Effects of pressure on the compressibility and crystallization of fiber-forming polymers

The effects of pressure on the compressibility and crystallization of three fiber-forming polymers, poly(tetramethylene terephthalate), nylon 66, and Qiana® nylon, have been studied. The Instron capillary rheometer was adapted as a high-pressure dilatometer for all the high-pressure experiments. The compressibility results reaffirmed that polymers are highly compressible, and their compressibilities are nonlinear at temperatures above the glass transition temperatures. Polymer melts show higher compressibility than do polymers in the solid state. The kinetics of crystallization of these polymer melts under high pressures were studied. Analysis of the data revealed low Avrami exponents at high pressures. It seems that the kinetics of crystallization of these polymers from the melt under high pressure are different from those at normal pressure. Crystallization temperatures of these polymers were also measured. The crystallization temperatures are considerably higher at higher pressures.     

Thermodynamics of crystalline linear high polymers. V. Extended-chain copolymers of polyethylene

Ethylene—propylene and ethylene—butene-1 copolymers with up to 1.7 side groups per 100 carbons have been crystallized at 227°C. and under 4100–4900 atm. pressure. The resulting crystalline polymers are at least partially of extended-chain crystal morphology. Comparison with the same polymers crystallized at atmospheric pressure, which gives folded-chain crystal morphology, revealed: (1) a density higher by 0.008–0.019 g./cm.³ depending on copolymer content; (2) a similar decrease of crystallinity with side group concentration; (3) a similar decrease of the beginning of melting from 125°C. for homopolymer to 65°C. for 1.7 side groups per 100 carbons; (4) a higher (138 ± 0.8°C.) experimental maximum melting point which, in contrast, is independent of copolymer content and seems to vary only with the fraction of low molecular weight material; (5) a decreasing amount of high-melting crystals with increasing copolymer content (72–8%) and an increasing amount of low-melting crystals (27–53%) with increasing copolymer content. In addition, superheating, which reached 5.5°C. for 50°C./min. heating rates, was detected. It was concluded that high-pressure crystallization leads, at least for part of the crystals, to solid solution formation, while atmospheric pressure crystallization does not. Which mode of crystallization is achieved seems kinetically determined. Experimental techniques were dilatometry, DTA, and calorimetry.     

Transient and athermal effects in the crystallization of polymers. II. Nonisothermal crystallization

Nonisothermal crystallization of several polymers was investigated with differential scanning calorimetry and optical microscopy. The results indicated that as in the case of isothermal processes, crystallization starts with nucleation on noncompletely melted crystalline residues. It is assumed that if the crystalline residues are subcritical at melting temperatures, they can become stable by an athermal mechanism during cooling. There is also some contribution of nucleation on heterogeneities. The next mechanism of nucleation is a classical homogeneous process occurring by thermal fluctuations. The results showed the non‐steady‐state character of the nonisothermal crystallization of polymers. In the investigated range of cooling rates, the non‐steady‐state character of nonisothermal crystallization of polymers is dominated by the transient thermal effects. In the range of high temperatures, the transient homogeneous nucleation can be interpreted with the Ziabicki model, and the steady‐state rate determined from nonisothermal experiments coincides with the rate determined in isothermal crystallization. The athermal nucleation occurring at the beginning of crystallization from noncompletely melted aggregates seems to be independent of the applied cooling rate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 68–79, 2003     

Extended-chain crystals. I. General crystallization conditions and review of pressure crystallization of polyethylene

This is the first paper of a series of reports concerning extended-chain crystals of flexible, linear high polymers. The general conditions for crystal growth are discussed. Polymer crystallization is described as a two-step process: nucleation of each crystallizing molecule to a folded-chain conformation, followed by an increase in fold length in a solid-state reorganization step. This reorganization step is enhanced in the case of polyethylene by crystallization at high temperature under elevated pressure. Mechanical deformation during crystallization is also able to produce extended-chain crystals. The most promising method, however, is crystallization during polymerization. Previous work on crystallization of polyethylene under elevated pressure is critically reviewed.     

The effect of pressure on the mechanical properties of polymers. IV. Measurements in torsion

Stress relaxation was studied in torsion under superposed hydrostatic pressure using a newly constructed device. Two materials, a styrene–butadiene rubber and a butadiene rubber, were studied in the range from ?60 to 30°C at pressures up to 500 MPa. The time–temperature–pressure superposition of the data can be described by the FMT form of the free-volume theory which uses input from relaxation experiments at high pressure. The applicability of the Havlí?ek–Ilavský–Hrouz form of the Adam–Gibbs theory was also examined. This theory, which does not require information from high-pressure relaxation experiments, offers less flexibility than the FMT theory and is less successful in predicting superposition. The data are also examined in light of an adaptation of the Simha–Somcynsky equation of state to the free-volume theory. Prediction of the effect of pressure by the theory requires a single adjustable parameter. It was possible to calculate the free-volume parameters of several polymers without use of information from high-pressure experiments.     

Infrared study of high-pressure crystallization of polyethylene

The high-pressure crystallization of polyethylene in a diamond cell has been studied by infrared spectroscopy. The splitting of the CH₂ rocking band at 720–730 cm^?1 as a function of pressure was analyzed. It was found that pressure alone up to 3 kbar will not change the distance between methylene groups in the unit cell. However, this distance can be shortened by crystallization at this pressure. Intensities of selected crystalline (1176 and 1050 cm^?1) and amorphous (1303, 1352, and 1368 cm^?1) bands were measured on samples before and after high-pressure crystallization, and also on samples of various densities crystallized under atmospheric pressure. The increase in the intensities of crystalline bands and concomitant decrease in amorphous bands, together with density changes, indicate that the crystallinity can be enhanced by crystallization under high pressure. Nevertheless, the crystallinity of polyethylene crystallized at high pressure is comparable with that of polyethylene crystallized at atmospheric pressure at low undercooling for long periods of time.     

Organometallic polymers. XXIX. Synthesis and characterization of ferrocene-containing siloxane polymers from bis(dimethylamino)silane–disilanol condensation

A new monomer, 1,1′-bis(dimethylaminodimethylsilyl)ferrocene, was synthesized by two routes and polymerized with three aryl disilanols: dihydroxydiphenylsilane, 1,4-bis(hydroxydimethylsilyl)benzene, and 4,4′-bis(hydroxydimethylsilyl)biphenyl, yielding three different polysiloxanes. Melt polymerizations carried out at 1 torr pressure and 100°C resulted in the highest molecular weight polymers. Intramolecular cyclization competed with intermolecular chain extension in polymerization of the bis(aminosilane) with dihydroxydiphenylsilane, resulting in isolation of a bridged derivative, 1,3,5-trisila-2,4-dioxa-1,1,5,5-tetramethyl-3,3-diphenyl[5]ferrocenophane. Cyclization did not compete significantly during the formation of polymers from this bisaminosilane and the two remaining diols, as evidenced by higher yields and greater molecular weights. These polymers could be cast as tough flexible films, and fibers could be drawn from their melts. TGA and DSC data showed the polymer formed from 1,1′-bis(dimethylaminodimethylsilyl)ferrocene and 1,4-bis(hydroxydimethylsilyl)benzene to be at least as thermally stable as an arylene siloxane polymer which differed from the ferrocenylsiloxane structure only in the replacement of the ferrocene moiety with a p-substituted phenylene linkage. The ferrocene-containing polymers were generally hydrolytically stable under conditions of refluxing THF–H₂O(10 : 1) for 1 hr. The polymer-forming reaction was found to follow second-order kinetics, and the specific rate constants for formation of two of the polymers were measured.     

DFT studies on 7-nitrotetrazolo [1,5]furazano[4,5-b]pyridine 1-oxide: crystal structure,detonation properties,sensitivity and effect of hydrostatic compression

A new high energy density compound 7-nitrotetrazolo[1,5]furazano[4,5-b]pyridine 1-oxide (NFP) was studied. The molecular geometrical and electronic properties, heat of formation and detonation properties were predicted. Two crystal polymorphs of NFP were also predicted and compared well with experimental results. According to the constitution of the frontier energy bands, the tetrazol ring of NFP may be the active position of thermolysis. The calculated band gaps indicate the sensitivity of α-NFP is slightly lower than that of β-NFP. The effects of hydrostatic compression on the more stable form α-NFP were investigated in the pressure range of 0–100 GPa. α-NFP has an anisotropic compressibility. The band gap reduction is more pronounced in the low-pressure region than in the high-pressure region and the gap drops to nearly zero at 15 GPa, which means that the crystal changes its electronic character toward a metallic system. The analysis of density of states indicates that the electronic nonlocality increases under the influence of pressure.     

High-pressure phases in polymers. V. Crystallization studies of synthetic cis-polyisoprene

The effects of elevated pressure on the morphology and crystallization kinetics of cis-polyisoprenes containing 2–2.5% trans units have been determined. Lamellar growth rates of both α and β crystals are enhanced by elevated pressure. The degree of enhancement of α-crystal rates is much greater resulting in an effective suppression of β growth. Differences in lamellar growth rates between these polymers and cis-polyisoprene result from different preexponent values. Hedritic or axialitic growth, presumably due to low-molecular-weight fractions, is observed in shish-kebabs present in strained films. The high-pressure hexagonal phase cannot be grown in these polymers.     

Polyethylene-polystyrene gradient polymers. II. The swelling-induced crystallization in the PE-PS gradient polymers and modified by styrene LDPE samples

In this paper, the swelling-induced crystallization effect observed in gradient polymers and in low density polyethylene modified by styrene is discussed. The polymerization-induced crystallization in the PE-PS gradient polymers is demonstrated and its influence on the crystalline phase stability in the LDPE matrix exhibited. Some new information about the specific, internal structure of the gradient polymers is presented, which confirms the differences between formation of these substances and other gradient polymers previously investigated.     

Some recent developments in SPM of crystalline polymers

Some recent advances in the application of atomic force microscopy to crystalline polymers are detailed. Ultra‐high resolution imaging of crystal surfaces, combined with the analysis of computer generated Connolly surfaces, enables the unambiguous identification of features on the cellulose crystal surface at near‐atomic resolution. The electronic enhancement of the quality factor of the cantilever when tapping in liquids enables a considerable improvement in force sensitivity to be obtained, allowing the fully saturated surface of an isotactic polystyrene gel to be imaged under the solvating molecule, at nanometre resolution. A series of experiments are detailed in which processes such as crystallization, crystal thickening and crystal deformation are followed in situ, in real time, providing significant new insights into long standing problems in polymer science.     

Transient and athermal effects in the crystallization of polymers. I. Isothermal crystallization

The isothermal crystallization of poly(propylene) and poly(ethylene terephthalate) was investigated with differential scanning calorimetry and optical microscopy. It was found that the induction time depends on the cooling rate to a constant temperature. The isothermal crystallization of the investigated polymers is a complex process and cannot be adequately described by the simple Avrami equation with time‐independent parameters. The results indicate that crystallization is composed of several nucleation mechanisms. The homogeneous nucleation occurring from thermal fluctuations is preceded by the nucleation on not completely melted crystalline residues that can become stable by an athermal mechanism as well as nucleation on heterogeneities. The nucleation rate depends on time, with the maximum shortly after the start of crystallization attributed to nucleation on crystalline residues (possible athermal nucleation) and on heterogeneities. However, the spherulitic growth rate and the exponent n do not change with the time of crystallization. The time dependence of the crystallization rate corresponds to the changes in the nucleation rate with time. The steady‐state crystallization rate in thermal nucleation is lower than the rate determined in a classical way from the half‐time of crystallization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1835–1849, 2002     

Welding immiscible polymers with a supercritical fluid

Polymer adhesion between two immiscible polymers is usually poor because there is little interpenetration of one polymer into the other at the interface. Increasing the width of the interfacial zone can enhance adhesion and mechanical properties. In principle, this can be accomplished by exposing heterogeneous polymer materials to a high-pressure fluid. The fluid can act as a common solvent and promote interpenetration. It also increases chain mobility at the interface, which helps to promote "welding" of the two polymers. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state was used to investigate this phenomenon, especially the effect of the high compressibility of supercritical (SC) fluid on the compatibilization of two incompatible polymers. We calculate the interfacial density profile, interfacial thickness, and interfacial tension between the two polymers with and without the SC fluid. We find that the interfacial tension is decreased and the interfacial thickness is increased with high-pressure SC fluid for the ternary systems we have investigated. As the critical point is approached and the SC compressibility becomes large, no enhancement or deleterious effects on compatibilization were observed.     

Molecular-dynamics simulation of crystallization in helical polymers

The molecular mechanism of crystallization in helical polymers is a fascinating but very difficult subject of research. We here report our recent efforts toward better understanding of the crystallization in helical polymers by use of molecular-dynamics simulation. With straightforward approaches to the problem being quite difficult, we adopt a different strategy of categorizing the helical polymers into two distinct types: one type is a simple bare helix which is essentially made of backbone atomic groups only and has smoother molecular contours, and the other is a more general helix having large side groups that would considerably hamper molecular motion and crystallization. Both types of helical polymers are here constructed by use of the united atom model, but they show quite distinct crystallization behavior; the crystallization of the former-type polymer is rather fast, while that of the latter-type polymer is extremely slow. We find that the bare helix, when rapidly cooled in free three-dimensional space, freezes into partially ordered state with limited intramolecular and intermolecular orders, and that remarkable improvement of order and growth of an ordered chain-folded crystallite occurs by very long-time annealing of the partially ordered state around the apparent freezing temperature. We also study crystallization of the bare helix upon a growth surface; the crystallization in this case proceeds much faster through highly cooperative process of the intermolecular and the intramolecular degrees of freedom. On the other hand, crystallization of the realistic model of isotactic polypropylene (iPP) having pendant methylene groups is found to be extremely sluggish. By restricting the spatial dimension of the system thereby fully disentangling the chain, we observe that the molecule of iPP crystallizes very quickly onto the crystal substrate made of the same iPP chain. Quite remarkable is that the molecule of iPP strictly recognizes the helical sense of the substrate chain and efficiently selects its chirality during crystallization.     

How many more polymorphs of ROY remain undiscovered

With 12 crystal forms, 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecabonitrile (a.k.a. ROY) holds the current record for the largest number of fully characterized organic crystal polymorphs. Four of these polymorph structures have been reported since 2019, raising the question of how many more ROY polymorphs await future discovery. Employing crystal structure prediction and accurate energy rankings derived from conformational energy-corrected density functional theory, this study presents the first crystal energy landscape for ROY that agrees well with experiment. The lattice energies suggest that the seven most stable ROY polymorphs (and nine of the twelve lowest-energy forms) on the Z′ = 1 landscape have already been discovered experimentally. Discovering any new polymorphs at ambient pressure will likely require specialized crystallization techniques capable of trapping metastable forms. At pressures above 10 GPa, however, a new crystal form is predicted to become enthalpically more stable than all known polymorphs, suggesting that further high-pressure experiments on ROY may be warranted. This work highlights the value of high-accuracy crystal structure prediction for solid-form screening and demonstrates how pragmatic conformational energy corrections can overcome the limitations of conventional density functionals for conformational polymorphs.

Crystal structure prediction suggests that the low-energy polymorphs of ROY have already been found, but a new high-pressure form is predicted.     

Specific reversible melting of polymers

Temperature‐modulated differential scanning calorimetry can detect a certain amount of reversible latent heat in flexible macromolecules. In short, one can identify a reversible melting in such polymers earlier thought to exhibit only fully irreversible crystallization and melting. Details of the reversible melting of isotactic polypropylene and ethylene‐1‐octene copolymers of low and medium densities have newly been measured and linked to the crystallization, annealing, or melting temperature. It is possible to assign the experimental reversibility of melting to specific crystal fractions that ultimately melt irreversibly at higher temperatures; that is, it is suggested that reversible melting mainly occurs only between the temperatures of their formation and their zero‐entropy‐production melting temperature, at which they change to a melt of the same degree of metastability. This is supported by the almost complete absence of reversibility below the temperature of crystal formation and the observation of a distinct relationship between the amount of irreversibly by annealing reorganized material and reversibility in the case of isotactic polypropylene. A given crystal fraction, characterized by its formation temperature and zero‐entropy‐production melting temperature, has a specific reversibility of the melt‐to‐crystal transition, which is represented by the ratio of the reversible latent heat to the total enthalpy change when the crystal fraction of interest ultimately melts. This specific reversibility is, for ethylene‐1‐octene copolymers, at least 25% at temperatures in the primary crystallization range, and this indicates that the reversible contribution to the total of the melting processes is much larger than expected from simple calculations by the excess apparent reversible heat capacity being referred to the heat of fusion of the polymer, as is commonly done. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2039–2051, 2003     

Crystallization and melting of polyethylene under high pressure. I. Crystallization by slow cooling from the melt

Crystallization and melting behavior of linear polyethylene under high pressures up to 6000 kg/cm² has been investigated with a high-pressure dilatometer. Crystallization was carried out at a cooling rate of 1°C/min from the melt at each pressure. The samples were characterized by differential scanning calorimetry, density, and electron microscopy. Folded-chain crystals are formed in the low-pressure region below 2000 kg/cm². Crystallization in the intermediate-pressure region between 2000 and 3500 kg/cm² gives a mixture of folded-chain and extended-chain crystals. The extendedchain crystals are the more stable and predominate at increasing pressure. At high pressures above 4700 kg/cm², two stages of crystallization and of melting can be observed. The phenomenon suggests that the two kinds of extended-chain crystals with different thermal stability, i.e., the ordinary extended-chain crystals and “highly extended-chain” crystals form through individual crystallization processes from the melt at high pressure.     

A new PvT device for high performance thermoplastics: Heat transfer analysis and crystallization kinetics identification

The quality of thermoplastic parts strongly depends on their thermal history during processing. Heat transfer modelling requires accurate knowledge of thermophysical properties and crystallization kinetics in conditions representative of the forming process. In this work, we present a new PvT apparatus and associated method to identify the crystallization kinetics under pressure. The PvT-xT mould was designed for high performance thermoplastics: high temperature (up to 400 °C), high cooling rate (up to 200 K/min) and very high pressure (up to 200 MPa). Specific volume measurements were performed at a low cooling rate to avoid a thermal gradient. The crystallization kinetics under pressure can be identified for a wide range of cooling rates by an inverse method taking into account the thermal and crystallinity gradients. Since identification is based on volume variations, the proposed methodology is non-intrusive. Furthermore, the enthalpy released by the crystallization was measured during the experiment by a heat flux sensor located in the moulding cavity.     

Organometallic polymers. IV. Organometallic modifications of halogen-containing polymers

The synthesis of ferrocene-containing polymers by chemical modification of chlorinated polyethylenes, polyvinyl chloride (PVC), and other halogenated polymers, under Friedel-Crafts conditions, is described. The effect of reaction conditions on the structure and composition of the products obtained with various substrates was investigated. Soluble polymers of up to 62% ferrocene content were obtained. In most cases, substitution was accompanied by dehydrohalogenation. The ferrocene-to-vinylene ratio was higher in the reaction products of chlorinated polyethylenes than in those of PVC.