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The use of analytical techniques for the rapid detection of microbial spoilage and adulteration in milkNicolaou-Markide, Nicoletta January 2011 (has links)
Milk is an important nutritious component of our diet consumed by most humans on a daily basis. Microbiological spoilage affects its safe use and consumption, its organoleptic properties and is a major part of its quality control process. European Union legislation and the Hazard Analysis and the Critical Control Point (HACCP) system in the dairy industry are therefore in place to maintain both the safety and the quality of milk production in the dairy industry. A main limitation of currently used methods of milk spoilage detection in the dairy industry is the time-consuming and sometimes laborious turnover of results. Attenuated total reflectance (ATR) and high throughput (HT) Fourier transform infrared (FTIR) spectroscopy metabolic fingerprinting techniques were investigated for their speed and accuracy in the enumeration of viable bacteria in fresh pasteurized cows' milk. Data analysis was performed using principal component-discriminant function analysis (PC-DFA) and partial least squares (PLS) multivariate statistical techniques. Accurate viable microbial loads were rapidly obtained after minimal sample preparation, especially when FTIR was combined with PLS, making it a promising technique for routine use by the dairy industry. FTIR and Raman spectroscopies in combination with multivariate techniques were also explored as rapid detection and enumeration techniques of S. aureus, a common milk pathogen, and Lactococcus lactis subsp cremoris, a common lactic acid bacterium (LAB) and potential antagonist of S. aureus, in ultra-heat treatment milk. In addition, the potential growth interaction between the two organisms was investigated. FTIR spectroscopy in combination with PLS and kernel PLS (KPLS) appeared to have the greatest potential with good discrimination and enumeration attributes for the two bacterial species even when in co-culture without previous separation. Furthermore, it was shown that the metabolic effect of L. cremoris predominates when in co-culture with S. aureus in milk but with minimal converse growth interaction between the two microorganisms and therefore potential implications in the manufacture of dairy products using LAB. The widespread and high consumption of milk make it a target for potential financial gain through adulteration with cheaper products reducing quality, breaking labeling and patent laws and potentially leading to dire health consequences. The time consuming and laborious nature of currently used analytical techniques in milk authentication enabled the study of FTIR spectroscopy and matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS) as rapid analytical techniques in quantification of milk adulteration, using binary and tertiary fresh whole cows', goats' and sheep's milk mixture samples. Chemometric data analysis was performed using PLS and KPLS multivariate analyses. Overall, results indicated that both techniques have excellent enumeration and detection attributes for use in milk adulteration with good prospects for potential use in the dairy industry.
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Estudo da ciprofloxacina através de cálculos ab-initio / Ab-Initio studies of ciprofloxacinCamargo, Arthur Prado 26 May 2017 (has links)
A Ciprofloxacina é um antibiótico muito relevante, porém com efeitos colaterais indesejáveis, como convulsões, rompimento de tendão entre outros. Com o intuito de reduzir estes efeitos colaterais e para a liberação do fármaco em locais específicos, o uso de materiais lamelares, como cápsulas de armazenamento e transportador com alvo específico para biomoléculas ou células, tem sido sugerido pela literatura. A combinação de estudos teóricos e experimentais pode fornecer uma melhor compreensão da estrutura de agregados lamelares com o antibiótico Ciprofloxacina. Neste trabalho estudamos os diferentes estados iônicos da Ciprofloxacina (Cipro), obtendo os espectros de vibração (Infravermelho, Raman), Ressonância magnética nuclear de carbono e ótico (Ultravioleta-Visual). Estes resultados teóricos são comparados a resultados experimentais para investigar e caracterizar o estado molecular após intercalação. Utilizamos cálculos de estrutura eletrônica desenvolvidos no âmbito Teoria do Funcional da Densidade (DFT). Nossos resultados de análise dos espectros teóricos de Uv-Vis e de deslocamento químico obtido por RMN de Carbono revelaram que os espectros dos quatro estados iônicos da Cipro aqui estudados são muito semelhantes, o que não permite a diferenciação destes estados através destas técnicas. Por outro lado, nossos resultados de análise vibracional demonstraram frequências características de cada um dos estados iônicos. Este fato é importante, uma vez que permite identificar, através do espectro vibracional, cada um dos compostos presentes em uma dada amostra como, por exemplo, um agregado lamelar, utilizado para fins de liberação controlada de fármacos. / Ciprofloxacin is an important antibiotic, but with undesirable side effects. The use of layered materials as drug storage capsules and drug carriers can enable the development of target-specific drugs with high specificity for biomolecules or cells, which allow the release of drugs in chosen locations, thus reducing side effects .The combination of theoretical and experimental studies can provide a better understanding of the structure of lamellar aggregates with Ciprofloxacin antibiotic. In this context, to assist in the complete characterization of Ciprofloxacin, we perform theoretical calculations in the framework of the Density Functional Theory (DFT). We study different ionic states, obtaining the vibrational (IR, Raman), C-NMR and optical (UV/Vis) spectra. These theoretical results are compared with experimental results in order to unravel the molecular state upon encapsulation. Our results have shown that the Uv-Vis and NMR chemical shifts are not able to clearly differentiate the ionic states studied here. On the other hand, our calculation for the vibrational spectra reveals characteristic fingerprints of the Ciprofloxacin ionic states. This may permit, the identification of the ionic state of Ciprofloxacin in a certain sample, as layered materials, when used as drug carriers.
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Approches modélisatrices des propriétés magnétiques, spectroscopiques et de commutation de complexes moléculaires / Ab initio modeling of magnetic properties, spectroscopic and switching of molecular complexesKabalan, Lara 01 March 2010 (has links)
Dans cette thèse, nous présentons une approche modélisatrice multi-échelles au sein de la théorie de la fonctionnelle densité (DFT) de différentes classes de complexes à propriétés magnétiques commutables essentiellement à base de Fe(II) (3d6). Le manuscrit est organisé en trois grandes parties : la première a été consacrée à la présentation de la chimie théorique (concepts et méthodes). Le magnétisme moléculaire été examiné au travers du calcul de la constante de couplage et discuté dans la partie II. L’analyse de la constante de couplage, du magnétisme, des structures électroniques et des liaisons chimiques a été présentée. D’autre part, l’étude des valeurs thermodynamiques pour [Fe(btz)2(NCS)2] ainsi que la famille de complexes à transition de spin [Fe(L)2(NCS)2] a formée la troisième partie. De deux approches complémentaires sont utilisées: i-moléculaire où l’entité isolée est examinée en utilisant des codes de calcul ciblés moyennant différentes fonctionnelles d’échange corrélation et bases ; ii-« tout solide » prenant en compte la structure cristalline étendue. Les résultats sont également appuyés par une étude semi-empirique au sein de la dynamique moléculaire / In this thesis, we present an multiscale approaches based on theoretical modeling within density functional (DFT) of different classes of complex magnetic properties switched from predominantly Fe(II) (3d6). The manuscript is organized into three main parts: the first was devoted to the presentation of theoretical chemistry (concepts and methods). The molecular magnetism was examined through the calculation of the coupling constant and discussed in Part II. The analysis of the coupling constant, magnetism, electronic structure and chemical bonds was presented. In the third Part, the study of thermodynamic values for [Fe(btz)2(NCS)2] and the family of spin crossover complexes [Fe(L)2(NCS)2] has formed the third party. Two complementary approaches are used: i-“molecular” which considers a fragment entity or isolated molecule using different computer codes targeted through various exchange correlation functional and basis; ii-"solid state" taking into account the extended crystal structure. The results are also supported by a semi-empirical study through molecular dynamics.
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Synthesis And Characterization Of Novel Rare Earth Phosphates And Rietveld Structural Analysis Of Rare Earth OrthoboratesSeyyidoglu, Semih 01 October 2010 (has links) (PDF)
This thesis covers the synthesis and the characterization of sodium lanthanide oxide
phosphates, rare earth added strontium pyrophosphates and the Rietveld structural
analysis of rare earth orthoborates. Solid state and microwave-assisted synthesis
method was employed for the synthesis of desired materials. The formation of the
produced phases was confirmed by X-ray Diffraction (XRD), Infrared FT-IR,
Raman, Scanning Electron Microscopy (SEM) methods. By using Rietveld
Refinement method, structural analysis of rare earth orthoborates were done and
three dimensional crystal structures were found.
In the first part of the thesis, some new sodium lanthanide oxide phosphates were
synthesized by solid state reaction method from Ln2O3 (where Ln= La, Nd, Sm, Gd,
Dy, Ho, Er, Yb), Na2CO3, NH4H2PO4 at 1100 oC. Na2LaOPO4, Na2NdOPO4, and
Na2SmOPO4 produced with the space group is Pmm2. With the help of the same
procedure new orthorhombic Na2DyOPO4, Na2HoOPO4, Na2ErOPO4, and
Na2YbOPO4 were synthesized for the first time in the literature at 1100 oC with the
same space group Pmm2.
v
In the second part of the thesis, Sr2P2O7 - ZrP2O7 solid solution was obtained by the
solid state reaction and they were characterized for the first time in literature and
subjected to thermoluminescence measurements showing Sr2P2O7 has glow curve
around 100 oC. Then CuO and some rare earth oxides (Y2O3, La2O3, CeO2, Pr6O11,
Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3)
0.5-15% (by weight) were added to pure Sr2P2O7. After structural determinations by
XRD, thermoluminescence studies showed two glow peaks of Pr, Ho, and Nd along
with Cu-added samples, one of them is always at around 90 oC and the other TLthermoluminescence-
peak around 180, 275, and 285 oC, respectively. This study
showed that rare earth added Sr2P2O7 materials can be promising material for
dosimetric applications.
In the third part of this work, time saving microwave-assisted synthesis method was
applied to produce pure LnBO3 (Ln=La, Nd, Dy, Ho) by using urea and sucrose as a
microwave active organic additive. For LaBO3 and NdBO3, space group found as
Pnma and for DyBO3 and HoBO3 powders crystallized in hexagonal unit cell with
P-6c2 space group. All microwave-assisted products have particle sizes lower than 1 micrometer.
In the final part of this study, pure LnBO3 (Ln=Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er,
Tm, Yb, Lu) powder samples were produced by using solid state reactions of Ln2O3
and H3BO3 (ratio=1:2) heated at 900 oC for 10 hours and 1000 oC for 5 hours. The
crystallographic studies conducted with rietveld structural refinement and unit cell
parameters, background functions, profile parameters, zero shift, atomic positions,
and unisotropic thermal parameters were refined. LaBO3 and NdBO3 were solved
based on Pnma orthorhombic structure while the crystal structure of YBO3, DyBO3
and HoBO3 were monoclinic C2/c. SmBO3 showed triclinic P-1 structure.
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New Developments in Nitridometalates and Cyanamides: Chemical, Structural and Physical PropertiesBendyna, Joanna 30 October 2009 (has links)
In the course of these investigations altogether 18 different compounds have been synthesized and their chemical, structural and physical properties were characterized (XRD, XANES, IR, Raman spectrum, magnetic susceptibility, electrical resistivity, low temperature and TG/DTA).
Up to now only nitridonickelates and nitridocuprates were known to exhibit exclusively low oxidation states of the transition metals between 0 and +2. In this work it has been presented that also nitridocobaltates belong to this group. We have proved that “Ca3CoIIIN3” do not exist and the real chemical formula can be regarded as Ca5[CoIN2]2.
In the thesis another seven new nitridocobaltates(I) have been described, these add to four already known structures. Among novel phases only Ba9Ca[Co2N3]3 may indicate higher valency state for cobalt with the [Co2N3]5- complexes. The XANES data supporting CoII state by comparison with other compounds possess this oxidation state. The crystal structure of Ba9Ca[Co2N3]3 is related to the perovskite type structure.
The remarkable structural features of Sr2[CoN2]0.72[CN2]0.28 ≈ Sr6[CoN2]2[CN2] nitridocobaltates [CoIN2]5- ions partially substituted by carbodiimides [N=C=N]2- ions. Up to now in the crystal structure no indications for a homogeneity range could be observed.
Both crystal structures of (Sr6N)[CoN2][CN2]2 and Sr6[CoN2]2[CN2] encompass nitridocobaltate [CoN2]5- and carbodiimide [N=C=N]2- ions. In the structures distorted rocksalt motif based on Sr-N partial structure can be distinguished.
Up to now in the system AE-Fe-N-(C) only four crystal structures were reported and in the thesis three new were refined Sr8[FeIIIN3]2[FeIIN2], Sr3[FeN3] and (Sr6N)[FeN2][CN2]2 and their physical properties were characterized. The system AE-Mn-N-(C) via this work was extended by Sr8[MnN3]3 and Sr4[MnN3][CN2].
Up to date the only nitridometalate containing different transition elements is Ba[Ni1-xCuxN]. In this work one more mixed nitridometalate has been described Sr8[MnIIIN3]2[FeIIN2].
The crystal structure of Sr4[MnN3][CN2] revealed some weak diffuse scattering lines. The general formula of Sr4[MnN3][CN2] can be written as Sr4[Mn0.96N2.90][C0.96N2] to emphasize possible homogeneity range. Any explanation of the phenomena and establishment of possible homogeneity range are still a challenge.
The structures of Sr8[MIIIN3]2[FeIIN2] (M = Mn, Fe) are related to Sr8[MnIVN3]2[MnIIIN3]. All these compounds are first mixed-valency compounds for respective systems and exhibit close relation to crystal structures of Sr3[MN3] (M = Mn, Fe). From the XANES data alike behaviour of all structures containing Mn was observed.
Due to some possible degree of Mn/Fe mixing in the crystal structure of Sr8[MIIIN3]2[FeIIN2] the chemical formula might be written as Sr8[MnN3]2-x[FeN3]x[FeN2]. This needs to be investigate in details.
Up to now in the literature the only crystallographic data of nitridometalates contain [NCN]2- ions include two compounds. In this work four novel nitridometalate carbodiimides and cyanamides Sr4[MnN3][CN2], (Sr6N)[MN2][CN2]2 (M = Co, Fe) and Sr6[CoN2]2[CN2] have been synthesized.
Predominant magnetic properties in the investigated nitridometalates are connected to some antiferromagnetic M-M interactions supported by AFM ordering. The electrical resistivity often shows at some semi-conducting character of these compounds. XANES spectroscopy provided many useful data about valency states of the transition elements, coordination environment around absorbing atoms and electronic structure. The influence of different parameters on the transition metals K-edges was studied in details. IR and Raman give general data about [NCN]2- ions.
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RUBBER-TO-METAL BONDING: AN INVESTIGATION OF CHEMICAL REACTIONS AND ADHESION AT THE INTERFACEBERTELSEN, CRAIG MICHAEL 11 October 2001 (has links)
No description available.
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Forensic and security applications of a long-wavelength dispersive Raman systemAli, Esam M.A., Edwards, Howell G.M., Cox, R. 18 February 2015 (has links)
No / A novel dispersive system operating at 1064-nm excitation and coupled with transfer electron InGaAs photocathode and electron bombardment CCD technology has been evaluated for the analysis of drugs of abuse and explosives. By employing near-IR excitation at 1064-nm excitation wavelength has resulted in a significant damping of the fluorescence emission compared to 785-nm wavelength excitation. Spectra of street samples of drugs of abuse and plastic explosives, which usually fluoresce with 785-nm excitation, are readily obtained in situ within seconds through plastic packaging and glass containers using highly innovative detector architecture based upon a transfer electron (TE) photocathode and electron bombarded gain (EB) technology that allowed the detection of NIR radiation at 1064nm without fluorescence interference. This dispersive near-IR Raman system has the potential to be an integral part in the armoury of the forensic analyst as a non-destructive tool for the in-situ analysis of drugs of abuse and explosives. Copyright (c) 2015 John Wiley & Sons, Ltd.
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Raman-Scattering Microscopy to Investigate Microplastic Accumulation in Coastal Environment at Can Gio Mangrove Biosphere ReserveKhuyen, Vo Thi Kim 12 December 2022 (has links)
Chapter 1 gives a general introduction into plastic polymer and microplastics including concepts, sources and distribution in the environment, microplastic sampling and analytical methods, and sampling area descriptions.
Chapter 2 represents all methods and followed equipment used in the thesis. A double-filtration procedure preferable to Raman microscopy technique was developed to collect marine microplastics in brackish water from Can Gio and seawater from the East Sea.
Chapter 3 is a comprehensive guideline on IR and Raman spectra interpretation of PE, PP, PVC, PS, PMMA, and polymer textiles, which is especially useful if the automatic library is not available. This chapter represents how to identify polymer type, predict sources and chemical behaviours of microplastics with the smallest size of 15 μm based on microscopic and spectroscopic data. Also, this chapter evaluates the sample handling workflows for salt, water and sand samples.
Chapter 4 demonstrates the change in microplastic pollution from 250 MPs/L in Saigon urban canals (the center of Ho Chi Minh City), through UNESCO Can Gio Mangrove Biosphere Reserve (10 – 20 MPs/L), to estuaries of Saigon-Đong Nai River, Soai Rap River, Long Tau River (Ganh Rai Gulf), and eventually to the East Sea (3 – 5 MPs/L).
Chapter 5 highlights the correlation of microplastic properties and compositions in beach sand and seawater in the coastal environment, particularly at Can Gio 30 April Tourist Beach. This is a pilot study to identify the differences and similarities in morphologies and compositions of microplastics accumulated in beach sand and distributed in seawater, thereby, concluding sources and transport routes of microplastics in the coastal environment. The results show that microplastics accumulated at concentrations from 0 to 92.56 MPs/kg from the surface to 20-cm sand layers. The seawater at Can Gio Beach and Đong Tranh Cape contained 6.44 and 3.75 MPs/L of microplastics, respectively. White polyethylene fragments predominated, and all the microplastics comprised small secondary microplastics with a minimum size of 25 µm and a maximum size of 260 µm for fragments and a length of 640 µm for fibers. The proportions of PE, PP, PS and PMMA were similar. The differing percentages of other compositions in sand and seawater are attributed to the morphology and density of the microplastics.
Chapter 6 deals with the detection and determination of microplastics in Vietnamese sea salts. As a result, there was a higher fluctuation in microplastic amount amongs non-branded salts compared with branded salts. An average of 133.62 MPs/kg salt, corresponding to 487.71 microplastics entering the human body per year via salt consumption. More importantly, this chapter provides a convincing evidence for microplastic contamination in marine salts from the seawater. There are similarities in percentage, shape, size and colour of microplastics, especially PE, PET and PP extracted from sea salt and seawater collected in 3 different regions in Southern Vietnam (Can Gio Reserve and Vung Tau).:Chapter 1. Introduction
1.1. Synthetic polymers and plastic products
1.1.1. Overview of polymers and plastics
1.1.2. Plastic applications and global productions
1.1.2.1. Conventional plastics
1.1.2.2. Bioplastics
1.1.3. The life cycle of plastics and plastic pollution
1.2. Microplastics – definitions, sources and fate
1.2.1. Definition and classification of microplastics
1.2.2. Sources and pathways of microplastics into the environments
1.2.3. Global distribution and behaviours of microplastics in the environment
1.2.3.1. Physical behaviours: temporal and spatial accumulations
1.2.3.2. Chemical behaviours: Degradation and Adsorption
1.2.3.3. Biobehaviours: Ingestion, Translocation and Biodegradation
1.3. Effects and bioavailability of plastics on ecosystems, creatures and humans 1.3.1. Aquatic ecosystem
1.3.2. Terrestrial ecosystem
1.3.3. Food safety and human healths
1.4. Microplastic sampling techniques and analytical methods
1.4.1. Microplastic sampling techniques
1.4.1.1. Water sampling
1.4.1.2. Sediment sampling
1.4.2. Sample preparations for microplastic analysis
1.4.2.1. Matrix removal – oxidation and tissue digestion
1.4.2.2. Microplastic separation – density flotation and filtration
1.4.3. Microplastic qualification and quantification methods
1.4.3.1. Visual identification methods
1.4.3.2. Spectroscopic identification methods
1.4.3.3. Destructive thermal techniques
1.4.3.4. Summarized workflow from samples to the results on microplastics
1.4.3.5. Data expression
Chapter 2. Materials and Methods
2.1. Materials
2.2. Microscopy-spectroscopy for microplastic quantification and qualification
2.3. Quality assurances (QA) and quality controls (QC)
2.4. Collected and interviewed data on the study areas
2.5. Water samples
2.6. Sand samples
2.7. Marine salt samples
Chapter 3. The comprehensive guideline on micro-spectroscopic interpretation and sample preparations for microplastic analysis
3.1. Abstract
3.2. Visual characterizations of microplastics
3.3. Interpretation of IR and Raman spectra for plastic identification
3.4. The specificity of spectroscopies for identifying polymer type and chemical behaviours of sampled microplastics
3.4.1. Poly-Ethylene (PE)
3.4.2. Poly-Propylene (PP)
3.4.3. Poly-Vinyl Chloride (PVC)
3.4.4. Poly-Styrene (PS)
3.4.5. Poly Methyl Metacrylate (PMMA)
3.4.6. Poly-Ethylene Terephthalate (PET)
3.4.7. Poly-Amides-6, Nylon-6 (PA-6)
3.4.8. Similarity in Raman bands of pure plastics and sampled microplastics
3.5. The evaluation of sample treatment procedures
3.5.1. Salt samples
3.5.2. Sand samples
3.5.3. Water samples
Chapter 4. Assessing microplastic prevalence and spatial dispersion from Saigon urban river network to East Sea by µ-Raman spectroscopy
4.1. Abstract
4.2. Microplastic pollution in the freshwater at Saigon urban canals
4.3. Microplastic pollution in the seawater at Can Gio Biosphere Reserve
4.4. Spatial and vertical dispersion of microplastics in the East Sea of Vietnam
4.5. Conclusions
Chapter 5. Comparison of Microplastic Pollution in Beach Sediment and Seawater at UNESCO Can Gio Mangrove Biosphere Reserve
5.1. Abstract
5.2. Microplastic pollution in the sand at Can Gio Beach
5.2.1. Spatial variation in the microplastic amounts along the tidal lines
5.2.2. The abundance and composition of microplastics accumulated in sand layers
5.3. Microplastic pollution in seawater at Can Gio Beach and Đong Tranh Cape
5.4. Comparison of microplastic pollution between seawater and beach sand
5.5. Conclusions and recommendations
Chapter 6. Microplastic contamination in Vietnamese sea salts
6.1. Abstract
6.2. The microplastics abundance in commercial sea salts
6.3. Microplastic pollution in the seawater taken at salt pans in Vietnam
6.4. Microplastic contamination in the sea salt collected at salt pans in Vietnam
6.5. Comparison of characteristics of microplastics in the seawater and sea salt
6.6. The enhanced toxicity of microplastics-contaminated salt consumption
6.7. Conclusions and recommendations
Final Conclusions and Future Recommendations
List of references
Appendix
Statistical data
Photos taken on the sampling trips
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Επίδραση της επαναμορφοποίησης στις ιδιότητες ανακτημένης ύλης από πολυαιθυλένιο και πολυπροπυλένιοΚανελλοπούλου, Γωγώ 18 March 2009 (has links)
Η παρούσα διατριβή είχε ως σκοπό τη μελέτη της επίδρασης της επαναμορφοποίησης στις μηχανικές κυρίως ιδιότητες δυο πολύ κοινών πολυμερών, του πολυαιθυλενίου και του πολυπροπυλενίου. Τα πολυμερή αυτά, χρησιμοποιούνται σε πολλές εφαρμογές και για αυτό το λόγο ο όγκος των απορριμμάτων τους αποτελεί ένα σοβαρό περιβαλλοντικό πρόβλημα. Παρόλο που αποτελούν υλικά εύκολα ανακυκλώσιμα, πολύ μικρό ποσοστό από τα απορρίμματα τους ανακτώνται. Περιβαλλοντικοί αλλά και οικονομικοί λόγοι οδήγησαν στην ιδέα να κατασκευαστούν κάποια προϊόντα χαμηλών απαιτήσεων, τα οποία μέχρι τώρα κατασκευάζονται από καθαρά πολυμερή, από πλήρως ανακτημένη πρώτη ύλη.
Η δυσκολία στην εφαρμογή των ανακτημένων υλικών έγκειται στο ότι αυτά περιέχουν διάφορα πρόσθετα, καταπονούνται αρκετά από την έκθεση τους σε περιβαλλοντικούς παράγοντες όσο διάστημα χρησιμοποιούνται ή βρίσκονται στους χώρους ενταφιασμού και οι πολλαπλές επαναμορφοποιήσεις τους είναι πιθανόν να προκαλέσουν υποβάθμιση του υλικού. Για αυτό το λόγο, μελετήθηκαν επαναμορφοποιημένα δείγματα από πολυαιθυλένιο και πολυπροπυλένιο άγνωστης προϊστορίας και καταπόνησης σε σύγκριση με τα αντίστοιχα καθαρά υλικά, προκειμένου να γίνει σύγκριση των ιδιοτήτων τους και κατ’ επέκταση μια εκτίμηση της επίδρασης του βαθμού επαναμορφοποίησης στη μηχανική τους συμπεριφορά. Παράλληλα, όλα τα δείγματα, επαναμορφοποιημένα και μη, μελετήθηκαν φασματοσκοπικά, ώστε να διαπιστωθεί αν η διαδικασία ανάκτησης έχει προκαλέσει μεταβολές στη χημική δομή των υλικών αυτών.
Από τις τεχνικές χαρακτηρισμού που χρησιμοποιήθηκαν (φασματοσκοπία υπερύθρου και Raman, DSC και TGA) διαπιστώθηκε ότι δεν έχει επέλθει αλλαγή στη χημική δομή των ανακυκλωμένων υλικών. Όσον αφορά τις διαφοροποιήσεις που εκείνα παρουσίασαν σε σχέση με τα αντίστοιχα καθαρά υλικά, αποδίδονται στην παρουσία προσθέτων, χρωστικών ουσιών κυρίως, που τα ανακτημένα υλικά περιείχαν. Η μηχανική συμπεριφορά των επαναμορφοποιημένων, ιδιαίτερα στην περίπτωση του πολυαιθυλενίου ήταν παρόμοια με αυτή των καθαρών δειγμάτων και τα αποτελέσματα συγκρίσιμα. Αντίθετα, στην περίπτωση του πολυπροπυλενίου η διαδικασία ανάκτησης είχε υποβαθμίσει πολύ το υλικό με αποτέλεσμα να εμφανίζει πολύ κατώτερες μηχανικές ιδιότητες.
Όλα τα επαναμορφοποιημένα υλικά είχαν υποστεί ως ένα βαθμό περιβαλλοντική γήρανση καθώς ήταν εκτεθειμένα για αρκετό χρονικό διάστημα σε περιβαλλοντικές συνθήκες. Η επίδραση της έκθεσης όμως δεν ήταν δυνατόν να αξιολογηθεί, αφού δε ήταν γνωστό το ακριβές χρονικό διάστημα καθώς και οι συνθήκες θερμοκρασίας, υγρασίας κ.λπ.
Για αυτό το λόγο, τόσο τα ανακτημένα όσο και τα καθαρά δείγματα, υπέστησαν τεχνητή επιταχυνόμενη περιβαλλοντική γήρανση, προκειμένου να μελετηθεί η επίδρασή της στις ιδιότητες των υλικών. Αυτό που παρατηρήθηκε και σε αυτές τις δοκιμές ήταν ότι, ανάλογα με τον βαθμό επαναμορφοποίησης στα μη γηρασμένα υλικά, η τεχνητή γήρανση επηρέασε κατά κύριο λόγο τις αντοχές των υλικών σε κάθε μηχανική καταπόνηση και δευτερευόντως τις φυσικές ιδιότητες τους.
Σε γενικές γραμμές, διαπιστώθηκε ότι τα επαναμορφοποιημένα δείγματα HDPE δεν παρουσιάζουν μεταβολές ως προς τη χημική δομή τους, ενώ δίνουν συγκρίσιμα αποτελέσματα στις μηχανικές δοκιμές τόσο στο μέτρο ελαστικότητας όσο και στην αντοχή. Μετά τη γήρανση, η αντοχή τους μειώνεται σημαντικά παρόλα αυτά, η συνολική τους μηχανική απόκριση κρίνεται ικανοποιητική. Αντίθετα τα επαναμορφοποιημένα δείγματα ΡΡ, εμφάνισαν ακόμα και πριν την τεχνητή γήρανση, αισθητά χαμηλότερες μηχανικές ιδιότητες (χαμηλότερο μέτρο ελαστικότητας και αντοχή σε σχέση με τα παρθένα υλικά), παρόλο που δεν παρουσίασαν καμία αλλαγή στη χημική τους δομή. / Reforming effect on thermoplastics mechanical properties was the subject of this thesis. More specifically, samples of polyethylene and polypropylene were chosen to be tested, as they are widely used in many applications and consequently there is a large amount of municipal waste of this kind. Even though, these polymers are easily recyclable compared to other polymers, only 2% of this kind of municipal waste gets recycled in Greece nowadays. Economical and environmental reasons, researchers led to the idea of constructing products out of completely recycled materials.
Recycling process faces many difficulties; the most important of these is the addition of pigments (additives) such as colors, coupling agents etc, which make polymer recycling heavier or even impossible in some cases. Moreover, these materials degrade signifantly because of their exposure to the environment while they are used in exterior application or get thrown in landfills after use. As the collection of completely recycled materials was quite impossible, virgin and reformed of known and unknown history samples of polyethylene and polypropylene, are examined, as for their chemical structure and mechanical properties, in order to get compared and finally reach a conclusion if reformed materials are appropriate for getting used in some applications.
Through Raman and Infrared Spectroscopy, it was observed no change in reformed materials’ chemical structure before and after reforming process. Also, their thermal behavior appeared many similarities between virgin materials and reformed ones. However, these similarities did not appear in mechanical tests. Even though, reformed HDPE of known and unknown history showed comparable and very close properties with these of virgin, it is observed a lack of stability in their mechanical behavior, especially in case of reformed unknown history polyethylene. In the case of polypropylene, the reformed samples were always inferior to the virgin ones, in all tests, probably to its degradation during reforming process.
In order to determine accurately, the weathering effect on samples behaviour, they were imposed to artificial ageing in oven, in controlled temperature, humidity etc. As in non aged samples, reforming ratio plays significant role in samples’ physical properties, which appear dominantly changed after ageing. As it was expected, mechanical behavior has changed after ageing, too. However, there were no significant reduce in moduli of elasticity in tensile, compression and flexural tests, a dramatic reduce in strength in every mechanical test was observed between samples before and after ageing.
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