UV curable epoxy acrylate-clay nanocomposites

UV curable epoxy acrylates were reinforced with two different organically modified montmorillonites (MMTs) and an unmodified MMT. Conversion and rate of polymerization was monitored by real time infrared spectroscopy (RTIR) and photo-DSC. Microstructures were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and optical clarity. Optical clarity of the films containing clay was quite good as only a slight decrease was observed. Physical properties of the reinforced films were examined by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), hardness and tensile testing. Enhancements in glass transition temperature (T_g), thermal stability and mechanical properties were observed. The films reinforced with the unmodified MMT exhibit the most significant enhancements in properties.     

Unique evolution of spatial and dynamic heterogeneities on the glass transition behavior of PVPh/PEO blends

Glass transition behavior of hydrogen bonded polymer blends of poly(vinyl phenol)(PVPh) and poly(ethylene oxide)(PEO) is systematically investigated using normal differential scanning calorimetry(DSC) and recently developed multifrequency temperature-modulated DSC(TOPEM),in combination with Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance(NMR) techniques,focusing on the effect of the PEO molecular weight on the spatial and dynamic heterogeneity.It is found,for the first time,that both the glass transition temperature(T_g) and activity energy(E_a) of the blends strongly depend on PEO molecular weight,and a common turning point,which separates the rapid and slow increasing regions,can be found.The interchain hydrogen bonding interactions,both determined by FTIR measurements and obtained from the Kwei equation,decrease with increasing PEO molecular weight,indicating a decrease of the componential miscibility.A series of parameters related to the microscopic spatial and dynamic heterogeneity,such as the activity energy, fragility,nonexponential factor and the size of cooperatively rearranging regions,are calculated from frequency dependency complex heat capacity measured using TOPEM.It is found that each of these parameters monotonically changes with increasing the PEO molecular weight during the glass transition process,demonstrating that hydrogen bonding interaction is the key factor in controlling the spatial and dynamic heterogeneity,thus the glass transition.NMR relaxation results reveal the existence of obvious phase separation large than 5 nm,implying that the cooperatively rearranging regions should be closely related to the interphase region between the two components.The above obtained origin and evolution of spatial and dynamic heterogeneity provide a new insight into the glass transition behavior of polymer blends.     

Polyvinyl chloride/ montmorillonite nanocomposites

Polyvinyl chloride (PVC)/organic-montmorillonite composites were prepared by melt intercalation. Their structures and properties were investigated with X-ray diffraction (XRD), differential scanning calorimetry (DSC) and mechanical testing. The results showed that PVC chains could be intercalated into the gallery of organically modified montmorillonite to form exfoliated PVC/organic-montmorillonite nanocomposites, and the glass transition temperatures of PVC/organic-montmorillonite composites were lower than that of neat PVC. However, the tensile strength, and both the Izod type and Charpy notched impact strengths of PVC/organic-montmorillonite nanocomposites were fitted with the linear expressions: t=535.07-6.39T _g, s _I=378.76-4.59T _g and s_C=276.29-3.59T _g, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

PMMA/organomodified montmorillonite nanocomposites prepared by in situ bulk polymerization

Kinetics of the in situ bulk polymerization of methyl methacrylate in the presence of organomodified montmorillonite (MMT) was investigated using differential scanning calorimetry (DSC) and gravimetrically. Different amount and types of MMT under the trade names Cloisite were employed. Using DSC, the amount of heat released versus time, under isothermal conditions, was recorded, and eventually, the time evolution of polymerization rate and monomer conversion was calculated. Results on the variation of monomer conversion with reaction time were in good agreement to corresponding from the gravimetric measurements. The nanocomposites prepared were characterized with WAXD, TEM and FTIR, and their glass transition temperature, T _g, was measured with DSC. Depending on the added amount of nano-MMT, either exfoliated or intercalated structures were obtained. An enhancement of the polymerization rate with the presence of the nanoparticles was observed especially in the gel effect region. This was accompanied by a higher T _g and average molecular weight, as measured by GPC, of all nanocomposites compared to neat PMMA.     

Vitrification during the isothermal cure of thermosets

The process of vitrification that occurs during the isothermal cure of a cross-linking system at temperatures below T _g∞, the glass transition temperature of the fully cured resin, has been studied by TOPEM, a new temperature modulated DSC (TMDSC) technique based upon the use of stochastic temperature pulses. A comparison is made between TOPEM and another TMDSC technique, and some advantages of TOPEM are considered. The TOPEM technique is used to show that the mobility factor is not always a reliable approach to predicting the cure rate during vitrification, in view of its frequency dependence. Also, the dependence of the apparent vitrification time on frequency is examined. There appears to be a non-linear relationship between the apparent vitrification time and log(frequency), which is further discussed in the second part of this series.     

Study of the α-relaxation of PVC, EVA and 50/50 EVA70/PVC blend

The dipole dynamics and α-relaxation behaviour of polyvinyl chloride PVC, poly(ethylene-co-vinyl-acetate) EVA₇₀ and blend of them EVA₇₀/PVC have been investigated by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The differential scanning calorimetry (DSC) thermograms measured on samples show a single glass transition in the analysed temperature range. These three polymers are wholly amorphous and pure PVC and pure EVA₇₀ are miscible in the ratio 1:1. The glass transition temperature T_g decreases significantly with presence of EVA₇₀. Furthermore, the values of apparent activation energies for molecular motions at the α-relaxation and the values of fragility index have also been determined for each sample using Moynihan expression for DSC results and Vogel-Fulcher-Tammann-Hesse (VFTH) form for DRS results. It is shown a large dependence of all the values of these parameters with the content of EVA₇₀. Comparing these three polymers, we found that the more fragile glass forming liquid is the PVC. Fragility decreases drastically with EVA₇₀ content. EVA₇₀ and EVA₇₀/PVC blend exhibit practically the same behaviour. The effect of inter- and intra-molecular interactions on fragility is discussed to explain these variations.     

The glass transition

This work deals with a comparison of data obtained from differential scanning calorimetry (DSC) and thermally stimulated depolarization current (TSDC) investigations. Measurements were performed on various poly(ethylene terephthalate) films: a wholly amorphous, a thermally crystallized and drawn samples. For each specimen, the TSDC complex spectra, resolved into elementary ones, led to the determination of the classical compensation temperature (T _c ). The glass transition temperature (T _g) and the fictive equilibrium temperature (T _f) were determined by means of DSC. It appears thatT _c is different fromT _g and very close toT _f.     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Preparation and characterization of rigid poly (vinyl chloride)/MMT nanocomposites

In this article, a Haake torque rheometer equipped with an internal mixer is used to study the influence of the amount of sodium montmorillonite (Na⁺‐MMT) and organically modified MMT (O‐MMT) on the characteristics of rigid poly (vinyl chloride) (PVC)/Na⁺‐MMT and PVC/O‐MMT nanocomposites, respectively. It is observed that the fusion time and temperature of the rigid PVC/Na⁺‐MMT nanocomposites are decreased with increasing the amount of Na⁺‐MMT. On the contrast, the fusion time and temperature of the rigid PVC/O‐MMT nanocomposites are increased with increasing the amount of O‐MMT. Results of X‐ray diffraction (XRD) and transmission electron microscope (TEM) indicate that MMT is partially encapsulated and intercalated in the rigid PVC/Na⁺‐MMT nanocomposites. However, results of XRD and TEM show MMT is partially intercalated and exfoliated in the rigid PVC/O‐MMT nanocomposites. Tensile strength, yield strength, and elongation at break of the rigid PVC/MMT (including PVC/Na⁺‐MMT and PVC/O‐MMT) nanocomposites were improved simultaneously with adding 1–3 wt % Na⁺‐MMT or O‐MMT with respect to those of pristine PVC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1465–1474, 2005     

季铵盐插层蒙脱土及其去除海洋卡盾藻的研究

利用插层法制备了5种季铵盐改性的蒙脱土,通过FTIR、XRD和DTG等表征表明5种季铵盐已成功插入蒙脱土中;随后以中国典型赤潮藻海洋卡盾藻(Chattonella marina)为研究对象,考察了5种季铵盐改性蒙脱土的除藻效果。发现以双溴化十四烷基二甲基乙基溴化铵改性的蒙脱土在用量为8mg·L-1时,24h内对海洋卡盾藻的去除率最高,可达100%,而未改性蒙脱土在相同条件下除藻率仅为5.64%;除藻效果与除藻剂的结构有密切关系,在官能团相同时,链长数为14的脂肪族季铵盐除藻率最高,24h可达67.03%;在链长数相同时,含吡啶官能团的季铵盐比脂肪族季铵盐除藻率高,24h为33.62%,且随时间延长明显提高。渗溢性评估实验显示,改性蒙脱土经72h浸泡后表观插层率从71.9%降低到69.6%,表明除藻剂在水体中基本不释放。     

Thermal transitions of gelatin evaluated using DSC sample pans of various seal integrities

Differential scanning calorimetry (DSC) has become a popular tool to investigate thermal transitions in food ingredients such as gelatin. Upon heating commercial gelatin samples beyond glass transition (T _g) and melting (T _m) temperatures, a relatively large endothermic transition (T _i) can be observed. We have observed that both the peak temperature and the enthalpy of the T _i transition are influenced by the integrity of the seal of the DSC pans used for the analysis. This study shows that escape of moisture from the DSC pan appears to be responsible for this effect. The effect of different types of DSC pans, as well as technique of sealing them on the T _i transition were evaluated using DSC, SDT, and TG–MS.     

The effect of storage temperature on interactions between dehydrated sugars and phosphatidylcholine

We studied the effects of storage temperature on the stability of dehydrated POPC (1-palmitoyl-2-oleoyl-phosphatidylcholine) mixed with sucrose, trehalose, or a sucrose/raffinose mixture. We used DSC to measure the gel-to-fluid phase transition temperature (T _m) of POPC after incubation either below or near the glass transition temperature (T _g) of the sugars in the mixture. Glass formation by the sugars around fluid-phase POPC led to the lowering ofT _m below that of the fully hydrated lipid. Phospholipid phase behavior did not change during storage belowT _g. In some samples stored aboveT _g, trehalose crystallized completely; in these samples, theT _g of POPC increased to that of the partially dehydrated phospholipid. Melting the crystalline sugar re-established its ability to lower POPC'sT _m. We conclude that prevention of complete sugar crystallization was important for stability in the dry state, and that storage belowT _g conferred long-term stability to the dehydrated sugar-lipid mixtures.     

Thermal properties and applications of low molecular weight polyhydroxybutyrate

The properties of the low molecular weight polyhydroxybutyrate (LMWPHB) and LMWPHB plasticized polyhydroxybutyrate (PHB) are studied using differential scanning calorimetry (DSC), thermogravimetric analysis, wide-angle X-ray diffraction (WAXD), polarized optical microscope (POM), mechanical, and biodegradation tests. The results of DSC, WAXD, and POM indicate that LMWPHB has a lower glass transition temperature (T _g), crystallinity, crystallization rate, melting temperature (T _m), and crystal size than PHB due to its much smaller molecular weight. The tensile strength, T _g, T _m, crystallinity, crystallization rate, and thermal stability of LMWPHB plasticized PHB decrease, while the flexibility and biodegradation rate increase with the increasing content of the added LMWPHB. It is confirmed that LMWPHB can be used to improve the brittleness and control the biodegradation rate of PHB.     

Application and analysis of a DSC-Raman spectroscopy for indium and poly(lactic acid)

Simultaneous measurement system of DSC-Raman spectroscopy and its analysis method are developed. The developed method was applied to the melting of Indium and the optimum laser irradiation condition was determined. The obtained result of the heat flow is similar to the modulated DSC and the precise melting temperature and the heat of fusion can be obtained from the analyzed DSC. DSC-Raman spectroscopy is also applied to PLLA. Analyzed data indicate the existence of the recrystallization behavior in addition to T _g and T _m. Corresponding to these transitions, Raman peak shifts, intensities, and widths varied. From those results, it is proved that DSC-Raman spectroscopy is useful for the analysis of thermal property of the polymer in connection with the polymer structure.     

Preparation and thermal properties of a novel flame retardant copolymer

A monomer, acryloxyethyl phenoxy phosphorodiethyl amidate (AEPPA), was synthesized and characterized using Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance spectroscopy (¹H NMR) and ³¹P NMR. The copolymer with various amounts of styrene (St) was obtained by the free radical bulk polymerization between AEPPA and St, and characterized using ¹H NMR. The thermal properties of the copolymers were investigated with thermogravimetric analysis (TGA) in air and nitrogen atmosphere, and differential scanning calorimetry (DSC). The TGA results in air indicated the copolymers with AEPPA show higher thermal stability than those without AEPPA. However, the TGA results in nitrogen showed that the decomposition temperature decreased and the char residue increased with the increase of AEPPA. The glass transition temperature (T_g) of the copolymers from DSC indicated that a inverse proportion was observed between T_g and the amount of AEPPA incorporated. The flammability of the copolymers was evaluated by microscale combustion calorimeter (MCC). The MCC results showed that AEPPA can decrease the peak heat release rate (PHRR) and the heat release capacity (HRC), and the sample CP10 shows the lowest PHRR and HRC.     

Linear unsaturated polyester + poly(?-caprolactone) blends: Calorimetric behaviour and morphology

Blends of a linear unsaturated polyester (LUP, commercially named Al100) with poly(?-caprolactone) (PCL) of different molecular weights have been studied. The miscibility and crystallinity have been analyzed through FT-IR spectroscopy, differential scanning calorimetry (DSC) and environmental scanning electronic microscopy (ESEM). All the blends were subjected to the same heat treatment consisting of crystallizing during 45 min at constant temperature (10, 20, 30 or 40 °C). The glass transition temperature, T_g, and fusion temperature, T_fus, have been determined in the whole composition range for each blend. The T_g-composition dependence and the high degree of crystallinity detected at intermediate blend compositions denote an anomalous behaviour that could indicate the lack of homogeneity (phase separation) in the different blends studied. The ESEM measurements confirm the lack of homogeneity of the amorphous region in blends with high content of LUP. The results have been discussed as a function of the crystallization temperature and the molecular weight of PCL.     

Mechanical and thermal properties of poly-ether ether ketone reinforced with CaCO3

CaCO₃/PEEK (poly-ether ether ketone) composites were prepared on a twin-screw extruder with different mass ratio of CaCO₃/PEEK from 0% to 30%. Four types of particles were used as filler in PEEK matrix. The influence of surface treatment with sulfonated PEEK (SPEEK) of the particles on the mechanical and thermal properties of the composites was studied. The experiments included tensile tests, flexural tests, notched Izod impact tests, TGA, DSC and SEM. The modulus and yield stress of the composites increased with CaCO₃ particles loadings. This increase was attributed to the bonding between the particles and the PEEK matrix, as can be proved by the SEM pictures of tensile fracture surface of the composites. The impact strength of the composites was modified by the SPEEK coated on the CaCO₃ particle surface. DSC experiments showed that the particle content and surface properties influenced the glass transition temperature (T_g) and melting temperature (T_m) of the composites. The T_g increased with the content of fillers while T_m decreased. In this study the fillers treated were found to give better combination properties, which indicated that SPEEK played a constructive role in the CaCO₃/PEEK composites.     

Studies on the thermal properties of caprolactam/long chain lactam copolymer

The thermal properties of caprolactam/long chain lactam copolymer were studied with a Perkin-Elmer DSC 7. The melting point (T _m), heat of fusion (δH _m), crystalline degree (X _c), crystallization temperature (T _c) and glass transition temperature (T _g) of the copolymers increase with decrease of the content of the log chain lactam. From the changes in the mechanical properties with corresponding changes in the thermal properties, it is clear that the copolymers are thermal plastic and elastic. In addition, it is found that the results at a heating rate of 10 deg·min^?1 are almost the same as that at 20 deg·min^?1 after thermal history is erased.     

The crystalline and mechanical properties of PLA/layered silicate degradable composites

The poly(lactic acid) (PLA)/montmorillonite (MMT) composites were prepared by melt blending in an internal mixer. The effect of MMT and organically modified MMT (OMMT) addition on crystallization and mechanical preferences has been studied. The DSC results show that the crystallization ability of PLA is improved by MMT or OMMT. The addition of MMT and OMMT increase the crystallinity of PLA from 27.3 to 32.8%, and the cold crystallization temperature (T_CC) of PLA decreases from 93.1 to 88.9°C with the MMT. However, the nucleating effect of MMT is better than that of OMMT due to the velvety surface resulted from the organic modification. The average size of the spherulites in PLA/MMT is smaller than that in PLA/OMMT. The addition of MMT or OMMT increases the tensile strength of PLA from 29.6 to 34.7 MPa and decrease the elongation at break of PLA. The modulus of PLA composites is enhanced rapidly from 338 to 660 MPa by the addition of MMT.