K5Cu0.5Hf1.5(MoO4)6: синтез, структура, термическое поведение и ионная проводимость
Аннотация
Цель статьи: Соединение K5Cu0.5Hf1.5(MoO4)6 синтезировано по керамической технологии. Установлена последовательность химических превращений, происходящих при образовании этого соединения. Обнаружено, что тройной молибдат плавится инконгруэнтно при температуре 634 °C.
Экспериментальная часть: Кристаллическая структура уточнена методом Ритвельда, соединение кристаллизуется в тригональной пр. гр. R3c с параметрами элементарной ячейки a = 10.5617(2) Å; c = 37.5017(7) Å; V= 3622.9(1) Å3, Rwp = 3.78. Методом ИК-спектрометрии, подтверждено наличие изолированных MoO4 группировок в его структуре. Показано, что проводимость K5Cu0.5Hf1.5(MoO4)6 достигает 7.5·10–4 См/см (550°C) при Еа = 0.9 эВ. Термические деформации исследованы методом высокотемпературной порошковой рентгенографии в интервале температур 30–500 °C.
Выводы: Полученный тройной молибдат относится к материалам с высоким тепловым расширением (αV = 45·10–6 °C–1 при 500 °C) и характеризуется слабой анизотропией. Результаты импедансной спектроскопии и высокотемпературной рентгенографии позволяют отнести наблюдаемый на кривой дифференциальной сканирующей калориметрии эндотермический эффект при 479 °С к фазовому переходу первого типа
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