Super-nucleation in nanocomposites and confinement effects on the crystallizable components within block copolymers, miktoarm star copolymers and nanocomposites
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In this paper we reexamine recent results obtained by our group on the crystallization of nanocomposites and linear and miktoarm star copolymers in order to obtain some general features of their crystallization properties. Different nanocomposites have been prepared where a close interaction between the polymer matrix and the nano-filler has been achieved: in situ polymerized high density polyethylene (HDPE) on carbon nanotubes (CNT); and polycaprolactone (PCL) and poly(ethylene oxide) (PEO) covalently bonded to carbon nanotubes. In all these nanocomposites a “super-nucleation” effect was detected where the CNTs perform a more efficient nucleating action than the self-nuclei of the polymer matrix. It is believed that such a super-nucleation effect stems from the fact that the polymer chains are tethered to the surface of the CNT and can easily form nuclei. For polystyrene (PS) and PCL block copolymers, miktoarm star copolymers (with two arms of PS and two arms of PCL) were found to display more compact morphologies for equivalent compositions than linear PS-b-PCL diblock copolymers. As a consequence, the crystallization of the PCL component always experienced much higher confinement in the miktoarm stars case than in the linear diblock copolymer case. The consequences of the topological confinement of the chains in block copolymers and nanocomposites on the crystallization were the same even though the origin of the effect is different in each case. For nanocomposites a competition between super-nucleation and confinement was detected and the behavior was dominated by one or the other depending on the nano-filler content. At low contents the super-nucleation effect dominates. In both cases, the confinement increases as the nano-filler content increases or the second block content increases (in this case a non-crystallizable block such as PS). The consequences of confinement are: a reduction of both crystallization and melting temperatures, a strong reduction of the crystallinity degree, an increase in the supercooling needed for isothermal crystallization, a depression of the overall crystallization rate and a decrease in the Avrami index until values of one or lower are achieved indicating a nucleation control on the overall crystallization kinetics.
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A decrease of Xc with φfiller is observed, and Xc reaches 10% or even zero when the content of CNT or SiO2 is higher than 10% or 95%, respectively.
“A decrease of X c with ϕ filler is observed and X c reaches 10 % or even zero when the content of CNT or SiO 2 is higher than 10 % or 95 %, respectively, as shown in Fig. 29 A.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [87]
Section 3.2 (page unavailable) reports that HDPE crystallinity decreases as CNT content rises. Section 3.4 (page unavailable) reports a sharp decline above roughly 10% CNT, reaching below 5% at the highest CNT contents studied. The copy does not support the claimed 10% crystallinity value or the assertion that crystallinity reaches zero above 95% SiO₂. (LLM, conf=0.88)
Experimental — accuracy not yet measuredThe Avrami index n exhibits a decreasing trend from 3 to 1 with increasing filler content in PEO/SiO2 and HDPE/CNT composites.
“The Avrami index or exponent n exhibits a decreasing trend from 3 to 1 with increasing filler content as shown in Fig. 29 B.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [87]
Section 3.4 reports that the Avrami index in HDPE/CNT composites decreases with increasing CNT content, reaching 1 or lower. It gives values of 1.9–2.4 for low-CNT composites, not a starting value of 3. Our copy does not report this trend for PEO/SiO2 composites; its PEO discussion concerns samples grafted to MWNTs. Page numbers are unavailable in the indexed passages. (LLM, conf=0.88)
Experimental — accuracy not yet measuredHigh loading of nanofiller could affect the non-isothermal crystallization kinetics in PEO/SiO2 and HDPE/CNT nanocomposites, in which fractionated crystallization was not found in the latter case.
“The high loading of nanofiller could affect the non-isothermal crystallization kinetics in PEO/SiO 2 [309] and HDPE/carbon nanotube (CNT) [87] nanocomposites, in which the fractionated crystallization was not found in the latter case.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [87]
For the HDPE/CNT part cited to this paper, Section 3.2 reports that higher CNT loading changes crystallization temperature and reduces crystallinity during cooling from the melt. Section 3.4 reports loading-dependent crystallization rates, but those measurements are isothermal. Our copy does not state that fractionated crystallization was absent in HDPE/CNT nanocomposites; the PEO/SiO2 part is attached to a different citation. (LLM, conf=0.84)
Experimental — accuracy not yet measuredDifferent chain topology, such as miktoarm star copolymers, can result in higher confinement than analogous linear copolymers.
“Different chain topology, such as miktoarm star copolymers, can result in higher confinement than analogous linear copolymers.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [87]
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References 82 · Cited by 115
Research works printed but not linked: 7
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- Prof. A.J. Müller (born 1960) is a Materials Engineer, with an M.Sc. in Chemistry (1983) and a Ph.D. in Physics (from Bristol University, U.K., 1989). He is presently the head of the Simón Bolívar University polymer group and holds the position of Full Professor in the Materials Science Department. He has co- authored more than 300 publications from which 155 have been published in interna- tional peer review journals (indexed in the SCI). He has tutored 82 B.Sc. thesis and 42 postgraduate thesis (both M.Sc. and Ph.D.). He has won several awards in Venezuela, including the Lorenzo Mendoza Fleury, Polar Prize for basic science. Prof. Müller has given keynote, ple- nary and invited lectures in more than 20 countries around the world. He has achieved an h index of 30 (December 2010). In July 2009 he became a ''corresponding member" of the Venezuelan National Academy of Engi- neering and Habitat (ANIH). His field of interests include: polymer solu- tion rheology, structured fluids, morphology, nucleation, crystallization and crystallization kinetics of semi-crystalline materials and of multi- phasic materials (in particular polymer blends, block copolymers, bio- polymers and nano-composites). He is the current president of the Venezuelan Polymer Association (ASOVENP).
- María L. Arnal is a Materials Engineer, with an M.Sc. and Ph.D. in Engineering (from Simón Bolívar University, Venezuela). She currently holds the position of full professor at the Materials Science department of Simón Bolí- var University (Caracas, Venezuela). She has co-authored 42 publications which have been published in international peer review jour- nals (indexed in the SCI) achieving an h-Index of 18. Fields of interest of María L. Arnal are: i) thermal analysis ii) morphology, nucleation and crystallization behavior of semi-crystal- line materials and semi-crystalline components within multiphasic materials (polymer blends, block copolymers and nanocomposites); ii)
- Authors
- Müller, A. J., Arnal, M. L., Trujillo, M., & Lorenzo, A. T.
- Affiliations
- Universidad Simón Bolívar (VE)
- Corresponding author
- Müller, Alejandro J.
- Venue
- European Polymer Journal
- Publisher
- Elsevier BV
- Published
- 2011-04
- Volume
- 47
- Issue
- 4
- Pages
- 614-629
- ISSN
- 0014-3057 (ISSN-L)
- OpenAlex
- W2003287266
- Cited by
- 115
- References
- 82
- Citations by year
- 2026: 6 · 2025: 3 · 2024: 6 · 2023: 7 · 2022: 12 · 2021: 7 · 2020: 10 · 2019: 7 · 2018: 9 · 2017: 11 · 2016: 6 · 2015: 11 · 2014: 8 · 2013: 4 · 2012: 4
- FWCI
- 3.17
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- European Polymer Journal (publishedVersion, cc-by-nc-nd)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Nanocomposites and Properties
- Keywords
- polymer crystallization, nanocomposites, block copolymers, miktoarm star polymers, carbon nanotubes, confinement effects, polystyrene, polycaprolactone, poly(ethylene oxide), high-density polyethylene, crystallization kinetics, Avrami exponent, isothermal crystallization, crystallinity, nucleation
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