Soluble Hf-containing polymers are significant processable precursors for the fabrication of ultra-high temperature ceramics.In this work,cyclic Hf-Schiff base polymers were synthesized via direct polymerization of ha...Soluble Hf-containing polymers are significant processable precursors for the fabrication of ultra-high temperature ceramics.In this work,cyclic Hf-Schiff base polymers were synthesized via direct polymerization of hafnium alkoxide and bis-salen monomers.The defined structure and molecular weight of the polymers were characterized by NMR spectroscopy,gel permeation chromatography and MALDI-TOF mass spectroscopy.The feed ratio of monomers regulated the molecular weight and solubility of the polymers.This synthetic strategy features simple operation under ambient conditions,efficient reaction with high yield and cyclic polymers as the main products.The Hf-Schiff base polymers were converted to HfC/C materials after pyrolysis under argon at 1600°C,which was identified by XRD measurements,elemental analyses and Raman spectroscopy.This work will inspire more precise and efficient synthesis and applications of metallopolymers.展开更多
Polymer-derived ultra-high-temperature ceramic(UHTC)nanocomposites have attracted growing attention due to the increasing demands for advanced thermal structure components in aerospace.Herein,hafnium carbide(HfC)whisk...Polymer-derived ultra-high-temperature ceramic(UHTC)nanocomposites have attracted growing attention due to the increasing demands for advanced thermal structure components in aerospace.Herein,hafnium carbide(HfC)whiskers are successfully fabricated in carbon fiber preforms via the polymer-derived ceramic(PDC)method.A novel carbon nanotube(CNT)template growth mechanism combined with the PDC method is proposed in this work,which is different from the conventional vapor–liquid–solid(VLS)mechanism that is commonly used for polymer-derived nanostructured ceramics.The CNTs are synthesized and proved to be the templates for fabricating the HfC whiskers,which are generated by the released low-molecular-weight gas such as CO,CO_(2),and CH4 during the pyrolysis of a Hf-containing precursor.The formed products are composed of inner single crystal HfC whiskers that are measured to be several tens of micrometers in length and 100–200 nm in diameter and outer HfC/HfO_(2)particles.Our work not only proposes a new strategy to prepare the HfC whiskers,but also puts forward a new thinking of the efficient utilization of a UHTC polymer precursor.展开更多
基金by the National Natural Science Foundation of China(No.21604090)。
文摘Soluble Hf-containing polymers are significant processable precursors for the fabrication of ultra-high temperature ceramics.In this work,cyclic Hf-Schiff base polymers were synthesized via direct polymerization of hafnium alkoxide and bis-salen monomers.The defined structure and molecular weight of the polymers were characterized by NMR spectroscopy,gel permeation chromatography and MALDI-TOF mass spectroscopy.The feed ratio of monomers regulated the molecular weight and solubility of the polymers.This synthetic strategy features simple operation under ambient conditions,efficient reaction with high yield and cyclic polymers as the main products.The Hf-Schiff base polymers were converted to HfC/C materials after pyrolysis under argon at 1600°C,which was identified by XRD measurements,elemental analyses and Raman spectroscopy.This work will inspire more precise and efficient synthesis and applications of metallopolymers.
基金supported by the National Natural Science Foundation of China(Grant Nos.52293373,52130205,and 52061135102)the National Key R&D Program of China(Grant No.2021YFA0715803).Also,we would like to thank ND Basic Research Funds of Northwestern Polytechnical University(Grant No.G2022WD)and China Scholarship Program,2020(Grant No.202006290179).
文摘Polymer-derived ultra-high-temperature ceramic(UHTC)nanocomposites have attracted growing attention due to the increasing demands for advanced thermal structure components in aerospace.Herein,hafnium carbide(HfC)whiskers are successfully fabricated in carbon fiber preforms via the polymer-derived ceramic(PDC)method.A novel carbon nanotube(CNT)template growth mechanism combined with the PDC method is proposed in this work,which is different from the conventional vapor–liquid–solid(VLS)mechanism that is commonly used for polymer-derived nanostructured ceramics.The CNTs are synthesized and proved to be the templates for fabricating the HfC whiskers,which are generated by the released low-molecular-weight gas such as CO,CO_(2),and CH4 during the pyrolysis of a Hf-containing precursor.The formed products are composed of inner single crystal HfC whiskers that are measured to be several tens of micrometers in length and 100–200 nm in diameter and outer HfC/HfO_(2)particles.Our work not only proposes a new strategy to prepare the HfC whiskers,but also puts forward a new thinking of the efficient utilization of a UHTC polymer precursor.
