Heterogeneous Crystallization Research Articles

About modification of foundry magnesium alloys

It is shown that the main modifiers of foundry magnesium alloys cannot create heterogeneous crystallization centers in melts during their solidification. Modification of alloy structures is an adsorption‑nanostructural process. It is shown that adsorbed hydrogen is a modifying element of the structures of foundry magnesium alloys. The mechanism of their modification consists in a large decrease in the concentration of adsorbed hydrogen in melts by significantly reducing the concentration of dissolved hydrogen.

A Graphene-Coated Silicon Wafer Plate Improves the Sensitivity and Reproducibility of MALDI-TOF MS Analysis of Proteins.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is widely used to analyze small and large molecules. However, proteins are difficult to analyze with MALDI-TOF MS in clinical applications because of their low ionization efficiency and heterogeneous crystallization with the matrix on the sample spots. Here, we investigate the potential of a customized graphene-coated silicon wafer (G/SiO2) plate for MALDI-TOF MS analysis of a clinically important protein, KPC-2, in comparison with a conventional stainless steel (SUS) plate. Our results demonstrate that the G/SiO2 plate outperforms the SUS plate in terms of sensitivity, reproducibility, and mass accuracy/precision across a wide range of molecular weights, even with highly complex samples. Furthermore, a five-day robustness test confirms the practical applicability of the G/SiO2 plate for the reliable identification of target protein(s) in MALDI-TOF MS analysis. Overall, our findings suggest that the use of the G/SiO2 plate holds great potential for improving the sensitivity and reproducibility of MALDI-TOF MS analysis for the identification of proteins, making it a promising tool for clinical applications.

The Influence of GGBFS as an Additive Replacement on the Kinetics of Cement Hydration and the Mechanical Properties of Cement Mortars

Granulated blast furnace slag (GBFS) is a byproduct of the iron production process. The objective of this study is to determine the effects of ground granulated blast furnace slag (GGBFS), used as a replacement admixture (0–40 wt.%) for ordinary Portland cement (OPC), on the setting time, the heat of hydration, and the mechanical properties of cement mortar. The influence of GGBFS as a replacement additive on the setting time shows that it has an accelerating effect on cement hydration. Calorimetric measurements were performed on the cement paste system to determine the effects of GGBFS on the hydration of OPC. Calorimetric measurements carried out show that the replacement of GGBFS in an amount up to 40 wt.% reduces the total heat of hydration by up to 26.36% compared to the reference specimen. The kinetic analysis performed on the calorimetric data confirms the role of GGBFS as an accelerator by shortening the time during which the process of nucleation and growth (NG), as the most active part of hydration, is reduced up to 2.5 h. The value of the Avrami–Erofee constant indicates polydispersity and heterogeneous crystallization. Mechanical tests of cement mortars were performed after 3, 7, 14, 28, 70, and 90 days of hydration and showed that replacement addition of GGBFS slightly reduced the mechanical properties in the early phase of hydration, while in the later phase of hydration it contributed to an increase in the mechanical properties.

Particle shapes and infrared extinction spectra of nitric acid dihydrate (NAD) crystals: optical constants of the β-NAD modification

Abstract. Satellite- and aircraft-based mid-infrared measurements of polar stratospheric clouds (PSCs) have provided spectroscopic evidence for the presence of β-NAT (nitric acid trihydrate) particles. Metastable nitric acid hydrate phases such as α-NAT and α-NAD (nitric acid dihydrate) have been frequently observed in laboratory experiments but not yet detected as a constituent of PSCs in atmospheric measurements. As for the β-NAD modification, its formation was first observed in X-ray diffraction measurements when the low-temperature α-NAD phase was warmed to a temperature above 210 K. Its infrared spectrum has been reported, but so far no optical constants have been derived that could be used as input for infrared retrievals of PSC composition. In this work, we show that β-NAD particles were efficiently formed in isothermal heterogeneous crystallisation experiments at 190 K from supercooled HNO3/H2O solution droplets containing an embedded mineral dust or meteoric smoke particle analogue. An inversion algorithm based on a T-matrix optical model was used to derive for the first time the mid-infrared complex refractive indices of the β-NAD modification from the measured extinction spectrum of the particles. In contrast to the heterogeneous crystallisation experiments, the α-NAD phase was formed when the HNO3/H2O solution droplets did not contain a solid nucleus and crystallised homogeneously. Using a light-scattering detector that recorded two-dimensional scattering patterns of the crystallised NAD particles, we were able to determine predominant shapes of the α- and β-NAD crystals. We found that α-NAD grew into elongated, needle-shaped crystals, while β-NAD particles were compact in shape. This agrees with previously reported images of α- and β-NAD particles grown on the cryo-stage of an environmental scanning electron microscope. While direct evidence for the existence of metastable NAD in the polar stratosphere is still lacking, our experiments add to the wealth of previous laboratory studies that have identified various conditions for the rapid growth of metastable compositions. In the atmosphere, these could be intermediate states that transform into thermodynamically stable NAT on longer timescales in aged PSCs.

Filler-induced heterogeneous nucleation of polymer crystals investigated by molecular dynamics simulations

Filler particles are known to act as nucleants for polymer crystallisation yet the connection between the filler surface properties and polymer crystallisation are not well understood. In this work, molecular dynamics simulations were used to investigate homogeneous and heterogeneous polymer nucleation and crystallisation using a generic linear bead–spring polymer model with a bond bending potential. The polymer systems were equilibrated at high temperature and then cooled at a constant rate. Without a surface present, polymers with stiff chains were found to crystallise more readily than more flexible polymers. The degree of crystallinity was estimated based on the mass fraction of straight chain segments which we equate to stem mass fraction. At a temperature Tc a sharp increase in density, radius of gyration and stem mass fraction occurred. After cooling, the systems were reheated and some systems showed hysteresis with a sharp decrease in these properties occurring upon melting at Tm>Tc. For slower heating rates, crystal growth occurred during heating from between the glass transition temperature, Tg, and Tc until just before melting at Tm. The presence of an isotropic surface was found to promote crystallisation in flexible systems that did not crystallise in the bulk, where the stem mass fraction and Tc increased with the interaction strength between the surface and the polymer beads. Changes in Tc and degree of crystallinity with cooling rate are consistent with experimental observations. This model captures polymer crystallisation phenomena and provides insight into heterogeneous nucleation, demonstrating that strong interfacial interactions promote crystallisation, thus aiding the choice or design of nucleants for control of polymer crystallisation and microstructure.

Plasmonic nanofillers-enabled solar membrane crystallization for mineral recovery

Recently, the excitation of localized surface plasmon resonances in metal nanoparticles (NPs) has been exploited in membrane science (especially, membrane distillation) to overcome temperature polarization. However, the prohibitive costs of state-of-the-art plasmonic NPs such as Ag and Au have opened the quest of alternative materials. Here, we show that nanoscale photothermal effects activated by light irradiation on nanocomposite membranes made of a thin microporous coating of polydimethylsiloxane (PDMS) loaded with NiSe or CoSe NPs supported on polyvinylidene fluoride might be exploited to achieve crystallization of dissolved salts in brines. Explicitly, we demonstrate that the embodiment of the plasmonic NiSe and CoSe NPs is capable to originate an increase of the vaporization of the water from brine once the nanocomposite membranes are irradiated with sunlight, with the possibility to reach the supersaturation conditions, with the subsequent heterogeneous nucleation and crystallization of dissolved salts.

Effect of nanocomposite pour point depressant EVAL/CNT on flow properties of waxy crude oil

The nanocomposite EVAL-CNT was produced by chemical grafting in the solution system through the esterification of ethylene-vinyl alcohol copolymer (EVAL) and carboxylated multi-walled carbon nanotubes (O-MWCNT), and its structural properties were characterized. The improvement of the rheological properties of the waxy oil system by the novel pour point depressant was investigated using macroscopic rheological measurements and microscopic observations. The results showed that EVAL-CNT nanocomposite pour point depressant (PPD) could significantly reduce the pour point and improve the low temperature fluidity of crude oil and had better performance than EVAL-GO at the same addition level. The best effect was achieved at the dosing concentration of 400 ppm, which reduced the pour point by 13 °C and the low-temperature viscosity by 85.4%. The nanocomposites dispersed in the oil phase influenced the precipitation and crystallization of wax molecules through heterogeneous crystallization templates, which led to the increase of wax crystal size and compact structure and changed the wax crystal morphology, which had a better effect on the rheological properties of waxy oil.

Assessment of the DCMD performances of poly(vinylidene difluoride) vapor-induced phase separation membranes with adjusted wettability via formation process parameter manipulation

Poly(vinylidene difluoride) (PVDF) membranes for direct contact membrane distillation (DCMD) are commonly modified to decrease their wettability by water. Yet, the vapor-induced phase separation (VIPS) process may be a suitable alternative to avoid complex and expensive modifications. Superhydrophobic membranes with a water contact angle >152° were prepared in one single step by adjusting the polymer concentration, dissolution temperature, relative humidity, and exposure time to vapors to 10 wt%, 40 °C, 80 % and 10 min, respectively with N-Methyl-2-pyrrolidone (NMP) as the solvent. Compared to commercial polytetrafluorethylene (PTFE) membrane, the VIPS PVDF membrane showed higher water vapor flux (38 LMH vs 36 LMH), lower flux decline ratio (22 % vs 39 %) and superior salt rejection (99.99 % vs. 99.90 %) in a 3 h-DCMD process. In wetting tests, the VIPS membrane failed for a sodium dodecyl sulfate concentration of 0.2 mM while 0.1 mM was enough to trigger wetting of the commercial membrane. The energy barrier to heterogeneous crystallization was slightly larger for the VIPS membrane, and a higher rejection was measured during scaling tests (99.8 % vs. 94.2 % for PTFE membrane). Finally, the VIPS membrane outperformed the commercial membrane in a long-term test (100 h). These results evidence the suitability of VIPS PVDF membranes for DCMD.

Preparation of ultra-pure ammonium metavanadate via heterogeneous self-assembly crystallization

Although the demand for ultra-pure V2O5 in industry is significant, the current technologies used to obtain the principal precursor, ammonium metavanadate, in high purity are costly and low-yielding. In this study, a cost-efficient and high-yielding heterogeneous self-assembly crystallization (HSC) process is proposed for obtaining large, high-purity NH4VO3 crystals. The method entails establishing a wide crystallization window, controlling the NH3 mass transfer rate and buffering the pH of the mother liquor with CO2 released during the pyrolysis of the ammonia source, (NH4)2CO3 to achieve the separation of chromium impurities, the most difficult-to-remove impurities in vanadium products, from the chromium-containing NaVO3 solution, and purification of NH4VO3 via reactive crystallization. Under the optimized crystallization conditions, namely an N/V mass ratio of 3.9, temperature of 60 °C, and pH of 12.5, the yield and purity of the obtained NH4VO3 in 20 g·L−1 V(V) simulated solution containing 0.05 g·L−1 Cr(VI) reached 93.09% and 99.99%, respectively, and the obtained NH4VO3 crystals were as large as 1.8 mm in size. In the case of a real leaching solution, the NH4VO3 yield and purity were higher than 80% and 99.99%, respectively, and the purity of final V2O5 reached 99.99%. The curbed pyrolysis rate of (NH4)2CO3 ensures heterogeneous nucleation and slow growth of NH4VO3 crystals to acquire large and pure crystals, and the excessive adsorption of Cr(VI) onto the crystal surface during self-assembly is avoided at the appropriate pH, thus guaranteeing efficient precipitation, crystallization, and purification. This study provides a reference strategy for the low-cost preparation to obtain high-purity V2O5.

High entropy coating from AlCoCrCuFeNi alloy, obtained by laser alloying

The structural-phase state of the Al-Co-Cr-Cu-Fe-Ni system high-entropy alloy obtained by laser alloying of technically pure aluminium surface layers was investigated by XRD, EDX and metallographic analyses. It is shown that in the process of laser alloying the formation of an an ordered multicomponent substitution solid solution based on BCC lattice took place, which is typical for high-entropy alloys. The process of heterogeneous crystallization of high-entropy alloys AlCoCrCuFeNi and Al3CoCrCuFeNi was modeled taking into account cooling rates of the melt. It is established that the formation of the obtained structure is a consequence of high cooling rates of the melt and high content of aluminum in the laser alloying zone. The microhardness of the alloyed surface was higher compared to high-entropy alloys of this system obtained under equilibrium conditions and was equal to 6.59 GPa. Additional reasons that may affect the high values of microhardness are analysed.

Molecular rotations trigger a glass-to-plastic fcc heterogeneous crystallization in high-pressure water.

We report a molecular dynamics study of the heterogeneous crystallization of high-pressure glassy water using (plastic) ice VII as a substrate. We focus on the thermodynamic conditions P ∈ [6-8] GPa and T ∈ [100-500] K, at which (plastic) ice VII and glassy water are supposed to coexist in several (exo)planets and icy moons. We find that (plastic) ice VII undergoes a martensitic phase transition to a (plastic) fcc crystal. Depending on the molecular rotational lifetime τ, we identify three rotational regimes: for τ > 20 ps, crystallization does not occur; for τ ∼ 15 ps, we observe a very sluggish crystallization and the formation of a considerable amount of icosahedral environments trapped in a highly defective crystal or in the residual glassy matrix; and for τ < 10 ps, crystallization takes place smoothly, resulting in an almost defect-free plastic fcc solid. The presence of icosahedral environments at intermediate τ is of particular interest as it shows that such a geometry, otherwise ephemeral at lower pressures, is, indeed, present in water. We justify the presence of icosahedral structures based on geometrical arguments. Our results represent the first study of heterogeneous crystallization occurring at thermodynamic conditions of relevance for planetary science and unveil the role of molecular rotations in achieving it. Our findings (i) show that the stability of plastic ice VII, widely reported in the literature, should be reconsidered in favor of plastic fcc, (ii) provide a rationale for the role of molecular rotations in achieving heterogeneous crystallization, and (iii) represent the first evidence of long-living icosahedral structures in water. Therefore, our work pushes forward our understanding of the properties of water.

Multistep Crystallization of Ge‐Rich GST Unveiled by In Situ synchrotron X‐ray diffraction and (scanning) transmission electron microscopy

Among many phase change materials, Ge‐rich GeSbTe (GST) alloys are of considerable interest due to their high thermal stability, a specification required for the next generation of embedded digital memories. This stability results from the fact that these alloys do not crystallize congruently but experience phase separation forming Ge and GST‐225 nanocrystals upon crystallization. However, the details of the crystallization process remain unclear. Combining in situ X‐ray diffraction studies during isothermal annealing and ex situ (scanning) transmission electron microscopy ((S)TEM) observations, the successive phases through which these alloys crystallize are identified. At low temperature (310 °C), the homogeneous amorphous material undergoes phase separation during wherein small regions of different Ge contents are formed. After a long incubation time, Pnma GeTe embryos first crystallize and trigger the heterogeneous crystallization of the Ge cubic phase. While the Ge phase progressively builds up through the addition of new small Ge crystals, cubic GeTe forms. At this point, the microstructure ceases to evolve, and Sb is still dispersed and contained within some remaining amorphous matrix surrounding Ge and GeTe crystals. Higher annealing temperatures (typically 400 °C) are needed to force Sb to diffuse and get incorporated into the GeTe grains to form cubic Ge2Sb2Te5.

Stabilization of uric acid mixed crystals by melamine

Melamine stabilizes heterogeneous nucleation of calcium crystals by increasing the retention time and decreasing the rate of dissolution. Stabilization of such mixed crystals limits the efficacy of non-invasive treatment options for kidney stones. Crystalline forms of uric acid (UA) are also involved in urolithiasis or UA kidney stones; however, its interactions with contaminating melamine and the resulting effects on the retention of kidney stones remain unknown. Since melamine augments calcium crystal formation, it provides an avenue for us to understand the stability of UA-calcium phosphate (CaP) crystals. We show here that melamine facilitates UA + CaP crystal formation, resulting in greater aggregates. Moreover, melamine induced mixed crystal retention through a time-dependent manner in presence and/or absence of hydroxycitrate (crystal inhibitor), indicating its abridged effectiveness as conventional remedy. CaP was also shown to modify optical properties of UA + CaP mixed crystals. Differential staining of individual crystals revealed enhanced co-aggregation of UA and CaP. The dissolution rate of UA in presence of melamine was faster than its heterogeneous crystallization form with CaP, although the size was comparatively much smaller, suggesting disparity in regulation between UA and CaP crystallization. While melamine stabilized UA, CaP and mixed crystals in relatively physiological conditions (artificial urine), the retentions of those crystals were further augmented by melamine, even in presence of hydroxycitrate, thus reducing treatment efficacy.

Synthesis and characterization of poly(tetramethylene oxide)-based segmented ionenes block copolymer with aliphatic or DABCO hard segments

In this study, the effects of the contents of the soft and hard segments as well as the type of hard segments (linear aliphatic and DABCO) on the properties of PTMO-based segmented ionenes were investigated. DSC revealed that soft segment weight fractions up to 75 wt% induced heterogeneous crystallization while the melting temperature decreased due to the lower degree of crystallization. DMA showed the formation of a higher degree of ionic aggregates in both linear aliphatic and DABCO-based PTMO ionenes with 25 wt% of soft segment resulting from strong Coulombic interactions between hard segments. DABCO-based ionenes showed a higher degree of phase separation compared to linear aliphatic analogs and displayed a long-range ordered lamellar structure. In contrast, linear aliphatic ionenes showed the formation of random ionic domains, which was confirmed by SAXS and AFM. TGA showed that the PTMO-based ionenes were thermally stable up to 250 °C and suggested that the DABCO hard segment has a weaker protective effect against the degradation of the PTMO soft segment at elevated temperatures compared to the linear aliphatic hard segment. Uniaxial tensile tests exhibited stress-induced crystallization of PTMO-based ionenes, high elongation at break with linear aliphatic hard segment compared to the DABCO hard segment, and the opposite trend of Young's modulus and ultimate tensile strength by changing the type of the hard segment.

Heterogeneous Nucleation in Protein Crystallization.

Protein crystallization was first discovered in the nineteenth century and has been studied for nearly 200 years. Protein crystallization technology has recently been widely used in many fields, such as drug purification and protein structure analysis. The key to successful crystallization of proteins is the nucleation in the protein solution, which can be influenced by many factors, such as the precipitating agent, temperature, solution concentration, pH, etc., among which the role of the precipitating agent is extremely important. In this regard, we summarize the nucleation theory of protein crystallization, including classical nucleation theory, two-step nucleation theory, and heterogeneous nucleation theory. We focus on a variety of efficient heterogeneous nucleating agents and crystallization methods as well. The application of protein crystals in crystallography and biopharmaceutical fields is further discussed. Finally, the bottleneck of protein crystallization and the prospect of future technology development are reviewed.

Template-induced crystallization of charged colloids: a molecular dynamics study.

By using a large enough number of particles and implementing a parallel algorithm on the CUDA platform, we have performed brute-force molecular dynamics simulations to study the template-induced heterogeneous crystallization in charged colloids. Six kinds of templates, whose patterns include the planes of fcc(100), fcc(110), fcc(111), bcc(100), bcc(110) and bcc(111), have been implanted into the middle of the simulation box. Except the fcc(111) template, whose structure benefits not only fcc but also hcp crystals resulting in a similar behavior to homogeneous crystallization, bcc-type templates favor the formation of bcc crystals and bcc-like precursors while fcc-type templates favor the formation of fcc crystals and fcc-like precursors. Therefore, for fcc(100) and fcc(110) templates, heterogeneous crystallization will definitely result in a fcc crystallite. However, the results of heterogeneous crystallization that are induced by bcc-type templates are subtly different at different state points. At the state points where the interaction strength of charged colloids is weak and the fcc phase is thermodynamically stable, the bcc crystals formed with the promotion of bcc-type templates are not stable so as to tend to transform into fcc or hcp crystals. When the interaction strength of charged colloids is high, the predominant bcc crystals formed with the promotion of bcc-type templates can always persist within the time scale of simulation although not bcc but fcc crystals are thermodynamically stable.

Influence of Copper-Based Fillers on Structural and Mechanical Properties of Polylactic Acid Composites

The importance of promising composites in modern materials science is constantly increasing. The use of various fillers or additives is associated with their influence not only on the defining properties of the composite, but also on physical and mechanical characteristics of the material. In this case, the distribution of the additive and its wetting with a polymer play an important role. The problem highlighted in this article is the influence of different copper-containing fillers (copper (II) sulphate powder, micro-sized copper (II) oxide powder, and nano-structured copper (II) oxide-based hollow microspheres) on the technological and physical–mechanical properties of the composites based on polylactic acid (PLA). The hollow microspheres of copper (II) oxide have been obtained by ultrasonic spray atomization via pyrolysis of copper (II) nitrate. The structure of the copper-based additives has been studied using X-ray diffraction, scanning electron microscopy, and static light scattering. For the PLA-composites, scanning electron microscopy, differential scanning calorimetry, stress-strain properties testing, and density analysis have been performed. The plasticizing effect of polycaprolactone and polyethylene glycol has been studied for the highly filled PLA/CuSO4 composite. The samples of PLA with over 2 wt.% of CuO microspheres have a full volume-filling and percolation structure of the additive’s particles. Due to the regular spherical shape of the particles and a lower specific volume, CuO hollow microspheres are uniformly distributed in the PLA matrix acting as a structuring and reinforcing modifier. Differential scanning analysis showed heterogeneous crystallization on CuO particles with an increase in the degree of crystallinity and the melting point of the polymer. It has been shown that the pre-masterbatching technology and adding plasticizers to obtain PLA composites contribute minimizing defects and enhance mechanical properties.

Improvement of compatibility, mechanical, thermal and dielectric properties of poly(lactic acid) and poly(butylene adipate‐co‐terephthalate) blends and their composites with porous clay heterostructures from mixed surfactant systems

AbstractIn this study, nanocomposite poly(lactic acid) and poly(butylene adipate‐co‐terephthalate) (PLA/PBAT) blends were prepared through polymer blending in the presence of multi‐functional epoxy as a compatibilizer that could react with epoxy group and terminated end group of two phases to increase interfacial adhesion between PLA and PBAT and improve the toughness of PLA. The effects of porous clay heterostructure from mixed CTAB:CTAC surfactant in the mole ratio of 1:2 (B1C2‐PCH) were also investigated. The elongation at break of the blends reached 38%, which was eight times that of neat PLA. The cryo‐fractured surface demonstrated the interfacial adhesion caused by the interaction of the epoxy group of the reactive compatibilizer with the terminal carboxyl and hydroxyl groups of PLA and PBAT. Moreover, PBAT reduced the crystallization rate and percent crystallinity of the PLA matrix and further decreased when compatibilizer was used. Alternatively, B1C2‐PCH accelerated the heterogeneous nucleation and crystallization of the nanocomposite films. After adding small amount of B1C2‐PCH, the nanocomposite films demonstrated excellent dielectric properties. Therefore, the improvement of PLA/PBAT nanocomposite blends are capable to be further developed as polymeric capacitor films.

Oriented Low‐n Ruddlesden‐Popper Formamidinium‐Based Perovskite for Efficient and Air Stable Solar Cells

AbstractThe relatively lower crystallinity and random orientation of quantum well structures hinder carrier transport and limit the performance of formamidinium (FA) based low‐n 2D perovskite devices. In this work, the crystallization and quantum well orientation are fine tuned to achieve efficient low‐n FA based Ruddlesden–Popper perovskite solar cells. The effects of different ionic additives on the crystallization, orientation, and photovoltaic performance of FA based low‐n 2D perovskites are comparatively investigated. It is found that NH4+ and SCN− can significantly retard the heterogeneous crystallization of low‐n phases in the intermediate state, and drive the templated growth of quantum well structure with vertical orientation. The optimized photovoltaic device based on (BA)2(FA)3Pb4I13 achieved a power conversion efficiency (PCE) of 18.14%, setting the highest record for FA‐based low‐n 2D perovskite solar cells as far as it is known (average n = 4). The unencapsulated device exhibited excellent stability and maintained 93.3% of its original PCE at 85 °C, and 86.3% at 1 Sun illumination after 720 h in humid ambient condition.

Crystallization and polymorphic behaviour of melt miscible blends of crystalline homopolymers with close melting temperatures under confinement

The confined crystallization behavior of the crystalline/crystalline blends of poly(ethylene oxide) (PEO) and poly(butylene adipate) (PBA) in the electrospun nanofibers fabricated from the ternary blends of polystyrene (PS), PEO, and PBA, where PS was present as the majority component, was investigated. The electrospun nanofibers had PS as the matrix whereas the PEO/PBA mixed phase, with total weight fraction of 0.2 or less, constituted the dispersed domains having sizes of the order of only few hundred nanometers. Hence, the crystallization induced phase separation of PEO and PBA occurred within the confined domains. Despite extremely close melting temperature of PEO and PBA, faster crystallization kinetics of PEO led to entrapment of PBA in the intraspherultic regions of the former. Hence, further crystallization of PBA occurred under hierarchical confinement where the larger and smaller length-scale confinements were imposed by the glassy PS matrix and PEO crystals, respectively. Such a scenario resulted in crystallization occurring both via homogenous as well as heterogeneous crystallization mechanism. Interestingly, the homogenous nucleation of PEO was suppressed whereas the heterogeneous nucleation was enhanced in the ternary blend nanofibers even at very low weight fraction. Most significantly, it was observed, that during melt-recrystallization, memory of chain orientation is retained which favoured the formation of α-crystals in PBA. The present study highlights the role of confinement as well as chain orientation, on the crystallization behaviour, in crystalline/crystalline blend systems for which limited studies have been done so far.