Crystal Polymer Research Articles

Regulation of Two-Dimensional Platelet Micelles with Tunable Core Composition Distribution via Coassembly Seeded Growth Approach.

Seeded growth termed "living" crystallization-driven self-assembly (CDSA) has been identified as a powerful method to create one- or two-dimensional nanoparticles. Epitaxial crystallization is usually regarded as the growth mechanism for the formation of uniform micelles. From this perspective, the unimer depositing rate is largely related to the crystallization temperature, which is a key factor to determine the crystallization rate and regulate the core composition distribution among nanoparticles. In the present work, the coassembly of two distinct crystallizable polymers is explored in detail in a one-pot seeded growth protocol. Results have shown that polylactone containing a larger number of methylene groups (-CH2-) in their repeating units such as poly(η-octalactone) (POL) has a faster crystallization rate compared to poly(ε-caprolactone) (PCL) with a smaller number of -CH2- at ambient temperature (25 °C), thus a block or blocky platelet structure with heterogeneous composition distribution is formed. In contrast, when the crystallization temperature decreases to 4 °C, the difference of crystallization rate between both cores become negligible. Consequently, a completely random component distribution within 2D platelets is observed. Moreover, we also reveal that the core component of seed micelles is also paramount for the coassembly seeded growth, and a unique structure of flower-like platelet micelle is created from the coassembly of PCL/POL using POL core-forming seeds. This study on the formation of platelet micelles by one-pot seeded growth using two crystallizable components offers a considerable scope for the design of 2D polymer nanomaterials with a controlled core component distribution.

A facile strategy for tuning the density of surface-grafted biomolecules for melt extrusion-based additive manufacturing applications

AbstractMelt extrusion-based additive manufacturing (ME-AM) is a promising technique to fabricate porous scaffolds for tissue engineering applications. However, most synthetic semicrystalline polymers do not possess the intrinsic biological activity required to control cell fate. Grafting of biomolecules on polymeric surfaces of AM scaffolds enhances the bioactivity of a construct; however, there are limited strategies available to control the surface density. Here, we report a strategy to tune the surface density of bioactive groups by blending a low molecular weight poly(ε-caprolactone)5k (PCL5k) containing orthogonally reactive azide groups with an unfunctionalized high molecular weight PCL75k at different ratios. Stable porous three-dimensional (3D) scaffolds were then fabricated using a high weight percentage (75 wt.%) of the low molecular weight PCL5k. As a proof-of-concept test, we prepared films of three different mass ratios of low and high molecular weight polymers with a thermopress and reacted with an alkynated fluorescent model compound on the surface, yielding a density of 201–561 pmol/cm2. Subsequently, a bone morphogenetic protein 2 (BMP-2)-derived peptide was grafted onto the films comprising different blend compositions, and the effect of peptide surface density on the osteogenic differentiation of human mesenchymal stromal cells (hMSCs) was assessed. After two weeks of culturing in a basic medium, cells expressed higher levels of BMP receptor II (BMPRII) on films with the conjugated peptide. In addition, we found that alkaline phosphatase activity was only significantly enhanced on films containing the highest peptide density (i.e., 561 pmol/cm2), indicating the importance of the surface density. Taken together, these results emphasize that the density of surface peptides on cell differentiation must be considered at the cell-material interface. Moreover, we have presented a viable strategy for ME-AM community that desires to tune the bulk and surface functionality via blending of (modified) polymers. Furthermore, the use of alkyne–azide “click” chemistry enables spatial control over bioconjugation of many tissue-specific moieties, making this approach a versatile strategy for tissue engineering applications. Graphic abstract

Geometry-induced process and part characteristics in support-free powder bed fusion of polypropylene at room temperature

AbstractLaser-based powder bed fusion (LPBF) of semi-crystalline polymers enables the support-free layer-wise manufacturing of geometrically diverse, complex components. In contrast to the established quasi-isothermal powder bed fusion of polymers at elevated temperatures, non-isothermal, cold processing strategies allow to significantly extend the range of applicable material systems. Relying on the superposition of discretized, fractal exposure strategies and the implicit mesoscopic compensation of crystallization shrinkage, the support-free LPBF of polypropylene at room temperature is demonstrated. The present paper displays the temporally and spatially discrete exposure of superposed fractal, space-filling curves that enable the support-free LPBF of polypropylene through combining the mesoscopic compensation of crystallization shrinkage and the laser-induced minimization of thermal shrinkage through the implementation of pre-exposure scans. The non-isothermal processing regime was observed to exhibit an intrinsic robustness towards the influence of processing parameters on emerging peak temperatures while showing a significant extent of accumulated heat within manufactured parts. Complementary mechanical characterizations showed an orientation-dependent influence of the applied energy density on emerging mechanical properties, correlated with geometry-dependent temporal process characteristics that implicitly influence the available coalescence time and the timespan available for the thermal homogenization.

A thermo-mechanical constitutive model for triple-shape and two-way shape memory polymers

Abstract Semicrystalline polymers often have diverse molecular configurations in response to the variation of temperature, making it easier to realize multiple or two-way shape memory effects (SMEs). In order to provide guidance for the design of relevant smart structures, it is necessary to develop corresponding constitutive models to better characterize the thermal-mechanical behavior of such shape memory polymers (SMPs). For the first time, a thermo-mechanical finite deformation constitutive model is presented to reveal the deformation mechanism of the triple-shape two-way SME of semicrystalline SMPs in our work, based on the theory of thermodynamics with internal state variables. To verify the validity of the model, the model results are compared with the test data for a typical shape memory cycle. It is found that the model can be employed to describe the non-equilibrium response of semicrystalline SMPs with two types of crystallites in the vicinity of crystallization and melting. Since the model results fit well with the test data, the effectiveness of the model in predicting the triple two-way shape memory behavior is demonstrated.

Understanding the Impact of Chain Mobility on Conformational Evolution and Kinetics of Mesophase Formation in Poly(ʟ-lactide) under Low-Pressure CO2

Although the mesomorphic phase as an intermediate state has been introduced to understand polymer crystallization, the understanding of the mesomorphic phase is far from complete. Here, the effect of chain mobility on the mesophase structuring in melt-quenched poly(ʟ-lactide) (PLLA) treated in low-pressure CO2 at 1.6–2.0 MPa and 0 °C was investigated using infrared (IR) spectroscopy, differential scanning calorimetry (DSC), and atomic force microscopy (AFM). The IR and AFM results demonstrated that the final degree of order and the kinetics of structural evolution during the CO2-induced mesophase formation were critically dependent on the CO2 pressure. This was attributed to the distinct dynamics of conformational evolution (gg to gt conformer transition) due to the different CO2 pressures. The thermal behavior from the DSC results showed that CO2 pressure dominated both the scale and dynamics of the chain motion of PLLA. At a lower CO2 pressure of 1.6 MPa, smaller-scale segmental motion was not replaced by the larger-scale cooperative motion that occurred at a relatively higher CO2 pressure of 2 MPa, which was favorable for faster mesophase formation. Consequently, by inhibiting direct crystallization under limited mobility conditions, it was demonstrated that varying the chain mobility controlled by CO2 pressure and thus CO2 solubility impacted the dynamics of the mesophase formation of PLLA. The present results have implications for understanding the role of chain mobility in determining the intermediate structural phases in semicrystalline polymers.

Bio-Inspired Crystalline Core-Shell Guanine Spherulites.

Spherical particles with diameters within the wavelength of visible light, known as spherulites, manipulate light uniquely due to their spatial organization and their structural birefringence. Most of the known crystalline spherulites are branched, and composed of metals, alloys, and semi-crystalline polymers. Recently, a different spherulite architecture is discovered in the vision systems of decapod crustaceans - core-shell spherulites composed of highly birefringent ( ) organic single-crystal platelets, with exceptional optical properties. These metastructures, which efficiently scatter light even in dense aqueous environments, have no synthetic equivalence and serve as a natural proof-of-concept as well as synthetic inspiration for thin scattering media. Here, the synthesis of core-shell spherulites composed of guanine crystal platelets (( ) is presented in a two-step emulsification process in which a water/oil/water emulsion and induced pH changes are used to promote interfacial crystallization. Carboxylic acids neutralize the dissolved guanine salts to form spherulites composed of single, radially stacked, β-guanine platelets, which are oriented tangentially to the spherulite surface. Using Mie theory calculations and forward scattering measurements from single spherulites, it is found that due to the single-crystal properties and orientation, the synthetic spherulites possess a high tangential refractive index, similarly to biogenicparticles.

Physical-Entanglements-Supported Polymeric Form Stable Phase Change Materials with Ultrahigh Melting Enthalpy.

With the rapid development of new energy and the upgrading of electronic devices, structurally stable phase change materials (PCMs) have attracted widespread attentions from both academia and industries. Traditional cross-linking, composites, or microencapsulation methods for preparation of form stable PCMs usually sacrifice part of the phase change enthalpy and recyclability. Based on the basic polymer viscoelasticity and crystallization theories, here, a kind of novel recyclable polymeric PCM is developed by simple solution mixing ultrahigh molecular weight of polyethylene oxide (UHMWPEO) with its chemical identical oligomer polyethylene glycol (PEG). Rheological and leakage-proof experiments confirm that, even containing 90% of phase change fraction PEG oligomers, long-term of structure stability of PCMs can be achieved when the molecular weight of UHMWPEO is higher than 7000kg mol-1 due to their ultralong terminal relaxation time and large number of entanglements per chain. Furthermore, because of the reduced overall entanglement concentration, phase change enthalpy of PCMs can be greatly promoted, even reaching to ≈185 J g-1, which is larger than any PEG-based form stable PCMs in literatures. This work provides a new strategy and mechanism for designing physical-entanglements-supported form stable PCMs with ultrahigh phase change enthalpies.

Flexible and rigid block copolymers from recyclable polyesters

The paper addresses a study on the thermoplastic elastomers (TPE) that can be synthesized using monomers retrieved from the chemically recycled semi-aromatic polyesters, such as terephthalic acid from low value stream recyclable polyethylene terephthalate (rPET). In contrast to PET, because of their physical and mechanical properties, TPEs are often used as an engineering polymer in automotive and consumer goods. The understanding of the crystallization and phase behavior of these materials is crucial to fine-tune the molecular structure and properties. We explore the interplay between the crystallization and phase separation in these materials by performing experiments on model thermoplastic elastomers consisting of polybutylene terephthalate (PBT) and polytetrahydrofuran (PTHF). A common denominator in the synthesis of PBT is terephthalic acid that can be obtained from Dimethyl Terephthalate (DMT) or recycling used PET. We show that by varying the compositions and block length of different blocks, in PBT-PTHF block copolymers, morphological variations from spherulites to dendrites can be induced, which could be captured using optical microscopy. By performing rheological and small angle X-ray scattering studies, we correlate these morphological variations at microscopic length scales, to the chain architecture at nanometer length scales. Our observations reveal that at the higher rigid PBT content, the process of phase separation strongly influences the crystallization kinetics that promotes the lamellar structure of the semi-crystalline polymer, observed at room temperature. On the other hand, in the presence of higher soft block content, the crystal growth occurs with minimal influence of the microphase separation. In broader generality, no morphological differences in the TPEs synthesized using the terephthalic acid from rPET are found. However, when the monomer from rPET is used, enhancement in crystallization rate occurs in the TPEs having similar molar mass and molecular configuration. We attribute the enhanced crystallization rate to the catalyst residues present in the terephthalic acid obtained fom rPET.

Polymer Crystallization Kinetics and Thermodynamics of Some Industrial Polyamides

A comprehensive non-isothermal kinetics study on polymer crystallization processes taking place in a set of industrial polyamides comprising nylon 6, nylon 6,6, nylon 11 and nylon 12, individually, is reported. The kinetics studies elucidated that the phenomena of nucleation/diffusion underlying the nylons crystallization go to completion in a single-step. Notwithstanding, the nylons diffusion activation energies do not correspond to the universal value of segmental jump activation energy signifying polymer chains diffusion processes. The polymer chain transport phenomenon was probably the slowest one in the case of nylon 6 and nylon 6,6, and the fastest in the case of nylon 12, while intermediate for nylon 11. Furthermore, the nucleation barrier during the course of polymer crystallization was the highest for nylon 6,6, followed by nylon 6, nylon 11 and nylon 12. Our kinetics studies further predict that the crystallization of nylon 12 and nylon 11 follows, respectively, diffusion-controlled 2D growth of spherulites and a somewhat complicated nucleation/growth phenomenon. The thermodynamics of the nylons crystallization suggests that the highest structural orientation of the activated complex was attained in the case of the nylon 12 crystallization process. Interestingly, while the thermodynamics and majority of the kinetic parameters of nylon 6 and nylon 6,6 were similar/comparable, the two follow widely differing crystallization mechanisms. The most probable physical meanings of the obtained kinetics and thermodynamics parameters and their practical significance are given and discussed.

Strength and toughness of semicrystalline polymer fibers: Influence of molecular chain entanglement

The mechanical properties of oriented semicrystalline polymers fibers are mainly determined by the semicrystalline morphology in which lamellar crystals and disordered amorphous layers are in staggered arrangement. As a stress transmission channel, amorphous entanglement network can affect the strength and toughness of fiber together with crystalline phase. In this study, the relationship between mechanical properties and amorphous entanglement of oriented poly (l-lactic acid) fibers was clarified by studying the cyclic loading characteristics. Based on the Haward-Thakray model of semi-crystalline polymers, the energy contributions of the crystalline phase and the amorphous phase are separated. During the deformation of oriented fiber, the crystal will be broken under the action of tight entanglement network, and the entanglement network can transfer stress well without failure under the action of straight chain. Therefore, although the crystalline phase and the amorphous phase jointly bear the strength, the toughness and fracture behavior mainly affected by the entangled network of the amorphous phase.

Advancing spin-coating technique for semi-crystalline low-density polyethylene thin films

Polymeric thin films are widely used for coating substrates or as freestanding materials. They are prepared using physical/chemical vapor deposition, dip coating, solution casting, or spin coating. Among these, spin-coated films offer uniform thickness and reproducible results. These films are typically made from amorphous polymers, which are soluble in solvents at ambient temperature, making it easier to coat the polymer solution on the substrate. Despite the advantages of this technique, it has hardly been used for semi-crystalline polymers. In this work, we report the synthesis of freestanding porous thin films using semi-crystalline polymers, specifically low-density polyethylene (LDPE), through the utilization of spin coating. The effect of polymer concentration and porosity on thickness and strength was investigated. The as-prepared thin film was characterized by XRD, XPS, FTIR, and SEM techniques. The increase in crystallinity (14 % change) of the thin film was attributed to the rearrangement and uniform alignment of the polymer chains, which further resulted in relatively higher tensile strength.

Photopolymerizable semi-crystalline polymers for thermally reversible, 3D printable cast molds

ObjectivesThis study demonstrates the use of photopolymerization to create semi-crystalline linear polymers suitable for thermally reversible materials in dental cast moldings produced from 3D printing. MethodsAn aromatic diallyl, aliphatic dithiol chain extender, and monofunctional thiol were used in a photoinitiated system. The photopolymerization and crystallization kinetics as a function of chemistry and temperature were investigated using spectroscopy and calorimetry. These insights were used to realize vat photopolymerization-based 3D printing of functional objects that could be remotely melted and thereby removed using induction heating. ResultsThe addition of monothiol was shown to decrease the polymer molecular weight which correspondingly increased the crystallization rate. Photopolymerization kinetics are independent of temperature while crystallization was slowed as the temperature approaches the melting point of the materials. Through inclusion of chromium oxide, semicrystalline materials could be melted through induction heating. These materials were implemented in vat photopolymerization 3D printing to realize high-resolution objects that could be used as releasable dental molds following printing and induction heating. SignificanceThis work demonstrates a proof-of-concept methodology to realize directly printable, thermally reversible semicrystalline materials for potential use as dental molding materials.

Morphological structure and mechanical properties of a nucleated Polyoxymethylene (POM) homopolymer resin processed under conventional injection molding conditions

When injection molding semi-crystalline polymers, it is known that the resulting morphological and mechanical properties are strongly dependent on the processing conditions. Selectively influencing the performance of the final part as early as during processing is of great interest for industrial applications. To investigate the processing-structure-property correlation for a POM hompolymer resin, tensile specimens were manufactured under conventional injection molding conditions following a Design of Experimets (DoE). Morphological characterization was carried out by microscopy and X-ray measurements. Crystallinity was also measured by differential scanning calorimetry (DSC). Additionally, the (fracture) mechanical behaviour of the samples was assessed. Influences of the processing parameters on the crystalline structure and orientations within the material were identified. Furthermore, tensile tests were found to be sensitive to changes in morphology and processing, whereas the fracture behaviour did not change significantly despite the structural changes within the samples.

Influence of Polymer Surface Roughness on the Fractions of Transmitted, Reflected and Absorbed Energy in Operation of Laser Transmission Welding

AbstractThe study of energy fractions plays a fundamental role in laser joining operations: from their knowledge, it is possible to calculate the amount of laser beam energy that is effectively available during the formation of chemical and physical bonds, and how much energy is dissipated. This study examines semi-crystalline polymers of polyamide 6.6 (PA), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), and polypropylene (PP), semitransparent to light radiation, with the aim of studying the influence of surface roughness on the distribution of energy fractions, and in particular on the reflection portion. For this purpose, polymeric samples with different surface finishing were prepared and characterized by profilometric analysis. Subsequently, an experimental setup was implemented to directly measure the transmitted ratio, obtaining the reflected energy fraction from the Beer-Lambert law, and the absorbed ratio by energy balance. The results showed a decrease in the power transmitted by polymers subjected to surface treatment, due to an increase in the reflection fraction, a phenomenon particularly evident for PET, for which the reflection share increased from ~ 0.5% to ~ 15.3%, following P240 treatment. A lower influence was verified for PA and especially PTFE, due to a lower influence of the treatment on surface morphology. On the basis of the experimental results, it is hypothesised that roughening the lower section of the irradiated polymer could allow an increase in the total internal reflection fraction, favouring the joint at the interface point. Graphical Abstract

Effects of Trefoil Knots on the Initiation of Polymer Crystallization

Effects of Trefoil Knots on the Initiation of Polymer Crystallization

Influence of printing parameters and hinge structure on shape memory performance at the hinge in 4D origami structures

Four-dimensionally (4D) printing technology effectively demonstrates the advantages of portability, foldability, and improved mechanical properties in origami structures. This study highlights the significance of printing process parameters and origami hinge structures in ensuring rapid and complete deployment of origami structures. Polylactic acid based semicrystalline shape memory polymer was utilized to produce 4D printed origami structures. Through response surface analysis methods and bending tests, optimal printing parameters were determined, including layer thickness of 0.31 mm, extrusion speed of 17 mm s−1, and infill percentage of 71%. Additionally, the study designed a U-shaped hinge and analyzed its recovery mechanism through micromorphology of bending hinges and recovery experiments.

Industrially relevant injection moulding apparatus for in situ time-resolving small-angle X-ray scattering measurements

AbstractThis work presents the design and construction of an automated industrial injection moulding apparatus that can be used with a typical multi-user beamline such as the NCD-SWEET small-angle X-ray scattering at the ALBA Synchrotron Light Source. This apparatus is focused on developing an understanding of how the mould temperature and the injection temperature and pressure affect both the orientation and morphology of the semi-crystalline polymer used to fabricate the injected parts. The system design follows current industrial practice and enables the collection of time-resolved X-ray scattering data at several points within the mould cavity, so we can understand the 4D morphology. In this work we show the effectiveness of the equipment using some results from the injection moulding of a random copolymer of polypropylene and that it can be used with a more demanding material such as polyhydroxybutyrate. This can be seen as the first step toward a multiscale digital twin for injection moulding.

Strain Rate Dependence of Amorphous Phase Instability in Semicrystalline Polymers: Insights from the Scale of Lamellar Stacks

Strain Rate Dependence of Amorphous Phase Instability in Semicrystalline Polymers: Insights from the Scale of Lamellar Stacks

Crystallization of Polymers with a Reduced Density of Entanglements

Since methods for reducing macromolecule entanglements have been developed, it has become possible to better understand the impact of polymer chain entanglement on the crystallization process. The article presents basic information about the disentangling of macromolecules and the characterization of the degree of entanglement. The basic knowledge of polymer crystallization was also presented. Then, it was discussed how polymers crystallize during their disentangling. Non-isothermal and isothermal crystallization experiments using disentangled polymers, and for comparison using entangled polymers, are described in more detail. The influence of disentangling on both nucleation and crystal growth is highlighted. It is also shown how the crystallization of polymers changes when macromolecules re-entangle.

Additive Manufacturing of Composite Polymers: Thermomechanical FEA and Experimental Study.

This study presents a comprehensive approach for simulating the additive manufacturing process of semi-crystalline composite polymers using Fused Deposition Modeling (FDM). By combining thermomechanical Finite Element Analysis (FEA) with experimental validation, our main objective is to comprehend and model the complex behaviors of 50 wt.% carbon fiber-reinforced Polyphenylene Sulfide (CF PPS) during FDM printing. The simulations of the FDM process encompass various theoretical aspects, including heat transfer, orthotropic thermal properties, thermal dissipation mechanisms, polymer crystallization, anisotropic viscoelasticity, and material shrinkage. We utilize Abaqus user subroutines such as UMATHT for thermal orthotropic constitutive behavior, UEPACTIVATIONVOL for progressive activation of elements, and ORIENT for material orientation. Mechanical behavior is characterized using a Maxwell model for viscoelastic materials, incorporating a dual non-isothermal crystallization kinetics model within the UMAT subroutine. Our approach is validated by comparing nodal temperature distributions obtained from both the Abaqus built-in AM Modeler and our user subroutines, showing close agreement and demonstrating the effectiveness of our simulation methods. Experimental verification further confirms the accuracy of our simulation techniques. The mechanical analysis investigates residual stresses and distortions, with particular emphasis on the critical transverse in-plane stress component. This study offers valuable insights into accurately simulating thermomechanical behaviors in additive manufacturing of composite polymers.