###### Abstract  
We have developed an easy route to prepare (nano-ZrO2,nano-ZrC\({}_{3}\))@C composites with varying ZrO2/ZrC\({}_{3}\) content. The process consists of preparing a zirconium-loaded, imniodiacetate-functionalized styrene-divinylbenzene (STY-DVB) copolymer, and its subsequent carbonization in a tube furnace and/or a thermal plasma reactor. Depending on the zirconium salt used (zirconyl chloride, zirconyl nitrate or zirconium (IV) sulfate) in the Zr loading, the Zr-loaded resins resulted in ZrO2@C pre-pyridoxites with C to Zr molar ratios of 5.8, 6.8 and 6.60. This carbon surplus is sufficient for the partial or even complete reduction of ZrO2 into ZrC\({}_{0.58}\) at 1400 \({}^{\circ}\)C. The reaction products also contain 5 to 55 mass% residual free carbon. The plasma processing of the ZrO2@C composite formed at 1000 \({}^{\circ}\)C in a tube furnace led to ZrC\({}_{0.94}\)@C composites. The transformation of amorphous carbon content during the plasma treatment strongly depended on the atmosphere (He or H\({}_{2}\)) in the reactor and the anion type of the Zr salt. In the presence of He, amorphous carbon could be completely transformed into graphite. In the presence of H\({}_{2}\), amorphous carbon and graphite were found at roughly the same ratio. No ZrO2 could be detected in the plasma-treated samples, whilst different ZrO2 polymorphs were found in the samples prepared in the tube furnace, depending on the synthesis conditions. keywords: +
Footnote †: journal: _inorganics_  
for zirconium to be bound at an atomic level, enhancing the distribution of ZrC in the carbon matrix after carbonization. The chemical nature of functional groups (sulfonate or iminodiacetate) and DVB content in the STY-DVB copolymer have a significant influence on the chemical nature of metal compounds embedded in the carbon matrix during the carbonization of metal-loaded, functionalized, styrene-divinylbenzene (STY-DVB) copolymers, [6; 7; 8]. In fact, ZrC could be prepared by the carbonization of the quaternary ammonium group-containing and anionic Zr-loaded STY-DVB resins at 1350 \({}^{\circ}\)C [3], whereas only ZrO2@C composites were formed from the sulfonated resins [5]. Due to the moderate reactivity of ZrO2 in these composites, their subsequent RF plasma treatment in either a He or H2 atmosphere [5] only resulted in a partial conversion of ZrO2 into ZrC. Our goal was to study the effect of functional groups on the formation and composition of zirconium carbide using STY-DVB copolymer precursors functionalized with groups that differed from sulfonate or quaternary ammonium. Since no information is available on the carbonization reactions of Zr-loaded iminodiacetate-functionalized STY-DVB resins, we studied the formation of ZrC in the carbonization process of these resins in both a tubular furnace and/or a thermal plasma-assisted process. It is known that STY-DVB resins functionalized with iminodiacetate groups and loaded with a polyvalent element such as iron(III) have special properties due to the divalent selective iminodiacetate groups and the presence of a third, outer counter-ion neutralizing the third valence of iron(III) (X=Cl, nitrate or sulfate) [7; 9; 10]. Therefore, we conducted a detailed study of the influence of counter-ions such as chloride, nitrate, or sulfate on the chemical form of Zr in Zr-loaded iminodiacetate-functionalized STY/DVB copolymers. Hereinafter, the prepared materials are referred to as L-X, L-Zr-X, L-Zr-X-T-t, where L stands for the Lewatite resin skeleton, X stands for the anion in the mineral acid or Zr salt used in H or Zr loading, respectively. \(T\) corresponds to the pyrolysis temperatures (1000, 1200, 1400 \({}^{\circ}\)C), whereas \(t\) represents reaction time (2 or 8 h).