The Complex World of Thermoplastic Composites: Navigating Crystallinity Gradients

In the realm of high-performance materials, poly(aryletherketone)s (PAEKs), notably Poly(etherketoneketone) (PEKK), stand out for their superior mechanical properties, chemical resistance, and thermal stability. These materials have carved their niche in the aerospace industry, finding applications in structural parts like wing flaps, access panels, and floor panels. The allure of PEKK stems not only from its robust performance under demanding conditions but also from the diversity of grades available, each tailored for specific applications. This adaptability, however, comes with its own set of challenges, particularly when it comes to manufacturing processes like Automated Tape Placement (ATP).

ATP represents a leap forward in manufacturing efficiency, offering rapid production rates, automation, and high repeatability. Yet, the very speed that makes ATP attractive introduces complexities in achieving consistent crystallinity across composite parts. Crystallinity, or the degree of molecular order within the polymer, is a critical factor influencing a composite's mechanical, thermal, and chemical properties. Achieving uniform crystallinity is paramount, especially for semicrystalline thermoplastics like PEKK, where it dictates the final part's performance and reliability.

The challenge lies in the ATP process's inherent nature, where materials are subjected to high temperatures and pressures but for a limited duration. This constrained time frame can hinder the development of desired crystallinity levels, potentially compromising part quality and performance. The quest for uniform crystallinity across the thickness of CF/PEKK laminates manufactured via ATP is not just an academic pursuit but a pressing industrial need, highlighting the necessity for a deep dive into the crystallization kinetics and morphology of CF/PEKK composites.

This blog embarks on exploring these intricate details, aiming to shed light on the complexities of manufacturing high-performance thermoplastic composites through ATP. By delving into the crystallinity gradients and their implications on material properties, we aim to navigate through the challenges and uncover solutions that could revolutionize the manufacturing process, ensuring that the potential of PEKK composites is fully realized in high-stakes applications.

Crystallinity Gradients: A Barrier to Performance and Consistency

The pursuit of uniform crystallinity in high-performance thermoplastic composites like PEKK, particularly when manufactured through Automated Tape Placement (ATP), unveils a complex interplay between processing conditions and material properties. This section delves into the challenges of controlling crystallinity during manufacturing and its significant implications on composite strength, durability, and overall performance, shedding light on a critical issue for industry stakeholders.

Void content, crystallinity and ILSS (MPa) of CF/PEKK composites after undergoing different processing and post-processing conditions.
Void content, crystallinity and ILSS (MPa) of CF/PEKK composites after undergoing different  processing and post-processing conditions.

Impact of Crystallinity on Mechanical Properties:

  • Crystallinity levels directly influence the mechanical properties of thermoplastic composites. Higher crystallinity results in increased strength and stiffness due to tighter molecular and crystal packing, which enhances resistance to deformation and prevents material slipping within the crystal structures. Conversely, lower crystallinity yields a more ductile material with decreased strength and stiffness.

Challenges in Achieving Uniform Crystallinity:

Schematic of a laminate consolidated by Automated Tape Placement (left) and autoclave (right). Different shades of blue show crystallinity variation within the matrix. ATP schematic drawn after
Schematic of a laminate consolidated by Automated Tape Placement (left) and autoclave (right).  Different shades of blue show crystallinity variation within the matrix. ATP schematic drawn after
  • The rapid pace of ATP manufacturing processes limits the material's exposure to high temperatures and loads. This restriction poses a significant challenge in developing uniform crystallinity across the composite part, impacting the quality and performance of the final product.

Implications of Non-Uniform Crystallinity:

  • Non-uniform crystallinity can lead to variable mechanical properties across the composite, affecting its reliability and performance during service life. For instance, variations in crystallinity can influence the composite's interlaminar shear strength (ILSS) and flexural strength, potentially reducing these properties by significant margins.

Research Gaps and Future Directions:

  • Despite some understanding of crystallinity's effects on mechanical performance, comprehensive studies on CF/PEKK composites remain sparse. This gap underscores the need for further research to quantify and understand these materials' behavior under different manufacturing conditions, especially concerning the development of uniform crystallinity.

The Role of Processing Conditions:

  • Processing conditions such as temperature, pressure, and cooling rates play a crucial role in crystallinity development. Understanding how these parameters affect crystallinity across the thickness of CF/PEKK laminates manufactured via ATP is essential for optimizing manufacturing processes and improving composite performance.

Shedding Light on Crystallinity: Innovative Research Methods

In the journey to unravel the complexities of crystallinity in PEKK composites, this research employs state-of-the-art techniques such as Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM), enabling an in-depth analysis of the crystallization behavior and morphology of PEKK and its composites.

DSC thermograms of (a) unreinforced PEKK powder and (b) CF/PEKK prepreg tape while undergoing isothermal holds at different temperatures showing peak crystallisation kinetics times in minutes. In (a), samples undergoing 220 and 240°C isotherms crystallise before reaching the isothermal temperatures, and therefore do not show crystallisation peaks during the isothermal hold. In (b), the fastest crystallisation kinetics can be observed between 240 and 260°C
DSC thermograms of (a) unreinforced PEKK powder and (b) CF/PEKK prepreg tape while  undergoing isothermal holds at different temperatures showing peak crystallisation kinetics times in minutes. In  (a), samples undergoing 220 and 240°C isotherms crystallise before reaching the isothermal temperatures, and  therefore do not show crystallisation peaks during the isothermal hold. In (b), the fastest crystallisation kinetics  can be observed between 240 and 260°C

Differential Scanning Calorimetry (DSC):

  • Utilized for isothermal and non-isothermal crystallization analyses, the DSC technique plays a pivotal role in understanding the crystallization kinetics of PEKK. Samples of neat PEKK powder and CF/PEKK prepreg tape underwent rigorous testing to ensure repeatability, with specific attention to thermal history and crystallization rates across different cooling rates. This methodological approach aids in identifying optimal processing conditions by evaluating the impact of temperature and time on crystallinity.

Scanning Electron Microscopy (SEM):

SEM of cryofractured CF/PEKK samples after undergoing an isothermal hold of (a) 220°C, (b) 260°C and (c) 300°C from the melt. Red annotations highlight spherulitic structures, with a red dot providing an example of a nucleus location.
SEM of cryofractured CF/PEKK samples after undergoing an isothermal hold of (a) 220°C, (b) 260°C  and (c) 300°C from the melt. Red annotations highlight spherulitic structures, with a red dot providing an example  of a nucleus location.

SEM analysis complements the DSC studies by offering a microscopic view of the material's morphology. This technique was particularly instrumental in examining the interfacial adhesion and matrix morphology post-cryofracture, highlighting the influence of crystallinity on the composite's mechanical integrity. By sputter coating the samples with gold to enhance conductivity, SEM images reveal intricate details about the crystalline structures and void content, providing a qualitative assessment of failure behaviors and the underlying crystallization morphology.

Through these innovative research methods, the study provides a comprehensive understanding of the crystallization kinetics and morphology of CF/PEKK composites. The findings underscore the significance of controlling processing conditions to achieve desired crystallinity levels, ultimately influencing the mechanical properties and performance of the composites. This research approach not only advances our knowledge of PEKK composites but also sets a foundation for optimizing manufacturing parameters in high-performance applications.

From Insights to Applications: Advancing Thermoplastic Composite Manufacturing

The comprehensive study of crystallinity gradients in CF/PEKK laminates manufactured via Automated Tape Placement (ATP) has unveiled significant findings that stand to revolutionize the manufacturing of thermoplastic composites. This section highlights the key discoveries, including crystallization kinetics and modeling, and explores how these insights pave the way for enhanced manufacturing techniques and material quality.

Key Discoveries and Innovations:

  • The research meticulously applied Avrami-based models to understand both isothermal and non-isothermal crystallization kinetics. The adaptation of the Nakamura model for non-isothermal cases and the Velisaris-Seferis model for isothermal crystallization were particularly instrumental.
  • A pivotal finding was the identification of an optimal isothermal holding temperature range of 220–260°C for achieving superior spherulitic development in CF/PEKK composites, crucial for high-performance applications.
  • The study underscored the importance of processing conditions on the crystalline structure development, revealing that adjustments in processing cycles can significantly impact the final part's crystal structure and, by extension, its performance characteristics.
Time-temperature-transformation diagrams of relative crystallinity development for (a) unreinforced PEKK and (b) CF/PEKK at different isothermal holds. A relative crystallinity of 1 means the material has achieved its full crystallisation potential, based on the crystallinity values
Time-temperature-transformation diagrams of relative crystallinity development for (a) unreinforced  PEKK and (b) CF/PEKK at different isothermal holds. A relative crystallinity of 1 means the material has  achieved its full crystallisation potential, based on the crystallinity values

Implications for Manufacturing Techniques:

Schematic of ATP laying programme
Schematic of ATP laying programme

These findings equip manufacturers with the knowledge to fine-tune ATP processing parameters, thereby optimizing the crystallinity and, consequently, the mechanical properties of CF/PEKK composite parts.

  • By establishing a correlation between isothermal holding temperatures and crystallization rate constants, the research offers a methodology for predicting crystallization evolution under varied processing conditions, enhancing the precision of manufacturing processes.

Advancements in Material Quality:

  • The insights gained from this research are not merely academic; they provide a solid foundation for improving the quality of CF/PEKK composites. Understanding the crystallization behavior allows for the manufacturing of composites with consistent and predictable properties, crucial for their application in high-stakes industries like aerospace.
CF/PEKK prepreg tape
CF/PEKK prepreg tape
  • The detailed analysis of crystallization kinetics and the development of reliable modeling approaches mean that manufacturers can now anticipate the performance of their composites under different processing conditions, leading to composites that meet stringent performance criteria.

Limitations and Future Directions:

  • While the research marks a significant step forward, it also highlights the gap between laboratory-scale studies and industrial-scale manufacturing, underscoring the need for further research to bridge this divide.
  • Future studies are encouraged to explore the scalability of these findings, with an emphasis on tailoring processing parameters to maintain the crystallinity and performance of composites in large-scale production environments.

This research provides a clearer understanding of the crystallization behavior of CF/PEKK composites, marking a milestone in the pursuit of manufacturing excellence in thermoplastic composites. By translating these scientific insights into practical applications, the path is set for the development of next-generation thermoplastic composites that meet the demanding requirements of high-performance applications.

Reference

We extend our deepest gratitude to Helena Pérez Martín for her pioneering research on crystallinity gradients in high-performance thermoplastic composites manufactured by automated tape placement. Her doctoral thesis "Studying Crystallinity Gradients in High

Performance Thermoplastic Composites Manufactured by Automated Tape Placement" provides invaluable insights into the complexities of material science and has greatly enriched the content of this blog. Helena's dedication to advancing our understanding of thermoplastic composites has not only paved the way for future innovations in aerospace manufacturing but also inspired countless professionals and enthusiasts in the field of materials science. Thank you, Helena Pérez Martín, for your significant contribution to the world of high-performance composites.

What's Next!

Discover the future of composite manufacturing with Addcomposites! Here's how you can get involved:

  1. Stay Informed: Subscribe to our newsletter to receive the latest updates, news, and developments in AFP systems and services. Knowledge is power, and by staying informed, you'll always have the upper hand. Subscribe Now
  2. Experience Our Technology: Try our cutting-edge simulation software for a firsthand experience of the versatility and capability of our AFP systems. You'll see how our technology can transform your production line. Try Simulation
  3. Join the Collaboration: Engage with us and other technical centers across various industries. By joining this collaborative platform, you'll get to share ideas, innovate, and influence the future of AFP. Join Collaboration
  4. Get Hands-On: Avail our educational rentals for university projects or semester-long programs. Experience how our AFP systems bring about a revolution in composite manufacturing and leverage this opportunity for academic and research pursuits. Request for Educational Rental
  5. Take the Next Step: Request a quotation for our AFP systems. Whether you're interested in the AFP-XS, AFP-X, or SCF3D, we are committed to offering cost-effective solutions tailored to your needs. Take the plunge and prepare your production line for the next generation of composite manufacturing. Request Quotation

At Addcomposites, we are dedicated to revolutionizing composite manufacturing. Our AFP systems and comprehensive support services are waiting for you to harness. So, don't wait – get started on your journey to the future of manufacturing today!

‍

CF/PEKK Thermoplastic Composites Process: How Crystallinity Shapes the Future of Aerospace Manufacturing

August 28, 2024
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The Complex World of Thermoplastic Composites: Navigating Crystallinity Gradients

In the realm of high-performance materials, poly(aryletherketone)s (PAEKs), notably Poly(etherketoneketone) (PEKK), stand out for their superior mechanical properties, chemical resistance, and thermal stability. These materials have carved their niche in the aerospace industry, finding applications in structural parts like wing flaps, access panels, and floor panels. The allure of PEKK stems not only from its robust performance under demanding conditions but also from the diversity of grades available, each tailored for specific applications. This adaptability, however, comes with its own set of challenges, particularly when it comes to manufacturing processes like Automated Tape Placement (ATP).

ATP represents a leap forward in manufacturing efficiency, offering rapid production rates, automation, and high repeatability. Yet, the very speed that makes ATP attractive introduces complexities in achieving consistent crystallinity across composite parts. Crystallinity, or the degree of molecular order within the polymer, is a critical factor influencing a composite's mechanical, thermal, and chemical properties. Achieving uniform crystallinity is paramount, especially for semicrystalline thermoplastics like PEKK, where it dictates the final part's performance and reliability.

The challenge lies in the ATP process's inherent nature, where materials are subjected to high temperatures and pressures but for a limited duration. This constrained time frame can hinder the development of desired crystallinity levels, potentially compromising part quality and performance. The quest for uniform crystallinity across the thickness of CF/PEKK laminates manufactured via ATP is not just an academic pursuit but a pressing industrial need, highlighting the necessity for a deep dive into the crystallization kinetics and morphology of CF/PEKK composites.

This blog embarks on exploring these intricate details, aiming to shed light on the complexities of manufacturing high-performance thermoplastic composites through ATP. By delving into the crystallinity gradients and their implications on material properties, we aim to navigate through the challenges and uncover solutions that could revolutionize the manufacturing process, ensuring that the potential of PEKK composites is fully realized in high-stakes applications.

Crystallinity Gradients: A Barrier to Performance and Consistency

The pursuit of uniform crystallinity in high-performance thermoplastic composites like PEKK, particularly when manufactured through Automated Tape Placement (ATP), unveils a complex interplay between processing conditions and material properties. This section delves into the challenges of controlling crystallinity during manufacturing and its significant implications on composite strength, durability, and overall performance, shedding light on a critical issue for industry stakeholders.

Void content, crystallinity and ILSS (MPa) of CF/PEKK composites after undergoing different processing and post-processing conditions.
Void content, crystallinity and ILSS (MPa) of CF/PEKK composites after undergoing different  processing and post-processing conditions.

Impact of Crystallinity on Mechanical Properties:

  • Crystallinity levels directly influence the mechanical properties of thermoplastic composites. Higher crystallinity results in increased strength and stiffness due to tighter molecular and crystal packing, which enhances resistance to deformation and prevents material slipping within the crystal structures. Conversely, lower crystallinity yields a more ductile material with decreased strength and stiffness.

Challenges in Achieving Uniform Crystallinity:

Schematic of a laminate consolidated by Automated Tape Placement (left) and autoclave (right). Different shades of blue show crystallinity variation within the matrix. ATP schematic drawn after
Schematic of a laminate consolidated by Automated Tape Placement (left) and autoclave (right).  Different shades of blue show crystallinity variation within the matrix. ATP schematic drawn after
  • The rapid pace of ATP manufacturing processes limits the material's exposure to high temperatures and loads. This restriction poses a significant challenge in developing uniform crystallinity across the composite part, impacting the quality and performance of the final product.

Implications of Non-Uniform Crystallinity:

  • Non-uniform crystallinity can lead to variable mechanical properties across the composite, affecting its reliability and performance during service life. For instance, variations in crystallinity can influence the composite's interlaminar shear strength (ILSS) and flexural strength, potentially reducing these properties by significant margins.

Research Gaps and Future Directions:

  • Despite some understanding of crystallinity's effects on mechanical performance, comprehensive studies on CF/PEKK composites remain sparse. This gap underscores the need for further research to quantify and understand these materials' behavior under different manufacturing conditions, especially concerning the development of uniform crystallinity.

The Role of Processing Conditions:

  • Processing conditions such as temperature, pressure, and cooling rates play a crucial role in crystallinity development. Understanding how these parameters affect crystallinity across the thickness of CF/PEKK laminates manufactured via ATP is essential for optimizing manufacturing processes and improving composite performance.

Shedding Light on Crystallinity: Innovative Research Methods

In the journey to unravel the complexities of crystallinity in PEKK composites, this research employs state-of-the-art techniques such as Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM), enabling an in-depth analysis of the crystallization behavior and morphology of PEKK and its composites.

DSC thermograms of (a) unreinforced PEKK powder and (b) CF/PEKK prepreg tape while undergoing isothermal holds at different temperatures showing peak crystallisation kinetics times in minutes. In (a), samples undergoing 220 and 240°C isotherms crystallise before reaching the isothermal temperatures, and therefore do not show crystallisation peaks during the isothermal hold. In (b), the fastest crystallisation kinetics can be observed between 240 and 260°C
DSC thermograms of (a) unreinforced PEKK powder and (b) CF/PEKK prepreg tape while  undergoing isothermal holds at different temperatures showing peak crystallisation kinetics times in minutes. In  (a), samples undergoing 220 and 240°C isotherms crystallise before reaching the isothermal temperatures, and  therefore do not show crystallisation peaks during the isothermal hold. In (b), the fastest crystallisation kinetics  can be observed between 240 and 260°C

Differential Scanning Calorimetry (DSC):

  • Utilized for isothermal and non-isothermal crystallization analyses, the DSC technique plays a pivotal role in understanding the crystallization kinetics of PEKK. Samples of neat PEKK powder and CF/PEKK prepreg tape underwent rigorous testing to ensure repeatability, with specific attention to thermal history and crystallization rates across different cooling rates. This methodological approach aids in identifying optimal processing conditions by evaluating the impact of temperature and time on crystallinity.

Scanning Electron Microscopy (SEM):

SEM of cryofractured CF/PEKK samples after undergoing an isothermal hold of (a) 220°C, (b) 260°C and (c) 300°C from the melt. Red annotations highlight spherulitic structures, with a red dot providing an example of a nucleus location.
SEM of cryofractured CF/PEKK samples after undergoing an isothermal hold of (a) 220°C, (b) 260°C  and (c) 300°C from the melt. Red annotations highlight spherulitic structures, with a red dot providing an example  of a nucleus location.

SEM analysis complements the DSC studies by offering a microscopic view of the material's morphology. This technique was particularly instrumental in examining the interfacial adhesion and matrix morphology post-cryofracture, highlighting the influence of crystallinity on the composite's mechanical integrity. By sputter coating the samples with gold to enhance conductivity, SEM images reveal intricate details about the crystalline structures and void content, providing a qualitative assessment of failure behaviors and the underlying crystallization morphology.

Through these innovative research methods, the study provides a comprehensive understanding of the crystallization kinetics and morphology of CF/PEKK composites. The findings underscore the significance of controlling processing conditions to achieve desired crystallinity levels, ultimately influencing the mechanical properties and performance of the composites. This research approach not only advances our knowledge of PEKK composites but also sets a foundation for optimizing manufacturing parameters in high-performance applications.

From Insights to Applications: Advancing Thermoplastic Composite Manufacturing

The comprehensive study of crystallinity gradients in CF/PEKK laminates manufactured via Automated Tape Placement (ATP) has unveiled significant findings that stand to revolutionize the manufacturing of thermoplastic composites. This section highlights the key discoveries, including crystallization kinetics and modeling, and explores how these insights pave the way for enhanced manufacturing techniques and material quality.

Key Discoveries and Innovations:

  • The research meticulously applied Avrami-based models to understand both isothermal and non-isothermal crystallization kinetics. The adaptation of the Nakamura model for non-isothermal cases and the Velisaris-Seferis model for isothermal crystallization were particularly instrumental.
  • A pivotal finding was the identification of an optimal isothermal holding temperature range of 220–260°C for achieving superior spherulitic development in CF/PEKK composites, crucial for high-performance applications.
  • The study underscored the importance of processing conditions on the crystalline structure development, revealing that adjustments in processing cycles can significantly impact the final part's crystal structure and, by extension, its performance characteristics.
Time-temperature-transformation diagrams of relative crystallinity development for (a) unreinforced PEKK and (b) CF/PEKK at different isothermal holds. A relative crystallinity of 1 means the material has achieved its full crystallisation potential, based on the crystallinity values
Time-temperature-transformation diagrams of relative crystallinity development for (a) unreinforced  PEKK and (b) CF/PEKK at different isothermal holds. A relative crystallinity of 1 means the material has  achieved its full crystallisation potential, based on the crystallinity values

Implications for Manufacturing Techniques:

Schematic of ATP laying programme
Schematic of ATP laying programme

These findings equip manufacturers with the knowledge to fine-tune ATP processing parameters, thereby optimizing the crystallinity and, consequently, the mechanical properties of CF/PEKK composite parts.

  • By establishing a correlation between isothermal holding temperatures and crystallization rate constants, the research offers a methodology for predicting crystallization evolution under varied processing conditions, enhancing the precision of manufacturing processes.

Advancements in Material Quality:

  • The insights gained from this research are not merely academic; they provide a solid foundation for improving the quality of CF/PEKK composites. Understanding the crystallization behavior allows for the manufacturing of composites with consistent and predictable properties, crucial for their application in high-stakes industries like aerospace.
CF/PEKK prepreg tape
CF/PEKK prepreg tape
  • The detailed analysis of crystallization kinetics and the development of reliable modeling approaches mean that manufacturers can now anticipate the performance of their composites under different processing conditions, leading to composites that meet stringent performance criteria.

Limitations and Future Directions:

  • While the research marks a significant step forward, it also highlights the gap between laboratory-scale studies and industrial-scale manufacturing, underscoring the need for further research to bridge this divide.
  • Future studies are encouraged to explore the scalability of these findings, with an emphasis on tailoring processing parameters to maintain the crystallinity and performance of composites in large-scale production environments.

This research provides a clearer understanding of the crystallization behavior of CF/PEKK composites, marking a milestone in the pursuit of manufacturing excellence in thermoplastic composites. By translating these scientific insights into practical applications, the path is set for the development of next-generation thermoplastic composites that meet the demanding requirements of high-performance applications.

Reference

We extend our deepest gratitude to Helena Pérez Martín for her pioneering research on crystallinity gradients in high-performance thermoplastic composites manufactured by automated tape placement. Her doctoral thesis "Studying Crystallinity Gradients in High

Performance Thermoplastic Composites Manufactured by Automated Tape Placement" provides invaluable insights into the complexities of material science and has greatly enriched the content of this blog. Helena's dedication to advancing our understanding of thermoplastic composites has not only paved the way for future innovations in aerospace manufacturing but also inspired countless professionals and enthusiasts in the field of materials science. Thank you, Helena Pérez Martín, for your significant contribution to the world of high-performance composites.

What's Next!

Discover the future of composite manufacturing with Addcomposites! Here's how you can get involved:

  1. Stay Informed: Subscribe to our newsletter to receive the latest updates, news, and developments in AFP systems and services. Knowledge is power, and by staying informed, you'll always have the upper hand. Subscribe Now
  2. Experience Our Technology: Try our cutting-edge simulation software for a firsthand experience of the versatility and capability of our AFP systems. You'll see how our technology can transform your production line. Try Simulation
  3. Join the Collaboration: Engage with us and other technical centers across various industries. By joining this collaborative platform, you'll get to share ideas, innovate, and influence the future of AFP. Join Collaboration
  4. Get Hands-On: Avail our educational rentals for university projects or semester-long programs. Experience how our AFP systems bring about a revolution in composite manufacturing and leverage this opportunity for academic and research pursuits. Request for Educational Rental
  5. Take the Next Step: Request a quotation for our AFP systems. Whether you're interested in the AFP-XS, AFP-X, or SCF3D, we are committed to offering cost-effective solutions tailored to your needs. Take the plunge and prepare your production line for the next generation of composite manufacturing. Request Quotation

At Addcomposites, we are dedicated to revolutionizing composite manufacturing. Our AFP systems and comprehensive support services are waiting for you to harness. So, don't wait – get started on your journey to the future of manufacturing today!

‍

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