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Inkjet printing as a possible route to study confined crystal structures
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
YKI, Ytkemiska Institutet AB, Institute for Surface Chemistry, Sweden.
KTH, School of Engineering Sciences (SCI), Applied Physics, Nanostructure Physics.ORCID iD: 0000-0001-8534-6577
Intermodulation Products AB.
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2013 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 49, no 1, p. 203-208Article in journal (Refereed) Published
Abstract [en]

Inkjet printing is a technique for the precise deposition of liquid droplets in the pL-volume range in well-defined patterns. Previous studies have shown that inkjet printing is attractive in polymer technology since it permits the controlled deposition of functional polymer surfaces. We suggest that the technique might also be useful for studying crystallization, in particular confined crystallization. Inkjet printing is a non-contact deposition method with minimal risk of contamination, which allows the exact deposition of both polymer solutions and polymer melts. This paper demonstrates the possibility of utilizing the technique to create surfaces where polymer chains form isolated small structures. These structures were confined by both the low polymer content in each droplet and the time constraint on crystal formation that arose as the result of the rapid solvent evaporation from the pL-sized droplets. In theory, inkjet printing enables the exact deposition of systems with as few as a single polymer chain in the average droplet. With appropriate instrumentation, the versatile inkjet technology can be utilized to create whole surfaces covered with polymer structures formed by the crystallization of small, dilute and rapidly evaporating droplets. 110 pL droplets of a 10 -6 g L -1 poly(ε-caprolactone) solution in 1-butanol have been deposited and studied by atomic force microscopy. Small structures of ca. 10 nm thickness and ca. 50 nm diameter also seemed to exhibit crystalline features. Some of the small structures had unusual rectangular forms whilst others were interpreted to be early precursors to six-sided single crystals previously observed for poly(ε-caprolactone). The unusual forms observed may have resulted from the entrapment of crystal structures into metastable phases, due to the limited amount of polymer material present and the rapid evaporation of the droplets.

Place, publisher, year, edition, pages
2013. Vol. 49, no 1, p. 203-208
Keywords [en]
Confinement, Crystallization, Inkjet printing, Poly(ε-caprolactone)
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-109805DOI: 10.1016/j.eurpolymj.2012.10.001ISI: 000315306200021Scopus ID: 2-s2.0-84872291066OAI: oai:DiVA.org:kth-109805DiVA, id: diva2:584450
Funder
Swedish Research Council, 2006-3559 2009-3188
Note

QC 20130207

Available from: 2013-01-09 Created: 2013-01-09 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Different paths to explore confined crystallisation of PCL
Open this publication in new window or tab >>Different paths to explore confined crystallisation of PCL
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this work, different paths to confined crystallisation of poly(ε-caprolactone) (PCL) havebeen explored. Innate confinement effects due to the presence of bulky end groups wereshown to affect crystalline characteristics for strictly monodisperse ε-caprolactone oligomers. The interaction between end groups and end groups, as well as that between end groups andε-caprolactone repeating units, created an obstacle for unfolding the crystal structures that hadinitially formed even at the high-temperature limit of crystallisation where crystallisationoccurred over hundreds of hours. Very rapid X-ray imaging of the in situ crystallisationprocess showed that rapid shifts in the unit cell occurred during the first minute ofcrystallisation due to the difficulty of fitting the bulky end groups in a stable unit cell.Confinement effects also arose when polymer chains were crystallised in systems with smallpore sizes. For linear poly-ε-caprolactone, chains confinement depended mainly on thedimensionalities of the pores. Linear polymers with Mn = 10 000 and 42 500 were stronglyinhibited from forming crystal structures in 10 nm pore systems, but not hindered in 23 nmpore systems. Linear polymers with Mn = 80 000 also experienced limited confinement in the23 nm pores. A star-shaped oligomer with four arms of approximately Mn = 1 000 each evenexperienced confinement in 290 nm pores, although having smaller molecular size and radiusof gyration compared to the linear chains. The innate confinement created by the challenge ofpacking four arms amplified the effect of physical confinement. Another limitation wascreated on the crystallisation process by solving PCL in supercritical CO2 and depositingduring extremely fast phase transfer to gas-like state. The formed structures were limited bythe very low temperature that resulted from the phase change and by the rapid evaporation ofthe solvent. These limitations resulted in entrapment of crystal structures in metastablephases. As a consequence, crystals of hitherto unreported rectangular form were observed aswell as the common six-sided form. The former crystals had considerably lower melting pointcompared to the latter. X-ray analysis showed that two sets of lattice constants existed,supporting the notion of entrapment in metastable phases. Another way of achievingconfinement was precise deposition of droplets in the pikolitre volume range of highly dilutesolutions. The microcrystals which formed were confined by both the low polymer content ineach droplet and by the time constraint on crystal formation that arose by the rapidevaporation of the small droplets. Confinement led to entrapment into metastable phases,evident by the presence of unusual eight-sided and rectangular crystals.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. p. 72
Keywords
crystallisation, poly-ε-caprolactone, end groups, morphology, nanoconfinement, melting, monodisperse, RESS, injet printing
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-109792 (URN)
Public defence
2013-01-25, D3, Lindstedtsvägen 5, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Foundation for Strategic Research , 2006-3559, 2009-3188
Note

QC 20130109

Available from: 2013-01-09 Created: 2013-01-08 Last updated: 2013-01-09Bibliographically approved

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