Effect of casting conditions on polymorphism of nylon-12

Polymorphism in nylon-12 film, which appears on casting from a phenol-ethanol solution, has been investigated by x-ray diffraction and infrared absorption. The casting temperature was varied from 30 to 130°C and the ambient atmospheric pressure from 50 to 760 Torr. Casting at 30°C gives only the α form, while casting above 90°C yields only the γ form. At intermediate temperatures, both α and γ forms are obtained, with the γ content increasing as the casting temperature and/or the rate of evaporation of solvent are increased. The ethanol component of the casting solvent appears to act only as a melting-point depressant for phenol. In contrast, nylon-6 film cast from the same solvent system between 30 and 160°C gives only the α form. It is proposed that the difference in polymorphism of nylons-12 and -6 is caused by differences in molecular flexibility due to the length of the methylene chain.     

Structure of pressure-crystallized polypropylene

The structure of polypropylene crystallized at pressures up to 5000 atm. has been studied. Upon slow cooling from the melt at 320 atm., the γ modification, previously found only in low molecular weight and stereoblock fractions, begins to appear in small amounts in addition to the normal α monoclinic form. As the pressure is increased further, a larger proportion of the sample crystallizes in the γ form until, at 5000 atm., only the γ modification is present. X-ray and DTA studies show that the γ form of polypropylene transforms to the normal α modification at a temperature only slightly below the γ melting point. Evidence is presented which favors the occurrence of a solid-state transition as a model of transformation to the α form. Results from isothermal crystallizations at low supercoolings and annealing experiments under high pressure show that the melting point of the γ modification of polypropylene is very sensitive to crystallite perfection.     

Multiple melting in nylon 66

Either of the two endothermic melting peaks found by differential thermal analysis of nylon 66 may be converted to the other by appropriate choice of annealing conditions. The two peaks are considered due to the melting of two morphological species, forms I and II. Form I is relatively fixed in melting temperature, while the form II melting temperature varies with annealing conditions and can be either above or below form I. The two forms can be distinguished by whether or not the conversion I → II takes place; if the sample is in form II no change in the thermogram is observed under suitable conversion conditions. The conversion of form I to form II also takes place during cold drawing. It has been previously shown that form I results from rapid cooling from the melt, and form II results from slow cooling. Form I appears to be kinetically favored, while form II is thermodynamically preferred. The variability in the form II melting point is attributed to variable crystal size and/or perfection.     

Electron trapping and luminescence mechanism in thermoluminescence of irradiated polycarbonate

Thermoluminescence of polycarbonate irradiated by electron beams was observed in order to investigate the trapping of electrons and the luminescence mechanism. The thermoluminescence glow curve is composed of three components. The peaks appear at ?150°C (α peak), ?120°C (β peak), and ?30°C (γ peak). The α peak is attributed to recombination of cations with electrons released from trapping sites formed by carbonate groups. The β peak is attributed to small amounts of impurities. The γ peak is perhaps due to untrapping of electrons from the phenoxy anion. The luminescence intensity of the α peak is linearly dependent on the absorbed dose, and that of the β peak is approximately proportional to the cube of the dose. The appearance of these peaks is presumably closely related to local molecular motions.     

An examination of the crystal structures present in nylon-6 fibers

The variety of wide-angle x-ray scattering (WAXS) patterns exhibited by nylon-6 fibers with different fabrication histories is rationalized using a model comprising three limiting structures, viz., an α, a γ, and a pleated α structure. The γ and pleated α structures both have a single broad reflection in the range 2θ = 19° ?25°, but differ in their annealing behavior. At 205° (in vacuo), the pleated α structure converts to the normal α structure by removal of the pleats, without breaking any hydrogen bonds. The γ structure, however, remains unchanged under this annealing condition since it is necessary to break all the hydrogen bonding in the structure to convert it to the α form. Different fabrication routes produce fibers which resemble the three ideal structures to varying extents. Fibers extruded at low speeds (and hence low spinline tension) resemble a mixed conventional α/pleated α structure with only a small γ component. Increasing the take-up speed (and hence the spinline tension) of the as-spun fiber, or in-line drawing of the low orientation fiber (without prior storage), increases the γ content. If drawing of the low orientation fiber takes place after several hours storage (off-line drawing), a largely α structure is produced. The intensity of the 020 reflection in the γ structure is shown to be very dependent on the degree of crystalline orientation in the sample.     

Solution crystallization of nylon 12

Electron microscopy and x-ray diffraction data have been obtained on nylon 12 crystallized from 1-hexanol, 1,6-hexanediol, and hexylene glycol. Ribbonlike lamellar crystals of the γ form are obtained by crystallization from all the solutions and elongated flat crystals of the α form by crystallization from the 1-hexanol and hexylene glycol solutions. The direction of the hydrogen bond in these crystals is almost parallel to that of maximum crystal elongation. α- and γ-form crystals both grow from 1-hexanol and hexylene glycol at appropriate crystallization temperatures. γ-form crystals alone are obtained from 1,6-hexanediol solution at every crystallization temperature. The long periods measured by small-angle x-ray diffraction for the solution-grown crystals are in the range 7.6–10.6 nm. The melting behavior of the solution-grown crystals is examined and discussed. The melting temperatures of the γ form may be lower than that of the α form. An equilibrium melting temperature of 208.4°C for γ-form crystals is obtained by using a relation between thickness of lamellar crystals and their melting temperatures observed by differential scanning calorimeter measurements. Solvents affect the growth of the two crystalline forms in solution crystallization.     

Effects of swelling and annealing on the viscoelastic behavior of the melt-crystallized and solution-crystallized polypropylene

The effects of swelling and annealing treatments on viscoelastic behavior were studied in melt-crystallized and solution-crystallized samples of isotactic polypropylene (iso-PP) over the temperature range ?150 to 150°C. The log E″ versus T curves exhibited α, β, and γ peaks in order of decreasing temperature. The β peak of the melt-crystallized sample shifted to higher temperatures after annealing, but was not affected by swelling. The α peak of melt-crystallized polymer was affected by swelling treatments. It increased in height and shifted to lower temperatures almost linearly with the volume fraction of absorbed solvent. The magnitude of the shift was independent of the solvent species—toluene, p-xylene, tetralin, carbon tetrachloride—however, it depended significantly on the temperature at which the sample had been heat treated. For solution-crystallized polymer, no peaks in log E″ were observed in the temperature range of the β peak of melt-crystallized material, but the α peak appeared larger and broader, and at higher temperature than the corresponding peak in the melt-crystallized polymer. After swelling or annealing, the low-temperature component of the α peak of the solution-crystallized sample decreased in height and at the same time a new loss peak appeared at ?55 and 0°C, respectively, is swollen and annealed samples. In particular, in the case of annealing treatments, the high-temperature component of the α peak shifted to still higher temperatures. From these results on the solution-crystallized sample it can be deduced that the segmental motions in the amorphous phase are very strongly constrained by surrounding crystalline phases as compared with those in the amorphous phase of the melt-crystallized sample, and the constraints imposed on the segmental motions are released to a great extent by both treatments. Finally, swelling effects on the γ peak were examined. The γ peak of the melt-crystallized sample decreased in height after swelling. On the other hand, the γ peak of the solution-crystallized sample separated into two peaks, which might be attributed to the mechanical relaxations in the crystalline and amorphous phases.     

Melting behavior of highly stretched isotactic polypropylene film

Isotactic polypropylene film was stretched in poly(ethylene glycol) at 140°C and its melting behavior was investigated by using a differential scanning calorimeter (DSC-1B). The shape of the melting curve depends largely on the stretching ratio, v. A sample stretched to moderate extension (1 < v < 3.5–4) has only a single melting peak (163°C) in the thermogram. When the sample is stretched beyond v = 3.5–4, the thermogram becomes more and more complex with increase of v, and some peaks appear when stretched to 10 < v < 13. The lowest peak which is considered to be the melting peak of the intermolecular crystals produced by the unfolding of chain molecules in the lamellae develops gradually with increase of v. In the thermogram for v = 18 the lowest temperature peak is most pronounced, in contrast to the highest temperature peak which decreases markedly in intensity. The phenomenon shows that large amounts of lamellar crystals are converted to intermolecular crystals in this region. On further stretching (v > 20) a very sharp high temperature peak appears, whose half-width is about 1°C. Qualitatively similar results were obtained for the samples stretched in poly(ethylene glycol) at 150°C and in air at 140 and 150°C.     

Thermal analysis and X‐ray scattering study of metallocene isotactic polypropylene prepared by partial melting

In this study, we examine the effects of heating, nucleation, cooling, and reheating on the thermal properties and structure of metallocene isotactic polypropylene (m‐iPP) that had been prepared initially in a standard state containing nearly equal amounts of the crystallographic α and γ phases. Heat treatment was achieved through partial melting and annealing by the heating of samples to self‐nucleation temperatures (T_n's) that spanned and exceeded the entire range of melting of the standard state, from 122 to 160 °C. The relative amounts of α and γ crystals are determined from the area under the unique wide‐angle X‐ray reflections. The lower and upper endotherms are caused by the melting of γ and α crystals, respectively. Four distinct regions of T_n were identified on the basis of the thermal and structural parameters of m‐iPP. In region I, T_n is below the peak melting temperature of the γ phase. Here, γ crystals are annealed and α crystals are barely affected by T_n. In region II, T_n is above the peak of the lower endotherm but below the peak of the upper endotherm. γ crystals melt, and α crystals anneal. In both regions I and II, the portion of the sample melted at T_n recrystallizes epitaxially with existing parent α lamellae as the substrates, and the amount of α always exceeds the amount of γ. In region III, T_n is above the peak of the upper endotherm, and all γ crystals and some or all α crystals are melted at T_n. The number of α‐crystal nuclei steadily decreases as T_n increases, causing systematic depression of the crystallization and melting temperatures seen during cooling. Finally, in region IV, T_n exceeds the upper endotherm, and only small self‐nuclei or heterogeneous nuclei remain. Recrystallization is now suppressed to lower temperatures. For regions III and IV, a crossover behavior in the relative amounts of α and γ is observed during cooling from T_n. Because of the effective nucleating ability of α toward γ, as the temperature drops, the amount of γ increases and then exceeds the amount of α. With subsequent reheating, the reverse crossover occurs because of the lower melting point of γ. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1644–1660, 2002     

Thickening of crystals during rapid heating. I. Linear polyethylene and nylon-6

The change of long spacing in polyethylene and nylon-6 during heating at 18°C/min. was measured with an apparatus devised for rapid measurement of the small-angle x-ray diffraction. The apparatus made it possible to obtain a diffraction profile in 1.8 sec. Long spacings increased notably at high temperatures near the melting point, as has been observed during low-rate heating. However, the increase in long spacing during heating was very small in a methoxymethylated nylon-6 sample. This suggests that the increase in the long spacing at high temperature is due to the thickening of crystals. The long spacing in polyethylene samples in the vicinity of the melting point is apparently independent of thermal history.     

Dielectric and rheo-optical properties of some ethylene-carbon monoxide copolymers

Studies were made on films of copolymers of ethylene with 0.5 and 1.0 mole-% carbon monoxide. The carbon monoxide appeared negligibly to affect the degree of crystallinity, melting point, morphology, and dynamic mechanical spectra. Infrared dichroism showed that the orientation of the carbonyl groups was comparable with that of the crystalline CH₂ groups and indicated that the carbonyl groups are at least partially within the crystals. This is confirmed by x-ray measurements which indicate an expansion of the a-axis spacing and by an appreciable increase in the height of the α dielectric loss peak which has been assigned to crystalline motion. This α loss peak moves to a lower temperature with increasing carbonyl content, while the γ dielectric loss peak moves to higher temperatures. Activation energies of 25, 35, and 15 kcal/mole for the α, β, and γ peaks, respectively, were independent of carbonyl content and comparable with values for oxidized polyethylene.     

Studies on crystalline forms of nylon 6. II. Crystallization from the melt

The relative amounts of the α and the γ crystalline forms of nylon 6 obtained from the melt under different crystallization conditions have been studied by an x-ray diffraction procedure by comparison with a calibration curve obtained from the diffraction of standard samples. The weight fraction of the α form decreases with increasing crystallization temperature and that of the γ form increases. Growth of the α form is predominant in crystallization at 100°C and of the α form at 200°C. The amount of the α form tends to increase on annealing at 200°C for specimens crystallized at any temperature.     

α–γ transition in nylon 6

The α to γ transition that occurs in nylon 6 upon iodine treatment was investigated by infrared spectroscopy, differential thermal analysis, and x-ray diffraction techniques. Thin films of nylon (0.2 mil) were treated in either iodine–potassium iodide aqueous solution or in iodine vapor. Very short treatment times, in the order of 30 sec, were found to effect the transition when a solution 0.5M with respect to iodine was used. The infrared spectra of the iodine nylon complexes formed from either the α- or γ-nylon 6 treated in vapor or dissolved iodine were all similar. This is an indication that molecular iodine is the active species in forming the complex. The temperature of the washing solution used to remove the iodine from the nylon determines whether an α-nylon 6 or γ-nylon 6 is obtained from the complex after washing. Nylon 6 plaque surfaces and thin films are similar in their behavior towards the iodine treatment. The γ-nylon 6 is a stable modification at all temperatures below its melting point. The conversion of the γ form back to the α modification can occur only if the hydrogen bonding is severely affected, e.g., by phenol treatment, iodine treatment, melting, etc. Infrared spectroscopy provided no evidence for an α–γ transition in nylon 6 on heating the sample continuously through its melting point. The shapes of the melting peaks in the above two modifications of nylon 6 were sufficiently different to provide a means of identifying the two crystalline forms.     

热历史对尼龙1212熔融行为的影响

利用DSC方法研究了不同热历史条件对尼龙1212熔融行为的影响.不同的热历史条件下,在DSC曲线上,观察到尼龙1212产生2个或3个熔融峰,依据聚合物结晶理论,对各峰的来源进行了分析.在160℃下不同温度退火120 min的尼龙1212样品DSC曲线上,低温结晶熔融峰主要由低温结晶形成的一些微晶体或者片晶熔融产生,其晶体完善程度较差,熔融峰值较低,峰面积较小;主熔融峰是由样品在淬火过程中形成的晶体和升温过程中低温结晶形成的晶体的熔融重结晶形成较为完善的晶体熔融所产生,熔融峰值较高,峰面积较大.在不同的升温速率条件下,熔融峰温度有所移动,表明不同升温速率条件下产生的熔融峰的结晶晶型是相同的.在不同结晶时间下结晶,延长结晶时间对较高完善程度晶体的生长有利.在不同温度下依次退火处理的样品,熔融产生两个附加峰,这两个附加峰的峰温都比它们相应的退火温度高,而峰高和峰面积随退火温度降低而减小.根据等温结晶结果,由Hoffman方法确定了尼龙1212的平衡熔融温度为202.8℃.     

Hard-segment polymorphism in MDI/diol-based polyurethane elastomers

X-ray analyses of methylene-bis(4)phenyl isocynate(MDI)/diol/poly(tetramethylene adipate) polyurethane elastomers prepared using hexanediol (HDO), butanediol (BDO), and propanediol (PDO) point to the development of a second crystalline structure in the hard segments as a result of thermal elongation and annealing. The HDO polymer crystallizes initially in the fully extended conformation, but a second crystal structure, a contracted form, develops with stretching and annealing at 130°C. In contrast, the BDO and PDO polymers crystallize initially in contracted conformation, but fully extended forms develop as a result of elongation and annealing. Only a contracted conformation has been seen so far in hard segments prepared using ethylene glycol (EDO) as the chain extender. These results correlate very well with DSC data for the same polymers. The development of the new crystal structures is accompanied by the appearance of new hard-segment melting peaks in the DSC traces. For the HDO polymer, the new peak for the contracted form appears at a higher temperature than that for the original extended form; for the BDO and PDO polymers the new peaks for the extended forms appear at lower temperatures than those for the contracted forms. Only a single peak is seen for the EDO polymer, for which only one crystal structure has been detected for the hard segments. These results indicate that the development of polymorphic crystal structures must be taken into account in interpreting the multiple melting phenomena seen for the hard domains in polyurethane elastomers.     

Vibration-induced change of crystal structure in isotactic polypropylene and its improved mechanical properties

In order to understand the formation of different crystal structures and improve the mechanical properties of isotactic polypropylene (iPP), melt vibration technology, which generally includes shear vibration and hydrostatic pressure vibration, was used to induce the change of crystal structure of iPP. iPP forms α crystal structure in traditional injection molding. Through melt vibration, crystal orientated and its size became smaller, and a change of crystal structure of iPP from α form to β form and γ form was achieved. Therefore, the mechanical properties of iPP were improved. At high melting temperature (230 °C), only β form can be induced. At low melting temperature (190 °C), either β form or γ form can be induced, depending on the combination of frequency and vibration pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2385–2390, 2004     

Side-chain relaxation in stereoregular poly(isobutyl methacrylate)

The effects of stereoregularity on the low-temperature relaxation processes were studied by dynamic mechanical measurements on isotactic and syndiotactic polyisobutyl methacrylates (iso-PiBMA and syn-PiBMA). The α, β, and γ relaxation processes were observed in both stereoregular forms. Both the α, and β loss peaks were at lower temperatures for iso-PiBMA than for syn-PiBMA. The γ loss peak was observed at about ?155°C at 30 Hz for both forms, and the apparent activation energy of this process was same for both samples within experimental error (6.7 ± 0.5 kcal/mole). It was reduced from these results that the α and β processes are both considerably influenced by the isotactic configuration but the γ process is not.     

Melting of constrained drawn nylon 6 yarns

A differential scanning calorimeter (DSC) was used to study the melting behavior of drawn nylon 6 yarns which were prevented from shrinking during heating. The DSC curves exhibit a single melting peak at a higher temperature instead of the double peaks which, as reported previously, were observed in the unconstrained state. The curve is explained quantitatively in terms of the perfecting of the original crystals followed by monotonic melting of these crystals during heating. The single peak results from the absence of the partial melting–recrystallization process which plays an important role in the appearance of double peaks. The temperature of the melting peak for the constrained sample increases linearly with draw ratio, and is unaffected by drawing temperature and by annealing at constant length after drawing. The elevation of the melting temperature is discussed on the basis of the entropy effects predicted theoretically by Zachmann. Thermal analysis of constrained samples has proved to be useful for detecting oriented crystals which coexist with unoriented ones.     

Relations between dynamic mechanical properties and melting behavior of nylon 66 and poly(ethylene terephthalate)

Nylon 66 films exhibiting form I melting behavior show the γ mechanical relaxation at ?140°C. Samples which have form II melting behavior do not show this relaxation. The γ relaxation disappears when material having form I behavior is converted to material having form II behavior by annealing or by cold drawing. The form I and form II types of melting behavior are also found in poly(ethylene terephthalate); the interconversions and thermal behavior of the forms are analogous to the nylon 66 case. In poly(ethylene terephthalate), the β relaxation at ?40 to ?60°C is present only when form I melting behavior is found. Conversion to form II melting behavior by annealing or drawing (80°C) again causes the relaxation to disappear. No β relaxation was found in amorphous polymer. The γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) can therefore be associated with the crystalline structure responsible for form I melting behavior. Form I melting behavior has been associated with foldedchain crystals based on previous work. It is therefore postulated that the γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) are associated with motions in the chain folds. This assignment is not inconsistent with the change in the γ dispersion of nylon 66 with the number of backbone CH₂ units, since these will affect the fold structure.     

Molecular transitions in an alternating copolymer of ethylene and chlorotrifluoroethylene

Three transitions have been found with peaks at 130°C (α), 88°C (β), and ?65°C (γ), by mechanical relaxation techniques for a quick-quenched sample of an alternating copolymer of ethylene and chlorotrifluoroethylene. The intensity of the α transition was found to increase with an increase in crystalline content. It was observed at 150°C by infrared and x-ray diffraction techniques and by mechanical relaxation spectra on an annealed sample. X-ray diffraction and dichroic infrared measurements were conducted on oriented specimens as a function of temperature. These data showed that the β transition was accompanied by a change in lateral bonding distances in the crystalline phase and a conformational change attributed to an “unkinking” of the molecular chain. The β transition was found to be related to the amorphous phase and the onset of the β peak corresponded to the transition at 35°C found by infrared techniques and previously by a torsional modulus method. It was tentatively assigned to the glass transition. A more definitive assignment of the β transition would depend on a detailed structural analysis of the γ transition. The γ peak was not studied in detail in the present work.