Oxidation Resistance of Materials Based on Ti3AlC2 Nanolaminate at 600 °C in Air
© The Author(s). 2016
Received: 5 December 2015
Accepted: 3 August 2016
Published: 9 August 2016
The oxidation behavior of Ti3AlC2-based materials had been investigated at 600 °C in static air for 1000 h. It was shown that the intense increase of weight gain per unit surface area for sintered material with porosity of 22 % attributed to oxidation of the outer surface of the specimen and surfaces of pores in the bulk material. The oxidation kinetics of the hot-pressed Ti3AlC2-based material with 1 % porosity remarkably increased for the first 15 h and then slowly decreased. The weight gain per unit surface area for this material was 1.0 mg/cm2 after exposition for 1000 h. The intense initial oxidation of Ti3AlC2-based materials can be eliminated by pre-oxidation treatment at 1200 °C in air for 2 h. As a result, the weight gain per unit surface area for the pre-oxidized material did not exceed 0.11 mg/cm2 after 1000 h of exposition at 600 °C in air. It was demonstrated that the oxidation resistance of Ti3AlC2-based materials can be significantly improved by niobium addition.
Recently, new classes of materials based on layered carbide Ti3AlC2 have attracted great attention of material scientists due to their exceptional properties. This carbide belongs to the so-called MAX phases which have a chemical formula M n + 1AX n —where M is an early transition metal, A is an A-group element, and X is carbon and/or nitrogen. The crystal structure of MAX phases can be described as octahedral ternary metal carbide and/or nitride sandwiched by close-packed layers of A-element. These materials have good thermal and electrical conductivity, low density, high strength and Young’s modulus, excellent thermal shock resistance, high chemical resistance, relatively low thermal expansion coefficient, and good machinability [1–3]. Owing to such combination of properties, they have been suggested for various applications, especially as high-temperature structural materials. This requires comprehensive investigations of oxidation resistance of Ti3AlC2-based materials. Barsoum et al.  had demonstrated that for Tin+1AlXn compounds oxidized in the 800–1000 °C temperature range, the scale composed mainly of rutile-based solid solution (Ti1 − yAl y )O2 − y/2, where y < 0.05 and some Al2O3. The oxidation process occurred by the inward diffusion of oxygen and the outward diffusion of Al, Ti, C, and N. It was revealed that the formation of a thin layer of Al2O3 preceded the nucleation and growth of TiO2 at the early stages of oxidation . The scale formed at higher temperatures consisted of a continuous Al2O3 inner layer and outer layer, changed from rutile TiO2 at temperatures below 1200 °C to a mixture of Al2TiO5 and TiO2 at 1300 °C . Taotao  had reported that the scale of an un-dense Ti3AlC2 material containing 3 wt. % TiC oxidized at 1000 °C in air consisted of three layers, including an outer un-dense TiO2 layer adhering to a little Al2O3, a thick intermediate TiO2 + Al2O3 mixed layer, and a thin inner Al2O3 layer with some pores.
In spite of thorough research of oxidation behavior of Ti3AlC2-based materials at high temperature, only a few results obtained at intermediate temperatures have been reported [8, 9]. Taking into account the anomalously intense oxidation of Ti3AlC2-based material at 500 °C and especially at 600 °C , the investigation of oxidation behavior of these materials at intermediate temperatures has a great importance.
In this work, the Ti3AlC2-based materials have been oxidized at 600 °C in air for 1000 h. The influence of porosity, pre-oxidation treatment, and niobium addition on the oxidation resistance of these materials has been investigated.
The isothermal oxidation tests were carried out at the temperature of 600 °C in static air using tree rectangular bars with dimensions of 20 × 5 × 3 mm for each material. The specimens were cut by the electrical discharge method, abraded to 1000 grit with SiC paper, and polished by diamond past. The oxidation tests were divided into five stages which had the duration: first stage, 15 h; second stage, 245 h; and the last three stages, 250 h. Each stage consisted of heating to 600 °C in air, exposition during determined time, and cooling to room temperature. The weight of the specimens was measured before the test and after each stage by analytical balance. The accuracy of the weight measuring was ±10−4 g. The oxidation resistance of materials tested was characterized by weight gain per unit surface area ΔW/S. The phase composition of the materials was analyzed by X-ray diffractometry (Dron-3M, Russia). Diffraction data were processed by the Rietveld method using the PowderCell program. Scanning electron microscopy (EVO 40 XVP (Carl Zeiss, Germany)) coupled with energy dispersive spectroscopy (EDS) (INCA ENERGY 350 (Oxford Instruments, UK)) was used to study the structure and quantitative elemental content of the bulk material and the oxidized scale.
Results and Discussion
EDS analysis results of the Ti3AlC2-based materials with 1 % porosity (at. %)
Ti3AlC2 with Nb
Wang and Zhou  had demonstrated that the scale formed at 600 °C on the surface of a Ti3AlC2 material with 5 val. % TiC consisted of amorphous Al2O3, anatase, and rutile TiO2. The formation of anatase from Ti3AlC2 led to the increase of stress due to the difference of their volume expansion. Therefore, the rapid increase of ΔW/S value for the Ti3AlC2-based material with 1 % porosity on the first stage of the test can be associated with intense scale formation as well as with low protective property of the thin scale due to microcracks and also with penetration of oxygen through micropores into the bulk material (Fig. 4c). After long-term exposition, when micropores were covered with oxides and the scale thickness was increased (Fig. 4d), the inward diffusion of oxygen and outward diffusion of Ti and Al became slow. As a result, the oxidation kinetics was decreased. Based on these results, it can be assumed that the preliminary oxidation to form the protective layer of oxides would increase the oxidation resistance of Ti3AlC2-based materials. The pre-oxidation at 1000–1300 °C for 2 h provides the formation of a dense scale which consists of Al2O3 and rutile TiO2 without anatase TiO2 . In the present study, the pre-oxidation of the Ti3AlC2-based material with 1 % porosity was performed at 1200 °C in air for 2 h. The weight gain per unit surface area after pre-oxidation is 1.7 mg/cm2 . The long-term oxidation resistance was investigated at 600 °C in air for 1000 h. As can be seen in Fig. 3, the pre-oxidized material demonstrates the negligible increase of weight gain per unit surface area during all tests. The value of ΔW/S for this material not exceeds a 0.11 mg/cm2 after a 1000-h exposition.
The investigation of oxidation resistance of Ti3AlC2-based materials had been carried out at 600 °C in static air for 1000 h. The results showed that the weight gain per unit surface area for sintered Ti3AlC2-based materials with porosity of 22 % monolithically increased and after 437 h reached the value of 24 mg/cm2. The drastic increase of oxidation kinetics of this material caused by intense oxidation not only the outer surface of specimen but also the surfaces of pores. The weight gain per unit surface area for hot-pressed Ti3AlC2-based materials with 1 % porosity intensively increased for the first 15 h of oxidation, and then the oxidation kinetics slowly decreased. The pre-oxidation at 1200 °C for 2 h eliminated the initial oxidation of this material at 600 °C. It was revealed that the niobium addition significantly improves the oxidation resistance of the Ti3AlC2-based material.
AI performed the oxidation tests and microstructural and energy dispersive studies and drafted Fig. 1 and Table 1 and the “Experimental” and “Results and Discussion” sections. VP performed the microctructural studies and drafted Figs. 2 and 3 and the “Introduction,” “Results and Discussion,” and “References” sections. OO analyzed the literature data and test results and helped in the “Introduction,” “Results and Discussion,” and “Conclusions” sections. TP analyzed the literature data and test results; contributed in the development of the materials; and helped in the “Experimental,” “Results and Discussion,” and “Conclusions” sections. TB performed the phase compositions and microctructural studies and helped in the “Experimental” and “Results and Discussion” sections. All authors read and approved the final manuscript.
The authors declare that they have no competing interest.
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