Confinement Effects on the Crystallization Kinetics and Self‐Nucleation of Double Crystalline Poly(p‐dioxanone)‐b‐poly(ϵ‐caprolactone) Diblock Copolymers
Abstract
The morphology, crystallization and self nucleation behavior of double crystalline diblock copolymers of poly(p‐dioxanone) (PPDX) and poly(ϵ‐caprolactone) (PCL) with different compositions have been studied by different techniques, including optical microscopy (OM), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The two blocks crystallize in a single coincident exotherm when cooled from the melt. The self‐nucleation technique is able to separate into two exotherms the crystallization of each block. We have gathered evidences indicating that the PPDX block can nucleate the PCL block within the copolymers regardless of the composition. This effect is responsible for the lack of homogeneous nucleation or fractionated crystallization of the PCL block even when it constitutes a minor phase within the copolymer (25% or less). Nevertheless, we were able to show that decreasing amounts of PCL within the diblock copolymer still produces confinement effects that retard the crystallization kinetics of the PCL component and decrease the Avrami index. On the other hand evidence for confinement was also obtained for the PPDX block, since as its content is reduced within the copolymer, a depression in its self‐nucleation and annealing temperatures were observed.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The understanding of the complicated properties of double crystalline diblock copolymer systems is still at a nascent stage.
“Although there have been a number of prior reports on double crystalline diblock copolymer systems, the understanding of their complicated properties is still at a nascent stage. [5-16]”
Cited by
Sorted by citations
Lorenzo, A. T., Arnal, M. L., Albuerne, J., & Müller, A. J. (2006) · Polymer Testing · doi:10.1016/j.polymertesting.2006.10.005 · Cited by 704 · see citing works
Self-citationNucleation and Crystallization in Diblock and Triblock Copolymers
Müller, A. J., Balsamo, V., & Arnal, M. L. (2005) · Advances in Polymer Science · doi:10.1007/12_001 · Cited by 294 · see citing works
Self-citationCastillo, R. V., & Müller, A. J. (2009) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2009.03.002 · Cited by 253 · see citing works
Self-citationEffect of annealing time on the self-nucleation behavior of semicrystalline polymers
Lorenzo, A. T., Arnal, M. L., Sánchez, J. J., & Müller, A. J. (2006) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.20832 · Cited by 245 · see citing works
Self-citationDifferential Scanning Calorimetry of Polymers
Müller, A. J., & Michell, R. M. (2016) · Wiley eBooks · doi:10.1002/9781118892756.ch5 · Cited by 197 · see citing works
Self-citationMichell, R. M., Mugica, A., Zubitur, M., & Müller, A. J. (2015) · Advances in Polymer Science · doi:10.1007/12_2015_327 · Cited by 159 · see citing works
Self-citationCastillo, R. V., Müller, A. J., Lin, M.-C., Chen, H., Jeng, U., & Hillmyer, M. A. (2008) · Macromolecules · doi:10.1021/ma800859y · Cited by 111 · see citing works
Self-citationHamley, I. W., Parras, P., Castelletto, V., Castillo, R. V., Müller, A. J., Pollet, E., Dubois, P., & Martin, C. M. (2006) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600085 · Cited by 108 · see citing works
Self-citationFractionated crystallization in semicrystalline polymers
Sangroniz, L., Wang, B., Su, Y., Liu, G., Cavallo, D., Wang, D., & Müller, A. J. (2021) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2021.101376 · Cited by 102 · see citing works
Self-citationCrystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems
Yu, C., Xie, Q. M., Bao, Y., Shan, G., & Pan, P. (2017) · Crystals · doi:10.3390/cryst7050147 · Cited by 66 · see citing works
Fenni, S. E., Wang, J., Haddaoui, N., Favis, B. D., Müller, A. J., & Cavallo, D. (2019) · Thermochimica Acta · doi:10.1016/j.tca.2019.03.015 · Cited by 61 · see citing works
“The presence of coincident crystallization phenomena can be revealed by WAXS and/or selfnucleation techniques [3,4,7,23,24,39-41].”
BackgroundSelf-citationPolymeric Crystallization under Nanoscale 2D Spatial Confinement
Chung, T., Wang, T.-C., Ho, R., Sun, Y., & Ko, B. (2010) · Macromolecules · doi:10.1021/ma100998k · Cited by 49 · see citing works
Crystalline−Crystalline Diblock Copolymers of Linear Polyethylene and Hydrogenated Polynorbornene
Myers, S. B., & Register, R. A. (2008) · Macromolecules · doi:10.1021/ma800759b · Cited by 47 · see citing works
Isothermal Crystallization Kinetics of Polymers
Müller, A. J., Michell, R. M., & Lorenzo, A. T. (2016) · Wiley eBooks · doi:10.1002/9781118892756.ch11 · Cited by 47 · see citing works
Self-citationMolecular simulations of confined crystallization in the microdomains of diblock copolymers
Zha, L., & Hu, W. (2015) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2015.10.010 · Cited by 45 · see citing works
Palacios, J. K., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b02148 · Cited by 41 · see citing works
Self-citationNonisothermal and Isothermal Cold Crystallization Behaviors of Biodegradable Poly(p-dioxanone)
Zeng, J., Srinivansan, M., Li, S.-L., Narayan, R., & Wang, Y. (2011) · Industrial & Engineering Chemistry Research · doi:10.1021/ie102299y · Cited by 41 · see citing works
Li, S., Myers, S. B., & Register, R. A. (2011) · Macromolecules · doi:10.1021/ma201951j · Cited by 40 · see citing works
Crystallization in Nano‐Confined Polymeric Systems
Müller, A. J., Arnal, M. L., & Lorenzo, A. T. (2013) · Handbook of Polymer Crystallization · doi:10.1002/9781118541838.ch12 · Cited by 40 · see citing works
Self-citationDu, Z., Xu, J., Yang, Y., & Fan, Z. (2007) · Journal of Applied Polymer Science · doi:10.1002/app.26113 · Cited by 39 · see citing works
Lorenzo, A. T., Müller, A. J., Priftis, D., Pitsikalis, M., & Hadjichristidis, N. (2007) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/pola.22283 · Cited by 38 · see citing works
Self-citationTrilayered morphology of an ABC triple crystalline triblock terpolymer
Palacios, J. K., Tercjak, A., Liu, G., Wang, D., Zhao, J., Hadjichristidis, N., & Müller, A. J. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b01576 · Cited by 37 · see citing works
Self-citationNucleation and Crystallization of PLDA‐ b ‐PE and PLLA‐ b ‐PE Diblock Copolymers
Müller, A. J., Castillo, R. V., & Hillmyer, M. A. (2006) · Macromolecular Symposia · doi:10.1002/masy.200651025 · Cited by 36 · see citing works
Self-citationBoschetti‐de‐Fierro, A., Lorenzo, A. T., Müller, A. J., Schmalz, H., & Abetz, V. (2008) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200700434 · Cited by 31 · see citing works
Self-citationHuang, C.-L., Jiao, L., Zeng, J., Zhang, J., Yang, K., & Wang, Y. (2013) · The Journal of Physical Chemistry B · doi:10.1021/jp4059966 · Cited by 28 · see citing works
Hydrolytic Degradation of Double Crystalline PPDX‐b‐PCL Diblock Copolymers
Albuerne, J., Marquez, L., Müller, A. J., Raquez, J., Degée, P., & Dúbois, P. (2005) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200400524 · Cited by 28 · see citing works
Self-citationPalacios, J. K., Mugica, A., Zubitur, M., & Müller, A. J. (2018) · Crystallization in Multiphase Polymer Systems · doi:10.1016/b978-0-12-809453-2.00006-2 · Cited by 18 · see citing works
Self-citationManipulation of Crystallization Sequence in PEO-b-PCL Films Using Solvent Interactions
Brigham, N. C., Nardi, C., Carandang, A., Allen, K., & Horn, R. M. V. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b02004 · Cited by 17 · see citing works
Cao, Y., Zhu, P., Wang, Z., Zhou, Y. L., Chen, H., Müller, A. J., Wang, D., & Dong, X. (2018) · Polymer Crystallization · doi:10.1002/pcr2.10012 · Cited by 17 · see citing works
Self-citationCrystallization, morphology and self-assembly of double, triple and tetra crystalline block polymers
Palacios, J. K., Michell, R. M., & Müller, A. J. (2023) · Polymer Testing · doi:10.1016/j.polymertesting.2023.107995 · Cited by 17 · see citing works
“…and PEO, such as poly(butylene adipate) (PBA) [113], poly( γ -butyr- olactone) [114,115], poly( δ -valerolactone) [116], poly( p -dioxanone) [117,118], poly(2-isopropyl-2-oxazoline) [119], poly(ethylene brassy-late) [120], poly[oligo(3S-iso-butylmorpholine-2,5-dione)]-diol [121] (PIBMD),…”
Self-citationCrystallization of double crystalline symmetric diblock copolymers
Kundu, C., & Dasmahapatra, A. K. (2014) · Polymer · doi:10.1016/j.polymer.2013.12.047 · Cited by 14 · see citing works
Effect of block asymmetry on the crystallization of double crystalline diblock copolymers
Kundu, C., & Dasmahapatra, A. K. (2014) · The Journal of Chemical Physics · doi:10.1063/1.4889997 · Cited by 12 · see citing works
Palacios, J. K., Zhang, H., Zhang, B., Hadjichristidis, N., & Müller, A. J. (2020) · Polymer · doi:10.1016/j.polymer.2020.122863 · Cited by 11 · see citing works
Self-citationMatxinandiarena, E., Múgica, A., Zubitur, M., Ladelta, V., Zapsas, G., Cavallo, D., Hadjichristidis, N., & Müller, A. J. (2021) · Polymers · doi:10.3390/polym13183133 · Cited by 12 · see citing works
Self-citationZhang, X., Ouyang, Z., Schulze, R., Keller, T. F., Jandt, K. D., & Su, Z. (2014) · RSC Advances · doi:10.1039/c3ra47499b · Cited by 11 · see citing works
Birefringence Control of Semicrystalline Block Copolymers by Crystallization under Confinement
Li, M., Chang, G.-W., Lin, T., Ho, R., Chuang, W., & Kooi, S. E. (2010) · Langmuir · doi:10.1021/la1034432 · Cited by 10 · see citing works
Cicolella, A., Scoti, M., Talarico, G., Müller, A. J., Girolamo, R. D., & Rosa, C. D. (2024) · Macromolecules · doi:10.1021/acs.macromol.4c01402 · Cited by 8 · see citing works
Self-citationEsteves, L. M., Marquez, L., & Müller, A. J. (2005) · Journal of Applied Polymer Science · doi:10.1002/app.21809 · Cited by 6 · see citing works
Self-citationWang, T., Zhao, H., Liu, Y., & Hao, J. (2013) · Journal of Applied Polymer Science · doi:10.1002/app.39486 · Cited by 4 · see citing works
Huang, C., Zeng, J., Jiao, L., & Yang, K. (2014) · Journal of Applied Polymer Science · doi:10.1002/app.40940 · Cited by 3 · see citing works
Crystallization of Double Crystalline Diblock Copolymer by Dynamic Monte Carlo Simulation
Kundu, C., & Dasmahapatra, A. K. (2015) · Macromolecular Symposia · doi:10.1002/masy.201400073 · Cited by 2 · see citing works
- Authors
- Müller, A. J., Albuerne, J., Esteves, L. M., Marquez, L., Raquez, J., Degée, P., Dubois, P., Collins, S., & Hamley, I. W.
- Affiliations
- Universidad Simón Bolívar (VE)
- University of Mons (BE)
- University of Leeds (GB)
- Venue
- Macromolecular Symposia
- Publisher
- Wiley
- Published
- 2004-08
- Volume
- 215
- Issue
- 1
- Pages
- 369-382
- ISSN
- 1022-1360 (ISSN-L)
- 1521-3900
- OpenAlex
- W1973105627
- Cited by
- 41
- References
- 0
- Citations by year
- 2024: 1 · 2023: 1 · 2021: 2 · 2020: 1 · 2019: 1 · 2018: 1 · 2017: 5 · 2016: 2 · 2015: 3 · 2014: 4 · 2013: 3
- FWCI
- 3.30
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecular Symposia (publishedVersion)
- PolyPublie (École Polytechnique de Montréal) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Keywords
- poly(p-dioxanone), polycaprolactone, diblock copolymers, confinement effects, crystallization kinetics, self-nucleation, Avrami exponent, nucleation, annealing temperature, polymer morphology
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review