. Sammanfattningsvist, visade materialen B, C och G de mest lovande resultaten med klara tecken på biologisk nedbrytning och de hade en snabbare nedbrytningstakt än de andra materialen som undersöktes. Material D visade klara tecken på biologisk nedbrytning på ytan men dess nedbrytningstakt var uppskattad att vara mycket långsammare. Därmed rekommenderas det att använda material A, B, D och G istället för konventionella icke biologiskt nedbrytbara material. Dessa material har potential att sänka den negativa inverkan och de långsiktiga riskerna av plastskräp för miljön. / Plastic debris has become a global crisis due to littering and misplaced waste management. The use of biodegradable materials can ease the problem, but it is not always the answer. Products made of biodegradable materials are still to be waste managed since biodegradation can be a long process and is highly dependent on the environment conditions. Hence, the use of biodegradable materials is justified only when retrieving the product after use is impossible or prohibitively expensive or separating it from organic matter is difficult. This study was made to investigate biodegradable materials that can be used in products that are operating in broad range of operational conditions and cannot be retrieved back after use in most cases. In the literature part of this study the biodegradation is defined along with properties and conditions that affect the biodegradation process. Biodegradation of polyesters and cellulose, and standards used in the biodegradation experiments were reviewed. Biodegradation standards were studied in order to have a clearer picture of the pursued degree of biodegradation and standardized properties in the biodegradation experiments. Review of different biodegradation tests and analysis methods are included as well to ensure that the experiments performed in this work are valid and comparable with other biodegradation studies.  In this study, the biodegradation experiment was conducted in freshwater and home compost environments. The aim was to determine if the materials were able to biodegrade in wide range of environments, to make sure they are less harmful than the conventional materials used in the industry and to estimate the rate of biodegradation. The duration of the experiments were 140 days with 10 different materials: A – J. The materials were analyzed 8 times during the aging period, except materials I and J, which were analyzed only once after 140 days. The samples were analyzed mechanically, structurally, and thermally using tensile test, FTIR and DSC measurements, respectively. Also, the samples weight changes were analyzed.  The degradation was visually observed from the surfaces of the samples and from mechanical testing in both experimental environments. Home compost environment showed clear signs of biodegradation where reinforcement fibers became visible and changed the color of some of the samples. Also, home compost samples had microorganisms growing on them, and biomass was developing around them. To conclude, material B, C and G had the most promising results with clear signs of biodegradation and had faster estimated biodegradation rate compared with the other studied materials. Material D had signs of biodegradation on the surface as well. However, the biodegradation rate was estimated to be much slower. In conclusion, it is recommended to use the studied materials A, B, D and G instead of the conventional non-biodegradable polymers. These materials have potential to lower the negative impact and long-term risks of plastic debris to the environment.

No / PURPOSE: To explore hot melt extrusion (HME) as a scalable, solvent-free, continuous technology to design cocrystals in agglomerated form. METHODS: Cocrystal agglomerates of ibuprofen and nicotinamide in 1:1 ratio were produced using HME at different barrel temperature profiles, screw speeds, and screw configurations. Product was characterized for crystallinity by XRPD and DSC, while the morphology was determined by SEM. Dissolution rate and tabletting properties were compared with ibuprofen. RESULTS: Process parameters significantly affected the extent of cocrystallization which improved with temperature, applied shear and residence time. Processing above eutectic point was required for cocrystallization to occur, and it improved with mixing intensity by changing screw configuration. Product was in the form of spherical agglomerates, which showed directly compressible nature with enhanced dissolution rate compared to ibuprofen. This marks an important advantage over the conventional techniques, as it negates the need for further size modification steps. CONCLUSIONS: A single-step, scalable, solvent-free, continuous cocrystallization and agglomeration technology was developed using HME, offering flexibility for tailoring the cocrystal purity. HME being an established technology readily addresses the regulatory demand of quality by design (QbD) and process analytical technology (PAT), offering high potential for pharmaceuticals.

No / PURPOSE: Self-emulsifying systems (SES) emulsify spontaneously to produce fine oil-in-water emulsion when introduced into aqueous phase. The self-emulsification process plays an important role during formation of emulsion. The objective of current work was to understand and explore the inner structuration of SES through controlled hydration and further to study the influence of additive on the same which ultimately governs performance of final formulation in terms of droplet size. METHODS: Droplet size of final formulations containing structural analogues of ibuprofen was determined. Microstructural properties of intermediate hydrated regimes of SES were investigated using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. RESULTS: The current work established inverse relationship between droplet size of the formulations containing structural analogues of ibuprofen and their Log P values. Microstructural analysis of intermediate hydrated regimes of the prepared samples showed formation of local lamellar structure. Structural analogues of ibuprofen significantly altered microstructure of lamellae which was well correlated with the droplet size of final formulations. In vitro drug release study showed increase in dissolution rate of lipophillic drugs when formulated as SES. CONCLUSION: The current work emphasizes the fact that tailor-made formulations can be prepared by controlling the properties of intermediate regimes.

Self-emulsifying systems are mixtures of oils and surfactants, ideally isotropic, sometimes including cosolvents, which emulsify under conditions of gentle agitation, similar to those which would be encountered in the gastrointestinal tract. The process of self-emulsification has remained the center of attraction for most researchers. Controlled hydration of self-emulsifying systems shows formation of an intermediate gel phase which upon rupture forms an emulsion. Current work was undertaken to understand and explore the microstructural properties of intermediate gel phase which are believed to influence the performance (droplet size) of the final formulation. The effect of additives on microstructural properties of intermediate gel phase has also been investigated. Microstructural elucidation of hydrated samples of intermediate regimes was done by using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. Samples from intermediate regimes showed formation of local lamellar structure which swelled with hydration. In the present work, the effect of addition of salt form of naproxen (sodium and potassium) and naproxen (base) on microstructural properties of intermediate regimes was investigated. Systems containing naproxen salts formed larger droplets whereas naproxen base formed smaller ones. Microstructural properties of intermediate lamellar structures were well correlated with performance of the final formulation. The current studies indicate that by controlling the properties of intermediate regimes optimized formulations with desired performance can be tailor-made.