Effect of additives, catalyst residues, and confining substrates on the fractionated crystallization of polypropylene droplets
Abstract
Abstract Fractionated crystallization of Ziegler‐Natta PP (ZN‐PP) droplets produced from ZN‐PP/polystyrene (PS) multilayered films resulted in four crystallization exotherms at 40, 64, 90, and 103°C. The origins of these crystallization peaks were investigated in this article. The nucleation of ZN‐PP droplets at various crystallization exotherms was attributed to (1) various additives in ZN‐PP and PS, (2) catalyst residues present in ZN‐PP, or (3) substrate nucleation by confining matrix. Effect of various additives on the fractionated crystallization an additive‐free grade of ZN‐PP (cPP) was investigated. Crystallization of cPP droplets from 200‐nm layers showed that Irganox was responsible for crystallization of droplets at 103°C. Irgafos and ZnS did not affect the crystallization of cPP droplets. We also investigated three grades of PP, which were synthesized using different catalysts. The PP grades were ZN‐PP, developmental PP (D‐PP) and metallocene PP (M‐PP). D‐PP droplets from 200‐nm layers showed crystallization at 100°C, while ZN‐PP resulted in crystallization at 90 and 103°C. It was suggested that the 90°C peak for ZN‐PP droplets was most likely due to the presence of Ziegler‐Natta catalyst residues. Crystallization of M‐PP droplets produced from 200 nm showed multiple crystallization exotherms (60 to 90°C). The effect of confining substrates on the fractionated crystallization of ZN‐PP droplets revealed heterogeneous nucleation by polycarbonate (PC) substrate. When the confining matrix was changed from polystyrene (PS) to polymethyl methacrylate (PMMA), the crystallization thermograms of ZN‐PP droplets were unaffected. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
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?
In iPP/PS multilayer films, for 12 nm iPP nanolayers containing Irganox, crystallization exotherms at large undercooling ascribed to homogeneous nucleation did not change significantly, suggesting Irganox particles were excluded from iPP droplets because droplet size was smaller than Irganox particles.
“For 12 nm iPP nanolayers containing Irganox ( Fig. 8 A), the crystallization exotherms at large undercooling, ascribed to homogeneous nucleation, did not change significantly for all the samples, suggesting that Irganox particles were excluded from the iPP droplets due to the droplets size being smaller than the size of Irganox particles.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
In iPP/PS multilayer films, iPP droplets from 200 nm nanolayers showed fractionated crystallization with two exothermic peaks at 112 and 90°C; increasing Irganox concentration increased the 112°C peak at the expense of the 90°C peak, indicating the high-temperature fractionated peak could be ascribed to Irganox or similar antioxidants.
“However, iPP droplets obtained from 200 nm iPP nanolayers with relatively larger diameters showed fractionated crystallization with two exothermic peaks centered at 112 and 90 °C, as shown in Fig. 8 B. With increasing the Irganox concentration, the intensity of 112 °C peak (peak A) increased at the expense of the intensity of 90 °C peak (peak B).The results of these elegant experiments indicated”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
Addition of nucleating agents can verify the hypothesis that fractionated crystallization originates from a lack of efficient nuclei.
“The origin of fractionated crystallization is ascribed to the lack of efficient nuclei, and this hypothesis can also be verified by the addition of nucleating agents.[ 8 , 13 , 32 , 46 , 4 8 , 4 9 ]”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
The origin of fractionated crystallization is the lack of efficient nuclei.
“The origin of fractionated crystallization is ascribed to the lack of efficient nuclei, and this hypothesis can also be verified by the addition of nucleating agents.[ 8 , 13 , 32 , 46 , 4 8 , 4 9 ]”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
iPP sub-micron droplets in PS or PMMA crystallized exclusively via homogeneous nucleation at about 40 °C, whereas in a PC matrix the majority crystallized at around 85 °C with a small fraction at the homogeneous crystallization temperature, ascribed to surface-induced nucleation.
“While both iPP sub-micron droplets crystallized exclusively via homogeneous nucleation at about 40 °C when in contact with PS or PMMA, fractionated crystallization was observed in the case of PC matrix.In this case, the majority of droplets crystallized at around 85 °C, with a small fraction of droplets crystallizing at the homogeneous crystallization temperature.The authors ascribed the effect to”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
The selected non-isothermal crystallization temperatures of iPP in isolated polymer domains are ascribed to the homogeneous nucleation mechanism.
“The selected temperatures are ascribed to the homogeneous nucleation mechanism.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [8]
Cites
Polymer Crystallization in 25-nm Spheres
Loo, Y., Register, R. A., & Ryan, A. J. (2000) · Physical Review Letters · doi:10.1103/physrevlett.84.4120 · Cited by 329 · see citing works
Polymer crystallization confined in one, two or three dimensions
Loo, Y.-L., Register, R. A., Ryan, A. J., & Dee, G. T. (2001) · Macromolecules · doi:10.1021/ma011521p · Cited by 324 · see citing works
Massa, M. V., & Dalnoki-Veress, K. (2004) · Physical Review Letters · doi:10.1103/physrevlett.92.255509 · Cited by 192 · see citing works
Nucleation of polymer droplets
Koutsky, J. A., Walton, A. G., & Baer, E. (1967) · Journal of Applied Physics · doi:10.1063/1.1709769 · Cited by 180 · see citing works
Self-citationAddendum to the thermal properties of polypropylene
Bu, H. S., Cheng, S. Z. D., & Wunderlich, B. (1988) · Die Makromolekulare Chemie Rapid Communications · doi:10.1002/marc.1988.030090205 · Cited by 155 · see citing works
Woo, E., Huh, J., Jeong, Y. G., & Shin, K. (2007) · Physical Review Letters · doi:10.1103/physrevlett.98.136103 · Cited by 152 · see citing works
Structure and thermal stability of polyethylene nanolayers
Bernal-Lara, T. E., Liu, R. Y. F., Hiltner, A., & Baer, E. (2005) · Polymer · doi:10.1016/j.polymer.2005.01.055 · Cited by 97 · see citing works
Castillo, R. V., Arnal, M. L., Müller, A. J., Hamley, I. W., Castelletto, V., Schmalz, H., & Abetz, V. (2008) · Macromolecules · doi:10.1021/ma0718907 · Cited by 96 · see citing works
Ghijsels, A., Groesbeek, N., & Yip, C. W. (1982) · Polymer · doi:10.1016/0032-3861(82)90217-8 · Cited by 90 · see citing works
Morales, R. A., Arnal, M. L., & M�ller, A. J. (1995) · Polymer Bulletin · doi:10.1007/bf00963138 · Cited by 69 · see citing works
Formation and transformation of smectic polypropylene nanodroplets
Jin, Y., Hiltner, A., Baer, E., Masirek, R., Piórkowska, E., & Gałęski, A. (2006) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.20839 · Cited by 55 · see citing works
Self-citationFractionated crystallization of polypropylene droplets produced by nanolayer breakup
Jin, Y., Hiltner, A., & Baer, E. (2007) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.21146 · Cited by 45 · see citing works
Self-citationThe solubility of stabilizing additives in polypropylene
Billingham, N. Ć., Calvert, P., Okopi, I. W., & Uzuner, A. (1991) · Polymer Degradation and Stability · doi:10.1016/0141-3910(91)90093-7 · Cited by 43 · see citing works
Transformation of isotactic polypropylene droplets from the mesophase into the α-phase
Langhe, D. S., Hiltner, A., & Baer, E. (2011) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.22357 · Cited by 39 · see citing works
Self-citationFractionated crystallization of α-and β-nucleated polypropylene droplets
Langhe, D. S., Keum, J. K., Hiltner, A., & Baer, E. (2011) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.22162 · Cited by 31 · see citing works
Self-citationCrystallization behavior and rheological properties of polycarbonate and polypropylene blends
Chun, Y. S., Jung, H. C., Han, M. S., & Kim, W. N. (1999) · Polymer Engineering and Science · doi:10.1002/pen.11618 · Cited by 20 · see citing works
Jin, Y., Hiltner, A., & Baer, E. (2007) · Journal of Applied Polymer Science · doi:10.1002/app.26584 · Cited by 18 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Onset of Flow-Induced Crystallization Kinetics of Highly Isotactic Polypropylene
Hamad, F. G., Colby, R. H., & Milner, S. T. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00386 · Cited by 104 · see citing works
Fractionated 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
Wang, B., Utzeri, R., Castellano, M., Stagnaro, P., Müller, A. J., & Cavallo, D. (2020) · Macromolecules · doi:10.1021/acs.macromol.0c01167 · Cited by 82 · see citing works
Horváth, Z., Gyarmati, B., Menyhárd, A., Doshev, P., Gahleitner, M., Varga, J., & Pukánszky, B. (2014) · RSC Advances · doi:10.1039/c4ra01917b · Cited by 50 · see citing works
Fiorentino, B., Fulchiron, R., Duchet‐Rumeau, J., Bounor‐Legaré, V., & Majesté, J. (2013) · Polymer · doi:10.1016/j.polymer.2013.03.057 · Cited by 40 · see citing works
Carmeli, E., Fenni, S. E., Caputo, M. R., Müller, A. J., Tranchida, D., & Cavallo, D. (2021) · Macromolecules · doi:10.1021/acs.macromol.1c01430 · Cited by 36 · see citing works
Crystallization Kinetics in an Immiscible Polyolefin Blend
Huang, D. E., Kotula, A. P., Snyder, C. R., & Migler, K. B. (2022) · Macromolecules · doi:10.1021/acs.macromol.2c01691 · Cited by 33 · see citing works
Understanding polymer nucleation by studying droplets crystallization in immiscible polymer blends
Fenni, S. E., Müller, A. J., & Cavallo, D. (2022) · Polymer · doi:10.1016/j.polymer.2022.125514 · Cited by 34 · see citing works
Ma, P., Hristova‐Bogaerds, D. G., Zhang, Y., & Lemstra, P. J. (2014) · Polymer Bulletin · doi:10.1007/s00289-014-1101-x · Cited by 29 · see citing works
Concomitant Crystallization and Cross-Nucleation in Polymorphic Polymers
Cavallo, D., & Alfonso, G. C. (2015) · Advances in polymer science · doi:10.1007/12_2015_330 · Cited by 18 · see citing works
Baeten, D., Cavallo, D., Portale, G., Androsch, R., Mathot, V., & Goderis, B. (2016) · Springer eBooks · doi:10.1007/978-3-319-31329-0_10 · Cited by 15 · see citing works
Wang, X., Wang, Z., Xiang, S., Peng, M., Li, G., & Huang, Y. (2024) · Additive manufacturing · doi:10.1016/j.addma.2024.104188 · Cited by 11 · see citing works
Wang, B., Mathew, A., & Napolitano, S. (2021) · ACS Macro Letters · doi:10.1021/acsmacrolett.1c00123 · Cited by 9 · see citing works
Wang, W., Buzzi, S., Fenni, S. E., Carmeli, E., Wang, B., Liu, G., Müller, A. J., & Cavallo, D. (2022) · Macromolecular Chemistry and Physics · doi:10.1002/macp.202200202 · Cited by 7 · see citing works
Li, Y., Kong, J., Xin, S., Han, C., & Xiao, L. (2016) · Journal of Thermal Analysis and Calorimetry · doi:10.1007/s10973-016-5992-7 · Cited by 7 · see citing works
Fractionated Crystallization in Polymer Blends
Langhe, D. S. (2017) · Elsevier eBooks · doi:10.1016/b978-0-12-809453-2.00009-8 · Cited by 6 · see citing works
Self-citationTian, J., Liu, G., Chen, X., Lü, J., Zhou, Z., & Huang, R. (2012) · Journal of Applied Polymer Science · doi:10.1002/app.38822 · Cited by 6 · see citing works
Istrate, D., Kleppinger, R., & Remerie, K. (2016) · Springer eBooks · doi:10.1007/978-3-319-31329-0_17 · Cited by 1 · see citing works
Yao, Y., Ju, W., Su, Y., & Wang, D. (2026) · Polymer · doi:10.1016/j.polymer.2026.130691
Peng, C., Wang, Z., Li, G., & Huang, Y. (2026) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.6c03788
- Authors
- Langhe, D. S., Hiltner, A., & Baer, E.
- Affiliations
- Case Western Reserve University (US)
- Corresponding author
- Langhe, Deepak S.
- ORCID
- Baer, Eric
- Venue
- Journal of Applied Polymer Science
- Publisher
- Wiley
- Published
- 2012-01-20
- Volume
- 125
- Issue
- 3
- Pages
- 2110-2120
- ISSN
- 0021-8995 (ISSN-L)
- 1097-4628
- OpenAlex
- W2003923705
- Cited by
- 21
- References
- 18
- Citations by year
- 2026: 3 · 2024: 1 · 2022: 3 · 2021: 3 · 2020: 1 · 2017: 1 · 2016: 3 · 2015: 2 · 2014: 2 · 2013: 1 · 2012: 1
- FWCI
- 1.51
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Applied Polymer Science (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Physical Sciences › Materials Science › Materials Chemistry › Thermal and Kinetic Analysis
- Keywords
- polypropylene, fractional crystallization, heterogeneous nucleation, polymer additives, crystallization exotherm, polycarbonate substrate
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
