Infrared spectroscopic characterization of oriented polyamide 66: Band assignment and crystallinity measurement

Having found much ambiguity in the infrared band assignments for polyamide 66 (PA66), we revisited some of these assignments before using infrared spectroscopy to assess microstructure changes resulting from multiple thermal treatments. We discovered that earlier assignments of the 1144 and 1180 cm⁻¹ bands to the amorphous (noncrystalline) phase were incorrect, whereas the bands at 924 and 1136 cm⁻¹ can be attributed unambiguously to the noncrystalline phase. We also confirmed that PA66 bands at 936 and 1200 cm⁻¹ are crystalline bands. The normalized absorbance of the 1224‐cm⁻¹ fold band increases in proportion to crystallinity, indicating that chain folding is the predominant mechanism of thermal crystallization in PA66. We demonstrated that infrared spectroscopy can be used to estimate the degree of crystallinity of PA66, and two methods were explored. One is a calibration method in which the band ratio of 1200 and 1630 cm⁻¹ is plotted against crystallinity measured by density. The other is an independent infrared method based on the assumption that PA66 satisfies a two‐phase structure model. The crystallinity determined by the independent infrared method showed good agreement with the crystallinity obtained from density measurements. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 516–524, 2000     

TRANSAMIDATION IN THE in situ BLENDING OF POLYAMIDE 1212 WITH POLYAMIDE 6 THROUGH ANIONIC POLYMERIZATION OF CAPROLACTAM

20 wt% polyamide 12(PA1212)pellets were dissolved in molten caprolactam.The caprolactam was then catalyzed at 180℃and polymerized by means of anionic ring-opening polymerization to produce in situ blends of the resultant polyamide 6(PA6)and PA1212.Mechanical blends with same ingredient were prepared through melt blending on a twin-screw extruder.Scanning electron microscopy(SEM)observation revealed that contrary to the mechanical blends with small spherulites embedded in the matrix,no phase-separation existed in the in situ blends.The results of thermal analysis by differential scanning calorimetry(DSC)showed that single melting peak and crystallization peak existed for the in situ blends,while two melting and crystallization peaks appeared for the mechanical blends.The in situ blend film and the mixed blend film,both cast from a dilute formic acid solution with a concentration of 0.5 g/L,remained similar crystallization and melting behavior as above.It is proved by solution ~(13)C-NMR analysis that transamidation took place during the in situ blending,and it is suggested that the combination of temperature increasing and the basic surrounding derived from NaOH during polymerization resulted in the occurrence of transamidation.Furthermore,it is proposed that the interchange reaction between PA1212 and PA6 also resulted from the degradative reaction during the anionic polymerization.     

Enhancement of the crystallization and thermal stability of polyhydroxybutyrate by polymeric additives

The crystallization and thermal degradation of polyhydroxybutyrate (PHB) blended with a small amount of carboxyl-terminated butadiene acrylonitrile rubber (CTBN) and biocompatible polyvinylpyrrolidone (PVP) are analyzed by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TG), gel permeation chromatography (GPC), polarized optical microscope (POM), and wide angle X-ray diffraction (WAXD). From results of DSC, TG, and GPC, it is shown that the presence of PVP or CTBN could affect the crystallization rate, crystallinity, melting temperature, and thermal stability of PHB. The changes of crystal sizes by the added CTBN and PVP are also confirmed by the POM and WAXD analyses. The addition of the 1 wt% PVP or CTBN into PHB can significantly increase the crystallization rate and thermal degradation temperature, and affect the degradation kinetics of PHB due to the steric hindrance effects of the added PVP and CTBN on retarding the degradation reaction. The best improvement of the thermal stability is obtained from the PVP-modified PHB. The method of using CTBN or PVP to improve the thermal stability of PHB is of great processing advantages in industry because it is functional with low purity PHB, henceforth, saves the cost of the purification process.     

The way to measure quantitatively full dissolution and crystallization of polyamides in water up to 200 °C and above by DSC

The way to measure quantitatively full dissolution and crystallization of polyamides in water up to 200 °C and above by DSC is described. Stainless-steel high-pressure pans enable research on fully dissolving polyamides in water under vapor pressure. The results show clearly that polyamide 6 (PA6) is soluble in water under vapor pressure in the whole concentration range and that water acts as a crystallization and melting point suppressor. The maximum temperature depression is approximately 60 °C. This depression of the transitions is independent of concentration over a large range (10-70 mass% PA6 in water). When PA6 dissolves in water during heating, the polymer often sets to the sides of the DSC sample pan. Because of this the contact between the sample and the bottom of the pan reduces during measurement and therefore DSC heating curves are frequently curved. Adding steel wool to these stainless-steel high-pressure pans improves the measurements by increasing the thermal conductivity between the sample and pan bottom, and as a result the DSC curves become less curved. The interpretation of the measurements improves and the possibility of reproducible peak area calculations also in heating comes in sight.     

Influence of maleic anhydride-grafted EPDM and flame retardant on interfacial interaction of glass fiber reinforced PA-66

In this paper, the effects of melamine polyphosphate flame retardant (MPP-FR) and maleic anhydride-grafted EPDM (MA-EPDM) on the interfacial interaction of PA66/GF were investigated by means of scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), rheological behavior and mechanical properties. The experimental results demonstrate that MPP-FR and MA-EPDM could effectively improve interfacial interactions between the PA66 and GF. Based on SEM, good interfacial adhesion between PA66 and GF in PA66/GF/FR and PA66/GF/FR/MA-EPDM composites was observed, however, MPP-FR destroyed the PA66 matrix. DMA results show that MPP-FR increased glass transition temperature (T_g) and storage modulus, and lower tan δ, while MA-EPDM showed a little effect on them in PA66/GF/FR/MA-EPDM composite compared with PA66/GF/FR. MPP-FR made PA66 crystallization temperature and the activation energy of the macromolecular segments transport increase clearly, and enhanced crystallization degree of PA66 according to DSC results. These results demonstrate MPP-FR presented the nucleate effect for the crystallization of PA66. At the low shear rate, MPP-FR and MA-EPDM obviously enhanced apparent viscosities of the composites. This is attributed that MPP-FR improved the interfacial interaction of the composites, and MA-EPDM promoted the formation of high molecular weight structures by the reactions between MA and amine groups. All results in this paper were consistent, and showed the good interaction among PA66, GF, MPP and MA-EPDM, which were proved by the mechanical properties of the composites.     

半芳香尼龙6T/66的合成和非等温结晶动力学的研究

采用成盐、预聚合、固相聚合三步法制备高分子量的PA6T/66,用差示扫描量热法(DSC)研究了PA6T/66的非等温结晶动力学,结果表明:结晶温度随着降温速率的增大而降低;半结晶期T1/2随降温速率Ф的增大呈指数下降,表明结晶速率随降温速率的增大而提高;由用R-T法可以得到在不同结晶度下lgΦ对lgT有较好的线性关系。用Kissinger方法计算得到PA6T/66(55/45)非等温结晶活化能分别为ΔE=-61.51kJ/mol。     

PA66/PA12/clay based nanocomposites: structure and thermal properties

In a previous paper the structure and the physical properties of melt mixed polyamide 66 (PA66)/polyamide 12 (PA12) blends characterized by different compositions have been investigated by means of morphological and physical analyses. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) was introduced in order to evaluate its effect on blends structure and components miscibility. This paper completes the characterization of these materials investigating their thermal properties by means of standard and modulated differential scanning calorimetry (DSC, MDSC), dynamic‐mechanical analysis (DMA), and thermogravimetric analysis (TGA). The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed by analyzing the glass transition temperature (T_g) dependence on composition as well as the existence of strong segmental interactions between polymer components. A compatibilizing action of OMLS has been observed because of a lowering of interfacial tension avoiding coalescence phenomena between particles during melt mixing process. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrogen bonding in polyamide 66/clay nanocomposite

Hydrogen bonding in polyamide 66/clay nanocomposite (PA66CN) was first investigated with temperature Fourier transform infrared (FTIR), the results of which were compared with that of pristine polyamide 66 (PA66) with the same thermal history. FTIR spectra at room temperature revealed that there is essentially 100% hydrogen bonding in both PA66CN and PA66, and the difference in hydrogen‐bonding status between them is tiny. Additionally, DSC showed that the crystalline degrees and melting temperatures of PA66CN and PA66 prepared by melt quenching are similar. However, the changes of hydrogen bonding with temperature in PA66CN and PA66 are different. As the temperature rose, the hydrogen bonding in PA66CN attenuated and dissociated considerably at a smaller rate than PA66. According to transmission electron microscopic morphology of PA66CN, we analyzed the effect of nanodispersion clay layers on the motion of a polymer chain and the thermal expansion of crystalline lamella for interpreting the observed phenomenon. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2313–2321, 2003     

COMPARISON OF POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES PREPARED FROM POLYAMIDE 6 AND POLYAMIDE 66 BASED MASTER-BATCHES

Two master-batches,polyamide 66 (PA66)/organo-montmorillonite (OMMT) and polyamide 6 (PA6)/OMMT, prepared by melt compounding with methyl methacrylate (MMA) as co-intercalation agent,have been used to prepare nearly exfoliated PA661montmorillonite (MMT) nanocomposites.The resulting nanocomposites are compared in view of their morphology and properties.Nano-scale dispersion of OMMT is realized in both types of nanocomposites,as revealed by XRD,TEM and Molau tests.PA66/MMT nanocomposites having superior me...     

Obtaining nanocomposites of polyamide 6 and cellulose whiskers via extrusion and injection molding

Nanocomposites of polyamides with cellulose whiskers are difficult to obtain by conventional processing of extrusion and injection molding because of the low thermal stability of the cellulosic nanostructures and the relatively high processing temperature of polyamides, which is higher than the temperature of thermal degradation of cellulose whiskers. Thus, in this study cellulose whiskers were coated with polyamide 6 (PA6) in order to increase their thermal stability and prevent the formation of agglomerates. This coating on cellulose whiskers allows their application to obtain nanocomposites with polyamides, whose processing temperatures are relatively high, around 250 °C. Cellulose whiskers (CWs) were obtained from cotton fibers by acid hydrolysis. The freeze-dried CWs were coated with PA6 by dispersing them in formic acid; PA6 was solubilized in this suspension. The cellulose-coated whiskers (CCWs) were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electron microscopy (SEM-FEG) and infrared spectroscopy. SEM-FEG and TG results showed that the PA6 coating on CWs prevented high agglomeration of dried CWs and promoted an increase in their thermal stability from 180 to 280 °C, allowing the use of CCWs to obtain nanocomposites with PA6 using conventional processing routes, such as extrusion and injection molding, at appropriate processing temperatures. In this way, 1 wt% CCWs was used to prepare nanocomposites with PA6. The PA6 + 1CW nanocomposites were compared to neat PA6 without CWs. The samples were characterized by tensile tests and DSC, and the results showed that the PA6 coating on CWs was effective in raising the thermal stability of CWs, improving the dispersion of CWs in the matrix of PA6, resulting in a 45 % increase in the elastic modulus of the nanocomposite with only 1 wt% of coated cellulose whiskers in comparison to neat PA6.     

Structure development of polyamide‐66 fibers during drawing and their microstructure characterization

Structure development during drawing was studied for three sets of polyamide‐66 (PA66) fibers with density, optical microscopy, wide‐angle X‐ray diffraction, and Fourier transform infrared spectroscopy. The crystallinity, estimated by density measurements, remained virtually constant with increasing draw ratios, indicating that stress‐induced crystallization did not occur for the PA66 fibers drawn at room temperature, but there was a rapid transformation from a hedrite morphology to a fibrillar one. The absence of stress‐induced crystallization differed from the behavior of polyamide‐6, and this was attributed to the stronger hydrogen bonding between polyamide chains and the higher glass‐transition temperature of PA66. Polarized infrared spectroscopy was used to measure the transition‐moment angles of the vibrations at 936 and 906 cm^?1, which were found to be 48 and 60°, respectively. The crystalline orientation was estimated from the band at 936 cm^?1, and the increase with an increasing draw ratio was in close quantitative agreement with X‐ray diffraction data; this showed that infrared spectroscopy could be used reliably to measure the crystalline orientation of PA66 fibers. Because we were unable to obtain the transition‐moment angle of the amorphous bands, the amorphous orientation was obtained with Stein's equation. The amorphous orientation developed more slowly than the crystalline orientation, which is typical behavior for flexible‐chain polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1940–1948, 2002     

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.     

Crystallization of polypropylene,nylon-66 and poly(ethylene terephthalate) at pressures to 200 MPa: Kinetics and characterization of products

The crystallization kinetics of polypropylene (PP), polyamide (PA66), and poly(ethylene terephthalate) (PET) were studied, using a pressure dilatometer (to 200 MPa) to follow the volume changes associated with the crystallization process. The commonly used Avrami equation fitted the isothermal/isobaric crystallization data of PP and PA66 well. The Avrami exponent n was between 1.3 and 1.7, independent of crystallization pressure and temperature. Lines of constant Avrami rate parameter Z in the P-T plane were essentially parallel to the pressure dependence of the melting points and crystallization temperatures. However, the Avrami equation was not suitable for PET. The Malkin, Dietz, and Kim equations provided better fits. The crystallization half-time of PET increased with pressure at constant supercooling, in contrast to PP and PA66, for which it remained essentially unchanged. X-ray diffraction, differential scanning calorimetry, and pressure dilatometry were used to study the effect of formation pressure on the crystal structure, the melting point, and the density of products which were crystallized for short times (minutes) at various temperatures and pressures. No new crystal structures were found for PA66 and PET, but a mixture of monoclinic and triclinic crystals existed in PP above a formation pressure of 50 MPa. The melting points increased with formation pressure for PET, but remained unchanged for PP and PA66. Density at ambient conditions decreased with formation pressure for PP, but increased for PET and PA66. © 1994 John Wiley & Sons, Inc.     

Study of the Crystallization of an Aromatic Poly-ether-ketone (PK99) by Calorimetric and X-ray Analysis

An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T _g) and the melting temperature (T _m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T _g. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biodegradable liquid crystalline aromatic/aliphatic copolyesters. Part I: Synthesis, characterization, and hydrolytic degradation of poly(butylene succinate-co-butylene terephthaloyldioxy dibenzoates)

To increase the thermal and mechanical properties of the aliphatic polyester poly(butylene succinate) (PBS), a series of potentially biodegradable liquid crystalline aromatic/aliphatic random copolyesters were prepared by melt polycondensation of new mesogenic monomers dimethyl 4,4′-(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and 1,4-butanediol. The synthesized copolyesters were characterized by means of proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), polarizing light microscopy (PLM) and mechanical property measurements. The MTB content was varied so that the effects of the mesogen content on the thermal and mechanical properties, degradable behaviours and mesophase were examined. It was found that introducing the rigid rod mesogens could increase the thermal stability and the mechanical properties, while it reduced the melting temperature (T_m), the crystallization temperature (T_c), the degree of relative crystallinity (X_c) and the hydrolytic degradation rate. Only the homopolyester poly(butylenes terephthaloyldioxy dibenzoates) was able to show the schlieren texture characteristic of nematics.     

Investigation of structural and thermal characteristics of PVDF/ZnO nanocomposites

The structural and thermal behavior of PVDF/ZnO nanocomposites have been investigated by employing scanning electron microscopy (SEM),TEM, DSC, powder X-ray diffraction (XRD), thermally stimulated discharge current (TSDC), and transient current techniques. SEM/TEM observation indicated the homogeneous dispersion of functionalized ZnO nanoparticles throughout PVDF matrix. DSC shows that the crystallinity is influenced by the presence of ZnO nanoparticles in the PVDF matrix because the filler acts as efficient nucleating agent to facilitate PVDF crystallization. DSC results indicated the enhancement of the glass transition temperature (T _g), melting temperature (T _m) and crystallization temperature (T _c) of nanocomposites compared to pristine PVDF. XRD shows that the full-width at half maximum decreases with increasing ZnO content, which is attributed to the improvement in crystallinity. The incorporation of ZnO nanoparticles influences the modification of polarization process in PVDF as observed by means of TSDC and transient current study.     

脂肪族聚酰胺热膨胀行为的研究

通过热膨胀测试,示差扫描量热分析(DSC)、广角X射线衍射(WAXD)与傅里叶变换红外光谱(FTIR)等方法研究了4种脂肪族聚酰胺玻璃化转变温度(Tg)、结晶行为以及氢键强度对热膨胀行为的影响,探索了影响脂肪族聚酰胺热膨胀的本质.DSC和X射线衍射结果表明,聚酰胺中结晶部分的热膨胀系数要低于无定形部分,但聚酰胺的熔融温度和结晶度对热膨胀的影响不够明确.相比较其它脂肪族聚酰胺,聚酰胺56(PA56)具有较高的玻璃化转变温度和较低的亚甲基/酰胺基(CH2/CONH)比例,表现出较低的热膨胀系数.研究发现,在相同条件下制备的脂肪族聚酰胺体系中,CH2/CONH比例或Tg与热膨胀系数具有明显的线性关系,随着CH2/CONH比例的降低或Tg的升高,热膨胀系数显著减小.FTIR的结果表明,聚酰胺分子链间的氢键密度和氢键强度随温度升高衰减的程度是影响其热膨胀行为的关键因素.     

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, ¹H NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times.     

Isothermal and nonisothermal crystallization kinetics of novel odd-odd polyamide 9 11

A study on isothermal and nonisothermal crystallization kinetics of odd-odd polyamide 9 11 was carried out by differential scanning calorimetry (DSC). The equilibrium melting temperature of polyamide 9 11 was determined to be 199.1 °C. The Avrami equation was adopted to describe isothermal crystallization of polyamide 9 11. Nonisothermal crystallization was analyzed using both the Avrami relation modified by Jeziorny and the equation suggested by Mo. The isothermal and nonisothermal crystallization activation energies of polyamide 9 11 were determined to be −310.9 and −269.0 kJ/mol using the Arrhenius equation and the Kissinger method, respectively.     

Thermal transfer simulation regarding the rotational moulding of polyamide 11

Simulation of thermal phenomena in rotational moulding is very important to follow the evolution of the temperature in various zones of this process. It was a question of modelling heat gradients developing in rotational moulding part. Thermal model tested take into account the temperature change (thermal transfer mechanism) of melting and crystallization pseudo-stages (enthalpy method). Series of tests in polyamide 11 (PA11) were carried out by means of rotational moulding STP LAB, and non-isothermal crystallization kinetics of rotational moulding PA11 grade are measured and analysed by DSC technique type TAQ20. A result of non-isothermal crystallization of the studied polyamide was confronted with Ozawa model. In order to test the validity degree of enthalpy method (layer to layer), another approach based on Ozawa model has also been used in the case of cooling pseudo-stage. As results, the rotational moulding of PA11 was successfully carried out. The simulation of the fusion and crystallization stages, by application of Ozawa model coupled with enthalpy method gave a good representation of experimental data.