Slow and fast crystallising poly aryl ether ketones (PAEKs) in 3D printing: Crystallisation kinetics, morphology, and mechanical properties

Nan, Yi; Davies, Richard J.; Chaplin, A. J.; McCutchion, Paul; Ghita, Oana

doi:10.1016/j.addma.2021.101843

Cited by 26 publications

(39 citation statements)

References 54 publications

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“…The thermal and crystallization behavior of PEKK 50/50 seems to meet the requirements for use in additive manufacturing and more specifically in LS: The crystallization kinetics is slow ( t 1/2 > 20 min for T C > 270 °C), similar to the one reported for PEKK 60/40 , and clearly slower than that of PEEK. , The reached crystallinity is high, around 30 wt %, higher than that of PEKK 60/40 ,,, or PEEK. , The crystallization kinetics, almost only primary, is very simple as compared to those of other PEKK or PEEK. ,,, …”

Section: Is Pekk 50/50 a Good Candidate For Ht-ls?supporting

confidence: 52%

“…• The crystallization kinetics is slow (t 1/2 > 20 min for T C > 270 °C), similar to the one reported for PEKK 60/ 40 17,47 and clearly slower than that of PEEK. 43,48 • The reached crystallinity is high, around 30 wt %, higher than that of PEKK 60/40 19,29,47,49 or PEEK. 48,50 • The crystallization kinetics, almost only primary, is very simple as compared to those of other PEKK or PEEK.…”

Section: Is Pekk 50/50 a Good Candidate For Ht-ls?mentioning

confidence: 95%

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Thermal and Crystallization Properties of the Alternated Tere/Iso PEKK Copolymer: Importance in High-Temperature Laser Sintering

Cherri

Iliopoulos

Régnier

et al. 2022

ACS Appl. Polym. Mater.

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High-temperature laser sintering (HT-LS) is a very promising additive manufacturing process for the production of parts of complex geometry for highly demanding applications. Poly(aryl ether ketone) polymers such as poly(ether ketone), poly(ether ether ketone), and poly(ether ketone ketone) (PEKK) have attracted increasing interest during the last decade for use in HT-LS. Among them, PEKK offers the advantage of exhibiting tunable melting temperature and crystallization rate due to its copolymer structure. Indeed, PEKK is synthesized by Friedel−Crafts polyacylation condensation of diphenyl ether with terephthaloyl chloride (T units) and isophthaloyl chloride (I units). In this work, we focus on a specific member of the PEKK family having a regular alternated T/I structure, PEKK 50/50, and study its isothermal crystallization from the melt at various crystallization temperatures (T C ), from 200 °C to 290 °C. A quantitative analysis based on X-ray scattering and differential scanning calorimetry experiments is performed. Primary crystallization dominates the process with a half-time of crystallization higher than 6 min and an Avrami exponent between 2.2 and 3. Stacks of periodic crystalline lamellae are first created, followed by lateral growth of these crystalline lamellae, leading to a gradual increase of the weight crystallinity. Crystalline form I, with traces of form III, is mostly observed regardless of T C . The amount and perfection of the crystalline phase increase with T C . The crystalline state achieved, as well as the thermal and rheological behavior of PEKK 50/50 during crystallization at high T C (∼280−290 °C), are promising for use in HT-LS manufacturing.

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Section: Is Pekk 50/50 a Good Candidate For Ht-ls?supporting

confidence: 52%

Section: Is Pekk 50/50 a Good Candidate For Ht-ls?mentioning

confidence: 95%

Thermal and Crystallization Properties of the Alternated Tere/Iso PEKK Copolymer: Importance in High-Temperature Laser Sintering

Cherri

Iliopoulos

Régnier

et al. 2022

ACS Appl. Polym. Mater.

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“…The dual Avrami model parameters are presented in Table 1. Recently, Ryu et al [ 37 ] and Yi et al [ 38 ] have reported good fits of this dual Avrami model to cyclic poly(ε‐caprolactone) and polyaryletherketone (Victrex PEEK 151 and AM 200). In each polymer,

n_{s} < n_{p}

reflects slower secondary crystallization kinetics.…”

Section: Resultsmentioning

confidence: 96%

Dual Nakamura model for primary and secondary crystallization applied to nonisothermal crystallization of poly(ether ether ketone)

Seo

Zhang

Schaake³

et al. 2021

Polymer Engineering & Sci

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Non‐isothermal crystallization kinetics has been traditionally predicted using the Nakamura crystal growth model, which is an integral form of the Avrami equation under the assumption that the non‐isothermal kinetics can be explained using a series of infinitesimal isothermal steps. However, the Nakamura model often overpredicts crystal fraction near the end of crystallization because of ignoring slower secondary crystallization kinetics. In this study, the dual Nakamura model is proposed to capture both primary and secondary crystallization kinetics of poly(ether ether ketone) (PEEK). First, non‐isothermal crystallization kinetics of PEEK is monitored at five constant cooling rates of 10, 30, 50, 70, and 90 K/min via differential scanning calorimetry. The dual Nakamura model, which contains a smaller secondary Avrami exponent (ns) to account for the secondary crystallization, is fitted to the exothermal heat flow curves. The dual Nakamura model successfully describes the final stage of crystallization at all cooling rates by reducing the crystal growth dimension from np = 3 for primary crystallization to ns≅1.

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“…The morphology of the crystals and their correlation with the Avrami index n is well documented in the literature. 33,34 The n value ranges from 2.50 to 2.88 (except for T i = 350 °C) related to disklike spherulites. Particularly, the n value decreases dramatically when the conventional 2D or 3D growth of polymer crystals is inhibited.…”

Section: Melt Memory Effect Of Bd-peskmentioning

confidence: 99%

Study on the Melt Memory Effect and Melt Recrystallization Behavior of Crystallizable Biphenylene Poly(arylene ether sulfone ketone)

Liu

Shang

et al. 2022

Macromolecules

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Poly(arylene ether sulfone) resins are usually a class of amorphous polymers, which makes them inferior to other semicrystalline aromatic polymers in solvent resistance, chemical stability, and mechanical strength. Herein, a crystallizable poly-(arylene ether sulfone ketone) with a high biphenylene content (BD-PESK) was designed and synthesized. BD-PESK showed excellent thermal stability with a T g of 241 °C and 5% weight loss temperature of 548 °C. Meanwhile, BD-PESK exhibited an obvious melt memory effect at 350−370 °C, but a weak melt memory effect would survive even above its equilibrium melting point due to the high segment rigidity. Under the guidance of this effect, the melt recrystallization of BD-PESK with a maximum crystallinity of 23% can be realized effectively, which made it have excellent solvent resistance similar to the PEEK resin. Semicrystalline BD-PESK showed a high tensile strength up to 86 MPa with a good elongation at break of 23%. Furthermore, due to the combination of high T g and semicrystallinity, BD-PESK could maintain 71% storage modulus at 240 °C and still 1.4% storage modulus at 300 °C, respectively, showing superior heat resistance to most thermoplastic polymers.

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Slow and fast crystallising poly aryl ether ketones (PAEKs) in 3D printing: Crystallisation kinetics, morphology, and mechanical properties

Cited by 26 publications

References 54 publications

Thermal and Crystallization Properties of the Alternated Tere/Iso PEKK Copolymer: Importance in High-Temperature Laser Sintering

Thermal and Crystallization Properties of the Alternated Tere/Iso PEKK Copolymer: Importance in High-Temperature Laser Sintering

Dual Nakamura model for primary and secondary crystallization applied to nonisothermal crystallization of poly(ether ether ketone)

Study on the Melt Memory Effect and Melt Recrystallization Behavior of Crystallizable Biphenylene Poly(arylene ether sulfone ketone)

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