These developmental grade samples were supplied by the Union Chemical Laboratories of Industrial Technology Research Institute(ITRI). The compositions of a series of copolyesters were identified by C1-NMR and H1-NMR. The ethylene terephthalate(ET) units are 8.9¡B33.7¡B37.9% and trimethylene terephthalate(PT) units are 91.1¡B66.3¡B62.1% in the copolyesters with sample codes of C2¡BC3¡BC4. Differential scanning calorimeter(DSC) was used to study the isothermal crystallization kinetics and melting behaviors and Polarizing Microscope(PLM) was used to study the spherulite growth rates and spherulite patterns. The Hoffman-Weeks linear plot and M-X nonlinear plot gave an equilibrium meiting temperature(Tmo ) oC of C2¡BC3¡BC4 are (240.6¡B275.5)¡B(208.8¡B247.0)¡B(194.3¡B229.4). The growth rates (£gm/s )of different samples in the different crystallination temperature(Tc) oC are C2(0.614~0.061, 180~207)¡BC3(0.112~0.021, 130~166)¡BC4(0.0213~0.003, 120~160). From the different equilibrium meiting temperature(Tmo ) and different T¡Û = ( Tg-30, Tg-51.6 oC) to analysis the regime transition temperature (T¢º¡÷¢») in units of oC are C2(234.0¡B237.1¡B240.6¡B275.5¡A195.9¡Ó0.3, 196.2¡Ó0.4)¡BC3(193.1¡B198.9¡B208.8¡B247.0¡A147.5¡Ó0.2, 147.5¡Ó0.1)¡BC4(184.1¡B187.9¡B194.3¡B229.4¡A133.3¡Ó0.4, 133.6¡Ó0.2). Compare the results with the results that using the half-time of crystallization(t1/2) from DSC (C2(193.6 oC)¡BC3(147.3 oC)¡BC4(1140.4 oC)). It can find that C2 is over 2.3 and 2.6 oC and C3 is the same and C4 is under 6.8 and 7.1 oC. From the morphology of spherulite patterns and regime transition temperature (T¢º¡÷¢») oC, the results indicated that the change from the morphology is closed to regime transition temperature. Regular spherlites were exhibited at temperature(Tc) between 180 and 196 oC and banded spherulites were observed between 197 and 208 oC in the C2. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 130 and 147 oC and banded spherulites were observed between 148 and 172 oC in the C3. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 120 and 134 oC and banded spherulites were observed between 135 and 160 oC in the C4. The band spacing increase with increasing crystallization temperature. Combine the results of M-X plot and spherulites pattern and melting behaviors at a heating rate of 80 oC/min . It indicated that the regime transition temperature (T¢¹¡÷¢º) oC are in the range of crystallization temperature of C2¡BC3¡BC4 are (210~213¡B174~178¡B160~164 oC). The heat of fusion (¡µHu) of C3 is 4.88¡Ó0.06 kcal/mol and B is 1.47¡Ó0.05 cal/c.c from the experimental. The heat of fusion(¡µHu) of C4 is 2.56¡Ó0.22 kcal/mol and B is 4.45¡Ó0.36 cal/c.c from the experimental. Compare the results with PET(¡µHu = 5.6 kcal/mol) and PTT(¡µHu = 7.2 kcal/mol). It indicated that PTT > PET > C3 > C4.

The glass forming ability (GFA) of the lightweight Mg65Cu25Y10 alloy has been widely studied. This alloy contains a medium sized Mg matrix (0.16 nm in atomic radius), a small sized Cu (0.14 nm) and a large sized Y (0.18 nm). The glass transition temperature Tg, supercooled temperature range

<p> This study is on the thermodynamics, electrical and diffusion properties of five bulk metal glasses, new materials of great importance in technology, and on a longstanding problem of the residual entropy of the glassy state. It describes (i) an investigation of spontaneous structural relaxation, (ii) discovery of memory effect, and (iii) an investigation of crystallization kinetics both isothermally and on rate heating of bulk metallic glasses by measurements of their enthalpy change with time, temperature, and annealing conditions. Furthermore, it provides a real-time electrical resistivity study of structural relaxation effects, and an electron microscopy study of the interdiffusion kinetics of atoms across a junction interface, i.e., the so-called Kirkendall effect. </p> <p> It is shown that structural relaxation occurs according to a stretched exponential kinetics and distribution of relaxation times leads to memory effect for a glass sample of complex thermal history. This mechanism is confirmed by real time electrical resistivity measurements at different temperatures and explained in terms of the Ziman model. Crystallization of ultraviscous melts occurs in several steps but the first and major step follows the Kolmogorov-Johnson-Mehl-Avrami kinetics based upon the Poisson distribution of nucleation sites. Several other processes also occur including a possible spinodal decomposition with one phase remaining in the rigid glassy state. Thermally activated interdiffusion of atoms across a junction interface is inconsistent with the vacancy diffusion model. Finally, it is shown that contrary to the recent arguments based upon the Boltzmann equation, a glass has residual entropy. </p> <p> Seven papers based upon this study have been published in Journal of Non-Crystalline Solids, Journal of Chemical Physics, Journal of Physical Chemistry, Thermochimica Acta, and Philosophical Magazine. </p> / Thesis / Doctor of Philosophy (PhD)

It was the objective of this research to develop high temperature and high performance polyimides that also display (a) thermal stability; (b) crystallinity in the initial material and ability to crystallize from the melt; (c) fast crystallization kinetics and (d) melt processability. This unique combination of properties is presently unavailable in any other polyimide. In this regard, the present work investigates the crystallization, morphology and thermal stability of two novel semicrystalline polyimides based on the same diamine, 1,3-bis (4-aminophenoxy) benzene (TPER), but two different dianhydrides, 3,3',4',4'-biphenyltetracarboxylic dianhydride (BPDA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA). Phthalic anhydride was used as an endcapper to improve the thermal stability of the polyimides. The BPDA based polyimide was also tested extensively as a structural adhesive using Ti-6Al-4V coupons. Additionally, these polyimides are based on monomers, that are presently commercially available. The bulk thermal stability of the polyimides was first evaluated using dynamic and isothermal thermogravimetric experiments. DSC was utilized to test the ability of the polyimides to crystallize from the melt after exposures to varying melt times and temperatures. Exceptional thermal stability was demonstrated by BPDA based polyimide with no change in the melting behavior after 40 min at 430°C or 30 min at 440°C. The semicrystalline morphology of the material was studied using hot stage polarized optical microscopy (OM) and atomic force microscopy. The spherulitic growth rates were determined as a function of crystallization temperature after quenching from various melt times and temperatures. The effect of crystallization temperature, previous melt time and melt temperature on the morphology was considered. The spherulitic growth rates increased with increasing undercooling in the temperature range studied (nucleation controlled), while the growth rate at a specific crystallization temperature decreased on increasing the previous melt time and temperature. The melting behavior was studied after different crystallization times and temperatures and also as a function of different heating rates. Crystallization kinetics was followed both isothermally and non-isothermally using DSC and OM. Avrami analysis was performed for TPER-BPDA and the obtained results were correlated with microscopic observations. Melt viscosity measurements were carried out as a function of melt temperature, melt time and frequency. The adhesive investigations for TPER-BTDA utilized lap-shear test, wedge test and double cantilever beam tests. The durability of the adhesive and the fracture surface was studied after exposure to various solvents and after high aging and testing temperatures. The polyimide demonstrated very high average room temperature lap-shear strengths (8400 psi or 59 MPa), excellent solvent resistance and durability of strengths at high aging and testing temperatures. / Ph. D.

Crystallization and multiple melting behavior of bisphenol-A polycarbonate (PC) was investigated using differential scanning calorimetry (DSC) for the monitoring of thermal behavior and atomic force microscopy (AFM) for the morphology study. The exceedingly slow crystallization kinetics of PC and the feasibility of obtaining near monodisperse fractions provide distinct advantages for the elucidation of the effects of crystallization time, temperature, and molar mass on crystallization kinetics. The effects of molar mass on the glass transition temperature (Tg) and heat capacity change at Tg, and the amorphous density of PC were investigated. Similar to many semicrystalline polymers, PC exhibits a multiple melting behavior upon heating. While for each PC sample, the coexistence of low and high temperature endothermic regions in the DSC heating traces is explained by the melting of populations of crystals with different stabilities, melting-recrystallization-remelting effects are observed only for the lowest molar mass samples. The effects of crystallization temperature and molar mass distribution on overall crystallization kinetics were studied for some of the fractions, including the commercial PC-28K (Mw = 28,000 g.mol-1) sample. Regarding the kinetics of secondary crystallization, particular attention was placed on understanding the effects of molar mass, initial degree of crystallinity prior to the secondary crystallization, and secondary crystallization time and temperature. The secondary crystallization of PC follows the same laws discovered in previous studies of PEEK, PET, it-PS and ethylene copolymers, and the results are discussed in the context of a bundle-like secondary crystallization model. During isothermal annealing of semicrystalline PC-28K around the high melting endotherm, a significant increase of melting temperature along with peak broadening with time was observed. Independently, morphological studies using AFM showed that mean lamellar thickness increases with time during isothermal annealing. These results are discussed in light of isothermal thickening of lamellar crystals. Lastly, almost 200 DSC melting traces of varying molar mass PC samples thermally treated under various conditions were analyzed to calculate crystallinity (Xc), rigid fraction (RF), and rigid amorphous fraction (RAF). The correlation between RAF vs Xc, Tg, and Tg broadening are discussed. / Ph. D.

Vitrocerâmicas contendo cristais de diopsídio (CaMgSi2O6 = CMS2) têm sido consideradas promissoras para diferentes aplicações. Entretanto, quando tratado termicamente, o vidro de diopsídio exibe somente cristalização superficial. Uma maneira de se obter cristalização no volume neste vidro é através da adição de agentes nucleantes em sua composição. O objetivo inicial desta tese de doutorado foi verificar a eficiência da adição dos compostos TiO2, ZrO2 e Fe2O3, como agentes nucleantes no processo de cristalização volumétrica no vidro de diopsídio. Os vidros foram obtidos pelo método de fusão-resfriamento e, em seguida, foram submetidos a um tratamento térmico de nucleação e crescimento de cristais. Os resultados mostraram que somente a adição de Fe2O3 acima de 7% molar ao vidro CMS2 favorece a cristalização no interior da amostra. O vidro contendo 9 mol% de Fe2O3 apresenta como característica principal uma distribuição homogênea de cristais no volume da amostra vítrea. As fases cristalinas originadas foram caracterizadas por Difratometria de Raios X e o mecanismo de nucleação de cristais foi estudado através do método de Análise Térmica Diferencial (ATD) e análise microestrutural quantitativa de amostras submetidas aos seguintes ciclos de tratamento isotérmico: i) dois estágios (o primeiro de nucleação e o segundo de crescimento de cristais) e ii) um único estágio de nucleação e crescimento de cristais. As amostras contendo 9 mol% de Fe2O3 apresentaram somente a fase cristalina diopsídio com os íons de ferro aparentemente incorporados em sua rede cristalina. Através da análise dos dados de ATD em regime isotérmico da amostra contendo 9 mol% de óxido de ferro foi possível determinar o valor médio do coeficiente de Avrami (n) como sendo próximo a 3,0 para temperaturas de 760, 770, 780 e 790 °C. De acordo com a literatura, estes valores de n indicam que o vidro CMS2 contendo 9 mol% de Fe2O3 exibe um mecanismo de cristalização volumétrica caracterizado pelo aumento e saturação do número de núcleos de cristais tridimensionais de diopsídio férrico e por um mecanismo de crescimento de cristais controlado por interface. Além disso, os resultados do método de microscopia para os dados experimentais correspondentes ao tratamento térmico de simples estágio mostraram que o mecanismo de cristalização volumétrica do vidro CMS2 9F é descrito pelo caso mais geral da equação de KJMAY, onde as taxas de nucleação e de crescimento são dependentes do tempo e podem variar ao longo do processo de cristalização isotérmica. / Glass-ceramics containing diopside crystals (CaMgSi2O6 = CMS2) have been considered promising for different applications. However, when thermally treated, diopside glass exhibits only surface crystallization. One way of obtaining volume crystallization in this glass is by the addition of nucleating agents in its composition. The initial objective of this PhD thesis was to verify the efficiency of the addition of the TiO2, ZrO2 and Fe2O3 compounds as nucleating agents in the process of volume crystallization in diopside glass. Glasses were obtained by the melt-cooling method and were then subjected to a nucleation and crystal growth heat treatment. The results showed that only the addition of Fe2O3 above 7 mol% to the CMS2 glass favors crystallization in the sample volume. Glass containing 9 mol% Fe2O3 has as main characteristics a homogeneous distribution of crystals in the sample volume. The crystalline phases originated were characterized by X-ray diffraction and the crystal nucleation mechanism was studied through the Differential Thermal Analysis (DTA) method and quantitative microstructural analysis of samples submitted to double - and single - stage thermal treatments. The samples containing 9 mol% of Fe2O3 presented only the ferric diopside crystalline phase with the iron atom apparently incorporated in its crystalline network. By analyzing the DTA data in the isothermal regime of the sample containing 9 mol% of iron oxide, it was possible to determine the average value of the Avrami coefficient (n) as being near to 3.0 for temperatures of 760, 770, 780 and 790 oC. According to the literature, these values of n indicate that CMS2 glass containing 9 mol% Fe2O3 exhibits a volume crystallization mechanism characterized by increase and saturation of the number of nuclei and an interface-controlled growth of ferric diopside three-dimensional crystals. In addition, the results of the microscopy method for the experimental data corresponding to the single-stage heat treatment showed that the CMS2 9F glass volume nucleation mechanism is described by the more general case of the KJMAY equation, where the rates of nucleation and growth are time dependent and can vary throughout the isothermal crystallization process.

Afin de mieux prévoir le type d’éruption (effusif ou explosif) des volcans d’arc, il est primordial d’étudier les vitesses d’ascension du magma dans le conduit volcanique. Un moyen d’appréhender ces modalités d’ascension est de déterminer les cinétiques des processus intervenant lors de la remontée magmatique. Ainsi, nous avons choisi d’étudier les cinétiques de cristallisation (vitesses de nucléation et de croissance) des microlites de plagioclase par une approche expérimentale, puis théorique, à partir de compositions synthétiques reproduisant le verre rhyolitique interstitiel du magma de la Montagne Pelée et son analogue simplifié (haplotonalite). Nos résultats révèlent que le magma décomprimé à partir de 200 MPa selon différentes vitesses de décompression (ΔP/Δt = 1200, 150 et 30 MPa/hr) jusqu'à une pression finale donnée entre 160 et 25 MPa, montre différentes modalités de cristallisation des plagioclases. En particulier, plus la vitesse de décompression est lente, plus la densité numérique de cristaux est élevée. Les vitesses de nucléation des plagioclases varient de 3.8E-03 à 1.5E-02 mm-2, tandis que celles de croissance variant peu, sont de l’ordre de 10-6 mm.s-1. La modélisation de la cristallisation nous a permis de i) mieux contraindre l’énergie d’interface plagioclase/haplotonalite, en déterminant des paramètres de forme et de rugosité du nucleus à appliquer à la théorie classique de la nucléation ii) démontrer que la vitesse de croissance des plagioclases est limitée soit par la diffusion, soit par les mécanismes à l’interface iii) et qu’une croissance des plagioclases par diffusion n’est pas systématiquement contrôlée par l’élément diffusant le plus lentement, et qu’elle dépend étroitement de la nucléation. Aussi, nous avons révélé l’importance de la composition du liquide silicaté sur les cinétiques de cristallisation, en particulier l’effet inhibiteur sur la nucléation de l’ajout de quelques ppm d’arsenic dans le liquide silicaté. / Magma ascension rate in volcanic conduit plays an important role in determining eruption dynamics of arc volcanoes (effusive or explosive). Investigating the kinetics of processes such as decompression induced crystallization may provide crucial information on the modality of magma ascent. We performed decompressioninduced isobaric crystallization-timed experiments starting with Mt Pelée rhyolitic glass composition and its simplified analogue (haplotonalite) to study plagioclase crystallization (nucleation and growth) kinetics. Our results reveal that a melt depressurized from 200 MPa to a given final pressure from 160 to 25 MPa according to different decompression rates (ΔP/Δt = 1200, 150 and 30 MPa/hr), shows various modalities of crystallization of plagioclases. In particular, the slower the decompression, the higher the numerical density. The crystallization modeling i) provides new constraints on the plagioclase/haplotonalite interfacial energy that controls the nucleation kinetics, by determining shape and roughness parameters ii) reveal that plagioclase crystallization is either controlled by diffusion or crystal/melt interfacial mechanisms, iii) demonstrates that plagioclase diffusion-controlled growth rate is not systematically controlled by the slowest diffusion element, and it closely depends on nucleation. Also, we revealed the importance of melt composition on crystallization kinetics, in particular the inhibitive effect on nucleation of trace arsenic addition in the melt.

Orientador: Victor Ciro Solano Reynoso / Banca: Walter Katsumi Sakamoto / Banca: Silvio Rainho Teixeira / Resumo: Os vidros preparados para diversas aplicações têm um ponto em comum: a possibilidade de nuclear e cristalizar novas fases, quando preparados a partir de uma massa fundida ou através de um tratamento térmico acima da temperatura de transição vítrea. Neste trabalho são apresentadas de forma sucinta as formulações teóricas de formação de vidros incidindo principalmente nos processos de nucleação e crescimento de fases. O estudo da cristalização de vidros pode ser feito através de métodos cinéticos baseados na descrição teórica formulada por Johnson-Mehl- Avrami (JMA). Estes métodos descrevem os processos de nucleação e cristalização utilizando dados provenientes das curvas de DTA/DSC. Uma delas é aquela proposta por Kurajica, que determina os parâmetros cinéticos utilizando um modelo para a resolução da sobreposição dos picos de cristalização. Para a aplicação deste modelo, foram utilizados vidros teluretos, de composição 80TeO2 - 10Nb2O5 - 8Li2O - 2V2O5 (mol%) denominados TNLV, e vidros fosfatos, de composição 50P2O5 - 36Na2O - 10CdO - 4La2O3 (mol%), dopados com 20 e 60mg de CeO2 denominados PNCL20 e PNCL60. O estudo cinético teve início com a identificação das fases cristalinas formadas, utilizando a difratometria de raios X (DRX). Considerando a formação de três fases cristalinas para cada sistema vítreo, a equação proposta por Kurajica foi aplicada, utilizando o software Origin 7.0, para determinação dos parâmetros cinéticos, a partir dos ajustes dos dados de DSC. Os coeficientes de Avrami (n) determinados mostraram que para o sistema TNLV o crescimento se dá em três dimensões com mecanismos diferentes, enquanto que para os sistemas PNCL20 e PNCL60, o crescimento ocorre em três dimensões com reação de interface. Foi observado que... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The glasses prepared for various applications have one common point: the possibility of new phases nucleation and crystallization, when prepared from a melt or through a heat treatment above the glass transition temperature. In this work are presented briefly the theoretical formulations of formation of glass focusing mainly in the processes of phases nucleation and growth. The study of glass crystallization can be done by kinetic methods based on the theoretical description formulated by Johnson- Mehl-Avrami (JMA). These methods describe the processes of nucleation and crystallization using data from DTA/DSC curves. One model is that proposed by Kurajica which determine the kinetic parameters resolving overlapping peaks of crystallization. To apply this model were used a tellurite glass, with composition 80TeO2 - 10Nb2O5 - 8Li2O - 2V2O5 (mol%) denominated TNLV, and two phosphate glasses of composition 50P2O5 - 36Na2O - 10CdO - 4La2O3 (mol%) doped with 20 and 60mg of CeO2 denominated PNCL20 and PNCL60. The kinetic study started us with the identification of crystalline phase, using the X-ray diffraction (XRD). Considering that three crystalline phases are formed for each glassy system, the Kurajica equation was applied using the Origin 7.0 software, for determining the kinetic parameters. The calculated Avrami coefficients (n) shown that for the TNLV system the growth occurs in three dimensions with different mechanisms, while for the PNCL20 and PNCL60 systems the growth occurs in three dimensions with an interface reaction. It was observed that the PNCL20 system has higher activation energy that the PNCL60 system and XRD patterns showed that the characteristic peaks of the phases containing CeO2, become higher and thinner in the system PNCL60. These results show that the cerium may favors the glass crystallization. / Mestre

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-27Bitstream added on 2014-06-13T19:32:46Z : No. of bitstreams: 1 costa_fb_me_ilha.pdf: 9510999 bytes, checksum: 9a5d3acde99bb0f41fcb579520ce6a76 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os vidros preparados para diversas aplicações têm um ponto em comum: a possibilidade de nuclear e cristalizar novas fases, quando preparados a partir de uma massa fundida ou através de um tratamento térmico acima da temperatura de transição vítrea. Neste trabalho são apresentadas de forma sucinta as formulações teóricas de formação de vidros incidindo principalmente nos processos de nucleação e crescimento de fases. O estudo da cristalização de vidros pode ser feito através de métodos cinéticos baseados na descrição teórica formulada por Johnson-Mehl- Avrami (JMA). Estes métodos descrevem os processos de nucleação e cristalização utilizando dados provenientes das curvas de DTA/DSC. Uma delas é aquela proposta por Kurajica, que determina os parâmetros cinéticos utilizando um modelo para a resolução da sobreposição dos picos de cristalização. Para a aplicação deste modelo, foram utilizados vidros teluretos, de composição 80TeO2 - 10Nb2O5 - 8Li2O - 2V2O5 (mol%) denominados TNLV, e vidros fosfatos, de composição 50P2O5 - 36Na2O - 10CdO - 4La2O3 (mol%), dopados com 20 e 60mg de CeO2 denominados PNCL20 e PNCL60. O estudo cinético teve início com a identificação das fases cristalinas formadas, utilizando a difratometria de raios X (DRX). Considerando a formação de três fases cristalinas para cada sistema vítreo, a equação proposta por Kurajica foi aplicada, utilizando o software Origin 7.0, para determinação dos parâmetros cinéticos, a partir dos ajustes dos dados de DSC. Os coeficientes de Avrami (n) determinados mostraram que para o sistema TNLV o crescimento se dá em três dimensões com mecanismos diferentes, enquanto que para os sistemas PNCL20 e PNCL60, o crescimento ocorre em três dimensões com reação de interface. Foi observado que... / The glasses prepared for various applications have one common point: the possibility of new phases nucleation and crystallization, when prepared from a melt or through a heat treatment above the glass transition temperature. In this work are presented briefly the theoretical formulations of formation of glass focusing mainly in the processes of phases nucleation and growth. The study of glass crystallization can be done by kinetic methods based on the theoretical description formulated by Johnson- Mehl-Avrami (JMA). These methods describe the processes of nucleation and crystallization using data from DTA/DSC curves. One model is that proposed by Kurajica which determine the kinetic parameters resolving overlapping peaks of crystallization. To apply this model were used a tellurite glass, with composition 80TeO2 - 10Nb2O5 - 8Li2O - 2V2O5 (mol%) denominated TNLV, and two phosphate glasses of composition 50P2O5 - 36Na2O - 10CdO - 4La2O3 (mol%) doped with 20 and 60mg of CeO2 denominated PNCL20 and PNCL60. The kinetic study started us with the identification of crystalline phase, using the X-ray diffraction (XRD). Considering that three crystalline phases are formed for each glassy system, the Kurajica equation was applied using the Origin 7.0 software, for determining the kinetic parameters. The calculated Avrami coefficients (n) shown that for the TNLV system the growth occurs in three dimensions with different mechanisms, while for the PNCL20 and PNCL60 systems the growth occurs in three dimensions with an interface reaction. It was observed that the PNCL20 system has higher activation energy that the PNCL60 system and XRD patterns showed that the characteristic peaks of the phases containing CeO2, become higher and thinner in the system PNCL60. These results show that the cerium may favors the glass crystallization.

Růst krystalů zásadně ovlivňuje morfologii a tím také mechanické vlastnosti semikrystalických polymerů. Tato PhD práce přináší alternativní pohled na popis kinetiky krystalizace v polyolefinech plněných slabě interagujícími částicemi. V nanokompozitních materiálech vysoký specifický povrch plniva i při nízkých plněních zásadně ovlivňuje dynamiku řetězců. V blízkosti povrchu plniva začíná hrát významnou roli zpomalená reptace způsobená jak vzájemnými interakcemi plnivo-polymer tak prostorovým omezením mezi nanočásticemi. Růst krystalů byl zkoumán pomocí polarizovaného optického mikroskopu vybaveného horkým stolkem. Výsledky byly korelovány s teoretickými modely a rozsáhlými počítačovými simulacemi na molekulární úrovni. Pozorovaný pokles rychlosti růstu sférolitů v závislosti na obsahu plniva a molekulové hmotnosti matrice je interpretován na základě imobilizační teorie, tedy, zpomalení reptačního pohybu.