Diffusion Of Polymer Chains Research Articles

Do Entangled Polymer Chains Reptate?

AbstractNeutron spin echo spectroscopy of entangled polymer melts [M. Zamponi, et al. J. Phys. Chem. B 2008, 112, 16220], and of tracer diffusion of short polymer chains in highly entangled polymer melt [M. Zamponi et al. Phys. Rev. Lett. 2021, 126, 187801.] and [M. Kruteva et al. Macromolecules 2021, 54, 11384] found the center‐of‐mass mean‐square displacements at shorter times are subdiffusive, heterogeneous, non‐Gaussian, and cooperative. These properties contradict the assumption of reptation within the tube in the tube‐reptation (TR) model, but are in accord with the predictions from the many‐chain cooperative dynamics in the theory of Guenza. The inadequacy of the TR model revealed by the microscopic experiments and theory motivates the author to reexamine previously published data of diffusion of entangled polymer chains from experiments and simulations used to test the TR model. The results reported in this study lead to the conclusion that the key predictions of the TR model are at variance with experimental and simulation data. The cause lies in the reptation hypothesis contradicting the cooperative nature of entangled chain diffusion proven by its dynamics being isomorphic to cooperative diffusion in other materials. The Coupling Model has predictions consistent with the cooperative diffusion properties in interacting materials [Prog. Mater. Sci., 2023, 139, 101130.]. Applied to the entangled polymers, the predictions successfully explain the data, especially those contradicting the TR model. Thus, diffusion of entangled polymer chains is a cooperative many‐chain process in having the universal properties of many‐body cooperative diffusion established in many other interacting materials, and the reptation hypothesis is unwarranted.

Enhancing the sensitivity of 3D printed sensors via ironing and void reduction

ABSTRACT Material Extrusion (MEX) Additive Manufacturing (AM) has risen as a promising technology to monolithically manufacture smart structures with embedded sensors. Despite all the benefits of MEX AM, 3D printed piezoresistive sensors still suffer from low sensitivity, making them unsuitable for the detection of low values of force, displacement and bending angle. In the present paper, a simple, effective, and inexpensive method to increase the sensitivity in 3D printed sensors is proposed, based on the leveraging of the ironing strategy, which resulted in an improvement in the sensitivity of 83% compared to traditional process parameter selection. The ironing strategy reduced intralayer porosity by 59%, as verified by X-Ray CT. Additionally, the ironing strategy involves an increased healing time, which promotes the polymer chain diffusion between layers, which translated into a greater stability of the sensor when cyclically stressed. Smart structures capable of detecting small forces (0.19 N of resolution against 1.96 N for traditional MEX scenario) and smart auxetic devices have been manufactured, demonstrating the potential of the proposed approach. The present research demonstrates the ability to reduce interlayer voids by using an intrinsic feature of the MEX process and consequently improve electrical performance of 3D printed sensors.

3D printed sequence-controlled copolyimides with high thermal and mechanical performance

Inadequate heat resistance and mechanical property limited the application of 3D printed polymer parts in aerospace industry. To address this restriction, a kind of sequence-controlled copolyimides with both amorphous segment and crystalline segment, suitable for fused deposition modeling 3D printing technique were designed and synthesized. The effect of content and distribution of crystalline segment on melt fluidity and crystallization behavior was disclosed. It was found that copolyimide with crystalline segment only distributed in the end of backbone exhibited good melt fluidity and slow crystallization rate. Microstructure change of the corresponding copolyimide during 3D printing and thermal annealing was revealed. Due to slow crystallization rate of copolyimide, no crystals formed during 3D printing. Thus, the diffusion and entanglement of polymer chain at interface were guaranteed. Thermal annealing at 350 °C facilitated diffusion and arrangement of polymer chain, leading to the enhancement of interfacial bonding and crystallization of copolyimide at interface and in filament. Therefore, the printed copolyimide specimens exhibited high heat resistance, high mechanical property and excellent interfacial bonding performance. The tensile strength of specimens printed in XY plane with 0° infill direction (XY-0), XY plane with 90° infill direction (XY-90) and XZ plane with 90° infill direction (XZ-90) were 110 MPa, 96 MPa and 57 MPa, respectively. The tensile strength of XY-0 printed specimen at 200 °C was 186 % higher than that of XY-0 printed amorphous polyimide specimen, reaching 40 MPa. This study expanded the kinds of polymeric materials suitable for fused deposition modeling, and provided the possibility of printing high performance engineering parts.

Crystallization, recrystallization and melting behaviors in supramolecular poly(l-lactic acid) bonded by metal-ligand coordination

The effect of metal-ligand coordination on crystallization and melting behaviors of polymers has not been comprehensively investigated. In this study, a series of supramolecular poly(l-lactic acid)s (SM-PLLAs) were prepared by changing various metal ions, length of polymer chains and stoichiometric ratio of ligands to metal ions (L/M). The complexation of metal ions with ligands in SM-PLLAs was confirmed by the intrinsic viscosity and UV–visible spectroscopy. It was found that crystallization rate and crystallinity of SM-PLLAs were strongly dependent on the chain length of precursor in both non-isothermal and isothermal crystallizations. With chain length of 1.6 kg/mol, crystallization of PLLA was completely suppressed regardless of the metal ions, whereas PLLA with longer chain length of 3.0 kg/mol exhibited strong dependence of the type of metal. During the heating process, melting behaviors can be tuned by the strength of metal-ligand coordination, temperature and the degree of complexation. Unlike PLLA precursor and SM-PLLA coordinated with Cu2+ exhibited multiple melting behaviors, only a single melting peak was appeared in PLLA bonded with Co2+, indicative of suppression of recrystallization during heating. With ratio of ligand to Co2+ increased from 1:1 to 6:1, crystallization and melting behaviors were tuned by the content of free and bounded PLLA chains. As compared to Cu2+, SM-PLLA coordinated with Co2+ exhibited higher complex modulus and viscosity due to the high bond strength, as well as a more stable structure underwent heating and shear, making diffusion of polymer chains and the structural adjustment more difficult. This work may shed light on understanding the intricate interplay of metal-ligand coordination effects on the crystallization and melting behaviors of polymers, which may be helpful with the design and making out the relationship between structure and properties of supramolecular polymers.

Study on self-healing mechanism of magnetic nano-powders functionalized fiber reinforced thermoplastic composites

At present, a variety of methods have been developed to realize the self-healing function of fiber-reinforced composites. However, the intrinsic mechanism of material damage recognition and self-healing initiation still lacks systematic research. In this paper, GF/(FeNip/PP) composites with multistage structures were prepared to study the self-healing properties and the mechanism of fiber-reinforced thermoplastic composites. The addition of a small amount of FeNip without affecting the melting peak temperature of the PP matrix (i.e., without reducing the use temperature of PP) can increase the electromagnetic loss (tanδ) of the composites by about 40% and the thermal conductivity by 36%. The cyclic stretching times of GF/(FeNip/PP) composites after microwave healing are doubled at 50% to 60%σmax load. It is indicated that FeNip endows the GF/PP composites with good microwave healing performance, and the purposeful repair can effectively extend the service life of the material. In addition, the self-healing mechanism of GF/(FeNip/PP) composites is discussed in detail from the aspects of microstructure change, multiphase interface effect, entropy enthalpy effect, starting and ending of self-healing procedures, etc. The magnetothermal effect, “entropy consumption” effect, and polymer chain diffusion are the fundamental reasons for the self-healing function of fiber reinforced thermoplastic composites.

Fabrication and characterization of tamarind seed gum based novel hydrogel for the targeted delivery of omeprazole magnesium

The tamarind seed gum based novel hydrogel was fabricated by varying concentration of polymer, monomer and crosslinker for the targeted delivery of omeprazole magnesium at stomach pH of 1.5. The free radical graft copolymerization of 2-acrylamido-2-methyl propane sulfonic acid with tamarind seed gum backbone resulted in hydrogel. The formation of sulfonic acid pendant groups in hydrogel was observed by the existence of an infrared absorption band at 1152 cm−1 for SO group. The conversion to semicrystalline nature on incorporation of drug evidenced by powder X-ray diffraction studies with peaks at 2θ = 20.4° 31.5° and 52.2°. The scanning electron microscopy images showed bigger voids which narrowed down for drug loaded matrix, supported by the presence of a peak for magnesium in the energy dispersive X-ray spectroscopy. The greatest swelling was observed at pH 7 with second-order rate constant 1.5371 (g/g)/min and drug release was found to be 97.85 ± 1 % over 1200 min at pH 1.5. The drug release transport was found combination of diffusion and erosion of polymer chain to be super case II diffusion and Hill equation model was good fit. The hydrogel drug conjugate found to be non-toxic at tested concentrations (17 mg/50 mg) on in-vivo testing in Drosophila model.

A new nanocomposite based on polylactic acid/butadiene rubber/clay: Morphology development and mechanical properties

AbstractIn this work, several samples based on poly(lactic) acid (PLA)/butadiene rubber (BR) blend with and without nanoclay (Cloisite 30B) were prepared using an internal mixer. Various methods were used to characterize the samples, including scanning electron microscopy (SEM), atomic force microscopy (AFM), x‐ray diffraction (XRD), rheometric mechanical spectrometer, stress–strain, and impact strength tests. The SEM results showed the droplet‐matrix morphology for all prepared samples. With the incorporation of nanoclay, the mean diameter of the BR droplets generated within the PLA matrix decreased. AFM test revealed the placement of nanoparticles in the PLA phase, which was consistent with the thermodynamic prediction of their location. The XRD test showed that the interlayer space of nanoclay expanded by 86% due to the diffusion of polymer chains between them. In the rheology test, this resulted in an increment in modulus and viscosity at low frequencies for the nanocomposites compared to the simple blend. The highest elongation at break was observed for the PLA/BR blend containing 10 wt% BR with approximately 40 times its value for the neat PLA, while the impact resistance increased up to three times.

Programming hydrogel adhesion with engineered polymer network topology

Hydrogel adhesion that can be easily modulated in magnitude, space, and time is desirable in many emerging applications ranging from tissue engineering and soft robotics to wearable devices. In synthetic materials, these complex adhesion behaviors are often achieved individually with mechanisms and apparatus that are difficult to integrate. Here, we report a universal strategy to embody multifaceted adhesion programmability in synthetic hydrogels. By designing the surface network topology of a hydrogel, supramolecular linkages that result in contrasting adhesion behaviors are formed on the hydrogel interface. The incorporation of different topological linkages leads to dynamically tunable adhesion with high-resolution spatial programmability without alteration of bulk mechanics and chemistry. Further, the association of linkages enables stable and tunable adhesion kinetics that can be tailored to suit different applications. We rationalize the physics of polymer chain slippage, rupture, and diffusion at play in the emergence of the programmable behaviors. With the understanding, we design and fabricate various soft devices such as smart wound patches, fluidic channels, drug-eluting devices, and reconfigurable soft robotics. Our study presents a simple and robust platform in which adhesion controllability in multiple aspects can be easily integrated into a single design of a hydrogel network.

Ultrasonic welding of fiber reinforced vitrimer composites

In this investigation, we present an exciting discovery that glass and carbon fiber-reinforced vitrimer composites (vGFRC and vCFRC) can be ultrasonically welded. The study shows that applying mechanical vibrational energy can facilitate dynamic bond exchange reactions in transesterification vitrimer composites, resulting in good weldability and mechanical properties. The results show that ultrasonic welding is potentially a practical and cost-effective option for assembling complex or large parts compared to oven curing, as it requires significantly less energy and time. Moreover, the healing properties of vitrimers make them a promising material for repeated processing and welding at the same spot. The study provides insight into the mechanisms of ultrasonic welding of vitrimers comprising bond exchange reactions and polymer chain diffusion at the surfaces. The composites with carbon fiber show better performance properties during welding compared to glass fiber-embedded composites. Lap shear failure surfaces show mostly cohesive failure. Additionally, the weld strength is also influenced by the catalyst concentration in the vitrimer composites. This investigation opens new avenues for vitrimer composites in industrial applications requiring rapid and energy-efficient welding.

A Transparent, Healable and Recyclable Alicyclic Poly(ether-b-amide) Multiblock Copolymer with Ultrahigh Toughness.

Self-healing polyamide multiblock copolymer with robust mechanical properties is highly desired. Here, an alicyclic diamine monomer, isophoronediamine (IPDA), with asymmetric structure and substantial steric hindrance was incorporated into the backbone of poly(ether-b-amide) multiblock copolymer. Based on the phase-lock effect, the mechanical properties and segmental mobility of copolymers can be modulated on a large scale via adjusting the molecular weight of hard segments. An extraordinary tensile strength of 32.0 MPa and an excellent elongation at break of 1881 % were simultaneously achieved, which leaded to a record-high toughness of 328.9 MJ m-3 for self-healable polyamide elastomers. The synergism between the dynamic H-bonding networks and the diffusion of polymer chains contributed to a balance between the mechanical performance and self-healing efficiency of copolymers. Due to the adjustable mechanical performance, rapid scratch self-healing ability and superior impact resistance, the resultant copolymers showed great potential in the fields of protective coatings and soft electronics.

Free-radical polymerization in a droplet with initiation at the interface

The free-radical polymerization inside monomer droplets surrounded by an immiscible liquid of the initiator solution is studied before the gel effect by means of the generalized method of moments taking into account diffusion of radicals and polymer chains. The influence of the droplet radius and initiator concentration in the surrounding phase on the polymerization kinetics and molecular mass characteristics of the synthesized polymer is analyzed. It is found that the polymerization kinetics matches the bulk polymerization when the droplet is small enough (kinetic regime). However, increasing the droplet radius leads to a diffusion-kinetic regime, in which the polymerization rate becomes significantly lower. As a result, the average length and the dispersity of the produced polymer chains depend significantly on the monomer droplet size. The dependence of the effective polymerization rate coefficient on the droplet radius and the initiator concentration is discussed.

Dynamic Propagation Depth in Substrate-Supported Polymer Films: A Molecular Dynamics Simulation

The properties of substrate-supported polymer films are strongly related to the properties of the substrate. This work studies the dynamic propagation depth of the substrate effect in polymer films using molecular dynamics simulations. From the layer-resolved diffusion of polymer chains, the dynamic propagation depth of the substrate effect into nonadsorbed chains λdyn is estimated to be about 2.3Rg (Rg is the radius of gyration of polymers in the bulk) and 3.5Rg for the weakly and strongly attractive substrates, respectively, much larger than the thickness of the adsorbed layer hads ≈ 1.2Rg. The dynamics of adsorbed and nonadsorbed polymers located below λdyn strongly depend on the substrate attraction strength. Our results reveal that the influence of substrate on the nonadsorbed polymer chains comes mainly from the tails of adsorbed chains and provides new insights into the molecular mechanism of the propagation of the substrate effect in polymer films.

Closed-Loop Composite Welding and Bonding System Using Radio-Frequency Heating and Pressure

Polymer parts often replace traditional metallic parts in load-bearing applications due to their high strength-to-weight ratio, with thermoplastics at the forefront. Conventional manufacturing processes rely on using fasteners or adhesives to hold composite assemblies together, but thermoplastics can be welded together. Ultrasonic welding is widely used but becomes challenging for complex geometries, and new parameters need to be developed for different polymers and specimen geometries. In this work, we developed a closed-loop welding machine that employs the recent discovery of radio-frequency (RF) heating of carbonaceous materials. The machine is successfully able to weld polylactic acid (PLA) coupons with graphitic RF susceptors at the bondline in less than 2 min and using less than 50 W of input RF power. We found that a higher areal density of the graphitic paint lowers the mechanical properties of the weld because the carbonaceous materials hinder polymer chain diffusion. A significant change was not observed in weld properties for welding pressure ranges between 0 and 0.3 MPa. However, increasing out-of-plane welding displacement increased the modulus and strength of the weld. This work provides an interesting new automated system for welding polymer composites using RF fields, with potential applications in various manufacturing industries.

Enhanced Mechanical Property of Polyamide-6/Graphite Sheet Composites with Segregated 3D Network Binary Structure for High Thermal Conductivity.

Segregated conductive polymer composites exhibit excellent electrical properties with a low percolation threshold. However, the mechanical properties of the segregated conductive polymer composites were always poor because the conductive fillers at the interfaces hinder polymer chain diffusion and thus lead to weak interfacial interaction between the conductive fillers and the polymer matrix. In this paper, polyamide-6 and polyamide-612 microspheres were synthesized via the in situ anionic ring opening of caprolactam and laurolactam. Segregated graphite sheets/polyamide-6(GS/PA6) and polyamide-612(PA612) composites with good mechanical properties were realized via high-pressure solid-phase compression molding. The microstructures of the composite samples were observed by scanning electron microscopy, which showed that the formation of a GS-conductive network at the PA6 granule interfaces in the segregated conductive structures and the adopting of PA612 considerably improved the interfacial adhesion of the composites. A superior impact strength of 5.1 kJ/m2 was achieved with 50 wt% PA612 loading owing to improvements in the interface compatibility between PA6 and GS. The composites possessed an ultralow percolation threshold, which was ascribed to the segregated network structure being successfully constructed inside the material. As for GS/PA6 composites, the combination of segregated GS-conductive networks achieved an ultralow percolation of 2.8 vol%. The percolation of 80PA6/20PA612-GS composites was slightly higher, measuring up to 3.2 vol%. Moreover, the thermal conductivity of the 80PA6/20PA612-GS composites increased from 0.26 to around 0.5 W/(m·K), which was 1.9 times larger than the pure polyamide.

Comparative study on annealing‐induced high‐impact toughness of linear and grafted polypropylene random copolymer

AbstractIn present work, the comparative study on annealing‐induced high‐impact toughness of linear and grafted polypropylene random copolymer (PPR and MPP) was performed. The changes of microstructure and mechanical properties of PPR and MPP upon annealing were investigated in detail. The results showed that maleic anhydride was grafted onto the backbone of PPR to form long‐chain branched structure. During the melt grafting process, the degradation reaction is dominant, giving rise to the decrease in molecular weight and degree of chain entanglement, and hence PPR demonstrates higher flexural modulus and impact strength, as well as lower elongation at break than MPP. The long‐branched chains perform the function of heterogeneous nucleation. The depressed chain entanglement facilitates the diffusion of polymer chains during the crystallization process, followed by higher total crystallization rate and crystallinity of MPP in contrast to those of PPR. Thermal annealing treatment promotes the secondary crystallization, and hence the crystallinity and crystal perfection of the polymer is elevated, resulting in enhanced mobility of the chain segments in the amorphous region. After annealing at 100°C for 3 h, the impact strength of MPP is 71% higher than that of its unannealed counterpart, while this value is increased remarkably by 153% for PPR. The existence of long‐branched chains may not be conducive to sufficient rearrangement of chain segments of MPP during the annealing treatment. As a consequence, the crystallinity and impact strength of PPR are elevated more pronouncedly in comparison with those of MPP after annealing treatment.

Simulation study on the effect of polydisperse nanoparticles on polymer diffusion in crowded environments.

The diffusion of polymer chains in a crowded environment with large and small immobile, attractive nanoparticles (NPs) is studied using Langevin dynamics simulations. For orderly distributed NPs on the simple cubic lattice, our results show that the diffusion of polymer chains is dependent on the NP-NP distance or lattice distance d. At low d where NPs are placed closely, subdiffusion occurs at a sufficiently high polydispersity of NPs, PD. Both the apparent diffusion coefficient and subdiffusion exponent of polymer chains decrease with increasing PD, attributed to the adsorption of polymers on NP clusters formed by larger NPs. At large d, normal diffusion is always observed, and the diffusion coefficient increases with increasing PD. The reason is that, at high PD, the difference between single large NP adsorption and double large NP adsorption is reduced, which increases the exchange of a polymer between the two adsorption states. Finally, the impact of size polydispersity of NPs on the diffusion of polymer chains in a crowded environment with randomly distributed NPs is also investigated. The results show that the position disorder of NPs enhances the subdiffusion of the system.

Calculation of the degree of crystallinity of HDPE/GNPs nanocomposites by using various experimental techniques: a comparative study

This work is a comparative study of four different techniques to determine the crystallinity of high-density polyethylene (HDPE) nanocomposites filled with different diameter sizes (5, 15 and 25 μm) of graphene nanoplatelets (GNPs) at various amounts (0.5–5 wt%). The structure of HDPE/GNPs nanocomposites was extensively studied by using different experimental methods, such as X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. To further provide a complete comparison, differential scanning calorimetry measurements were utilized to calculate the crystallinity values, while temperature-modulated DSC was employed to investigate the possible mechanism of the different crystalline structures. It was found that these methods can be used to estimate the crystallinity, but the sample parameters and experimental conditions must be taken into consideration. All the techniques showed that the crystallinity depends on GNPs size and content. The distance between dispersed platelets was substantial at low concentrations of GNPs, making it comparatively easy for additional nucleation sites to incorporate the polymer matrix, and the crystal nucleus was simply formed. However, at high concentrations of GNPs, the diffusion of polymer chains to the growing crystallites was hindered by large GNPs particles, despite the formation of additional nucleation sites.

Properties of compression molded ultra-high molecular weight polyethylene: effects of varying process conditions

Abstract Ultrahigh molecular weight polyethylene (UHMWPE) has been extensively used in various tribological systems because of its outstanding tribological properties and excellent overall performance. Compression molding is the main molding method for UHMWPE, and the process parameters of molding have a profound effect on its material properties. In this study, three groups of UHMWPE samples were prepared, and their physical, mechanical, and tribological properties under different molding process parameters were examined—with a particular focus on the frictional and wear behavior of the material under various heating-temperatures, pressing-temperatures and pressures—and the friction and wear mechanisms of UHMWPE were analysed. Studies have shown that the rise in heating-temperature promotes the diffusion of polymer chains, resulting in an increased friction coefficient and wear loss of UHMWPE. The main wear mechanism switches from plastic deformation to fatigue wear. With an increase in the pressuring-temperature, the friction coefficient first increases and then decreases, while the wear loss increases, and the dominant wear mechanism switches from fatigue wear and plastic flow to plastic flow. With an increase in pressure, the friction coefficient and wear loss first decrease and then increase, and the prime wear mechanism changes from plastic deformation and fatigue wear to fatigue wear.

Reducing the amount of coalescing aid in high performance waterborne polymeric coatings

One of the objectives of the waterborne coatings industry is to reduce or eliminate solvents out of latex paints, maintaining or increasing the mechanical performance in a way that makes industrial adaptation as plain and economical as possible. This task has been tackled by the use of temporary oligomer plasticizers (TOP) in this work. The aim of TOPs is to use oligomers to achieve the plasticisation during film formation without changing significantly the final properties of the film. The incorporation of oligomers in the polymer particles is obtained by in-situ formation with the help of a chain transfer agent added in the reactor at the end of the main polymerization step. The TOP concept is translated as well from a conventional copolymer acrylic composition to a commercial formulation with promising results. On the other hand, a study of the role of the plasticizer during film formation is carried out by measuring the chain interdiffusion rate using the Pyrene Excimer Fluorescence (PEF) technique. The reduction of the amount of co-solvent needed to produce films at room temperature by the use of TOP is therefore associated to a faster diffusion of polymer chains in the presence of oligomers.

Direct and indirect effects on molecular mobility in renewable polylactide-poly(propylene adipate) block copolymers as studied via dielectric spectroscopy and calorimetry.

In this work, we study a series of sustainable block copolymers based on polylactide, PLA, and poly(propylene adipate), PPAd, both polymers being prepared from renewable resources. Envisaging a wide range of future applications in the frame of a green and circular economy, e.g., packaging materials replacing conventional petrochemicals, the employment of PPAd aims at lowering the glass transition and melting temperatures of PLA and, finally, facilitation of the enzymatic degradation and compostability. The copolymers have been synthesized via ring opening polymerization of lactides in the presence of propylene adipate oligomers (5, 15 and 25%). The direct effects on the molecular mobility by the structure/composition are assessed in the amorphous state employing broadband dielectric spectroscopy (BDS) and calorimetry. BDS allowed the recording of local PLA and PPAd dynamics in all cases. The effects on local relaxations suggest favoring of interchain interactions, both PLA-PPAd and PPAd-PPAd. Regarding the more important segmental dynamics, the presence of PPAd leads to faster polymer chain diffusion, as monitored by the significant lowering of the dielectric and calorimetric glass transition temperature, Tg. This suggests the plasticizing role of PPAd on PLA (majority) in combination with the lowering of the average molar mass, Mn, in the copolymers from ∼75 to ∼30 kg mol-1, which is the actual scope for the synthesis of these materials. Interestingly, a strong suppression in fragility (chain cooperativity) is additionally recorded. In contrast to calorimetry and due to the high resolving power of BDS, for the higher PPAd fraction, the weak segmental relaxation of PPAd was additionally recorded. Overall, the recordings suggest a strong increase in free volume and two individual dynamic states, one for 0 and 5% PPAd and another for 15 and 25% PPAd. Within the latter, we gained indications for partial phase nano-separation of PPAd. Regarding indirect effects, these were followed via crystallization. Independent of the method of crystallization, namely, melt or cold, the presence of PPAd led to the systematic lowering of crystallization and melting temperatures and enthalpies. The effects reflect the decrease of crystalline nuclei, which is confirmed by optical microscopy as in the copolymers fewer although larger crystals are formed.