Common examples of preceramic polymer families

Polymer derived ceramics (PDCs) are ceramic materials formed by the pyrolysis of preceramic polymers, usually under inert atmosphere.[1]

The compositions of PDCs most commonly include silicon carbide (SiC), silicon oxycarbide (SiOxCy), silicon nitride(Si3N4), silicon carbonitride (Si3+xN4Cx+y)[2] and silicon oxynitride (SiOxNy).[3] The composition, phase distribution and structure of PDCs depend on the polymer precursor compounds used and the pyrolysis conditions applied.

The key advantage of this type of ceramic material is the versatility afforded by the use of polymeric precursors in terms of processing and shaping. Polymer derived ceramics can be additively manufactured (3D printed) by means of fused filament fabrication,[4] stereolithography that uses photopolymerization of preceramic polymers.[5] Such processing of PDCs is used in applications requiring thermally and chemically stable materials in complex shapes that are challenging to achieve through more conventional ceramic processing routes, such as powder sintering and slip casting. PDCs are also valuable for synthesis of porous and mesoporous materials[6] and thin films.[7]

Chemistry

PDCs are mainly fabricated through the pyrolysis of preceramic polymers.

PDC processing

In the families of preceramic polymers, polysiloxanes are the most famous preceramic polymers. The backbones comprise silicon and oxygen atoms. Poly(organo)siloxanes are polysiloxanes with organic groups in the backbones, e.g., polyborosiloxanes, poly(carbosiloxanes). Another important category of preceramic polymers are polycarbosilanes and poly(organo)carbosilanes, containing alternating carbon and silicone atoms in the backbones. Similarly, polymers made up of Si-N bonds are classified as polysilazane, poly(organosilazanes) and poly(organosilylcarbodiimides).[8] Different polymer compositions influence processing temperatures, microstructure transitions, ceramic yields and stabilities.[9]

The conversion of preceramic polymers to PDCs can be divided into four phases, shaping, cross-linking, pyrolysis, crystallization. Typically, PDC processing is completed at 1100 °C-1300 °C. To form a crystalline PDC, some materials require higher temperature to crystalize, usually over 1700 °C.[10]

Properties

PDCs are characteristic with many properties, including:[1]

The combination of PDCs and other materials with different properties can develop combining properties for PDC-based composite materials. PDC-based composite materials can extend functions and usages of PDCs to a wide range of areas, for example, in biological, medical, electrical, magnetic, engineering and optical applications.[11]

Uses

Coatings

Representative uses of polymer derived ceramics and polymer derived ceramic based materials

Compared with other coating methods, the thermal treatment (e.g. thermal spraying) of PDC processing is simple and low-cost. PDC coatings are good components in electronic devices and gas separation membranes. Due to the intrinsic stability of PDC materials, PDC coatings are also commonly used in environmental barrier coatings (EBCs).[10]

3D printing

Fused filament fabrication 3D printing-based polymers to use for PDC processing on a wide range of applications such as heat exchangers, heat sinks, scaffolding for bone tissue growth, chemical/ gas filters and custom open hardware.[12] Specific 3D printing techniques such as direct ink writing (DIW), stereolithography (SLA) and digital light processing (DLP) can control the structure of preceramic polymers from nanoscale to macroscale. 3D printing of PDCs can facilitate the fabrication and integration of advanced ceramic materials.[13]

Biomedical engineering

Biocompatible PDCs and PDC-based composites can be applied in various biological systems. They are usually used to produce interface or surface with multi-functionality and complex shapes for biomedical applications, such as tissue regeneration, implant design, drug delivery, and wound dressing.[14][15]

Electronics

Hybrid PDC materials are feasible and tunable for substrate manufacturing in lithium ion batteries, sensors, actuators, high temperature electrical devices, etc. Common processing strategies of PDC composites for electronic applications include chemical modification, blending with metal or metal oxides, and incorporating with functional fillers.[11]

References

  1. 1 2 Barrios, Elizabeth; Zhai, Lei (2020-12-14). "A review of the evolution of the nanostructure of SiCN and SiOC polymer derived ceramics and the impact on mechanical properties". Molecular Systems Design & Engineering. 5 (10): 1606–1641. doi:10.1039/D0ME00123F. ISSN 2058-9689. S2CID 229265961.
  2. Silicon carbonitrides, - A novel class of materials
  3. Polymer‐Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics
  4. Kulkarni, Apoorv; Sorarù, Gian Domenico; Pearce, Joshua M. (2020-03-01). "Polymer-derived SiOC replica of material extrusion-based 3-D printed plastics". Additive Manufacturing. 32: 100988. arXiv:1909.02442. doi:10.1016/j.addma.2019.100988. ISSN 2214-8604.
  5. Additive manufacturing of polymer derived ceramics published in Additive manufacturing 2019, vol. 27
  6. Polymer-Derived Ceramics with engineered mesoporosity: From design to application in catalysis
  7. Friction and Wear of Si Carbonitride films
  8. Colombo, Paolo; Mera, Gabriela; Riedel, Ralf; Sorarù, Gian Domenico (2010-06-07). "Polymer-Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics: Polymer-Derived Ceramics". Journal of the American Ceramic Society: no. doi:10.1111/j.1551-2916.2010.03876.x.
  9. Greil, P. (2000). "Polymer Derived Engineering Ceramics". Advanced Engineering Materials. 2 (6): 339–348. doi:10.1002/1527-2648(200006)2:6<339::AID-ADEM339>3.0.CO;2-K. ISSN 1527-2648.
  10. 1 2 Barroso, Gilvan; Li, Quan; Bordia, Rajendra K.; Motz, Günter (2019-01-29). "Polymeric and ceramic silicon-based coatings – a review". Journal of Materials Chemistry A. 7 (5): 1936–1963. doi:10.1039/C8TA09054H. ISSN 2050-7496. S2CID 104389084.
  11. 1 2 Francis, A (2018-06-29). "Progress in polymer-derived functional silicon-based ceramic composites for biomedical and engineering applications". Materials Research Express. 5 (6): 062003. doi:10.1088/2053-1591/aacd28. ISSN 2053-1591. S2CID 139400551.
  12. Kulkarni, Apoorv; Sorarù, Gian Domenico; Pearce, Joshua M. (2020-03-01). "Polymer-derived SiOC replica of material extrusion-based 3-D printed plastics". Additive Manufacturing. 32: 100988. arXiv:1909.02442. doi:10.1016/j.addma.2019.100988. ISSN 2214-8604.
  13. Zhou, Shixiang; Mei, Hui; Chang, Peng; Lu, Mingyang; Cheng, Laifei (2020-11-01). "Molecule editable 3D printed polymer-derived ceramics". Coordination Chemistry Reviews. 422: 213486. doi:10.1016/j.ccr.2020.213486. ISSN 0010-8545. S2CID 224936606.
  14. Francis, Adel (2021). "Biological evaluation of preceramic organosilicon polymers for various healthcare and biomedical engineering applications: A review". Journal of Biomedical Materials Research Part B: Applied Biomaterials. 109 (5): 744–764. doi:10.1002/jbm.b.34740. ISSN 1552-4981. PMID 33075186. S2CID 224813437.
  15. Abdollahi, Sorosh; Paryab, Amirhosein; Khalilifard, Rashid; Anousheh, Mohsen; Malek Khachatourian, Adrine (March 2021). "The fabrication and characterization of bioactive Akermanite/Octacalcium phosphate glass-ceramic scaffolds produced via PDC method". Ceramics International. 47 (5): 6653–6662. doi:10.1016/j.ceramint.2020.11.003. S2CID 228837741.
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