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Thermokinetic of the formation of α-Al2O3-nano from hydrated forms of γ-, γ’-, θ-, κ-Al2O3-nano powders at 570—1470 K

В.В.Гарбуз*,
 
Т.А.Сілінська,
 
Т.Ф.Лобунець,
 
О.І.Биков,
 
В.Б.Муратов,
 
Т.М.Терентьєва,
 
Л.М.Кузьменко,
 
В.А.Сидоренчук,
 
О.О.Васільєв,
 
О.І.Оліфан,
 
Т.В.Хомко
 

Інститут проблем матеріалознавства ім. І. М. Францевича НАН України , Київ
Garbuz.v1950@Gmail.com
Usp. materialozn. 2025, 10/11:100-117
https://doi.org/10.15407/materials2025.10-11.100

Анотація

Hydrated powders γ-, γ '-, θ-, κ-Al2O3-nanowere for the first timedirectly precipitated from alkaline solutions of Na [Al (OH)4], by-products of α-AlB12 synthesis, using nitric acid (at pH = 5,0—5,5). Precipitates were washed and dried at 570 K (SВЕТ = 213m2g-1, d = 5—10 nm). The powders, in the form of two parallel series, underwent step air treatment (SAT) for 2 hours at 570—1470 K with a step of 50—100 K. The samples of the first series («1») were heated in series (T0 → T1 → T2 → ··· Tn). The second (“2”) —once (T0 → T1; T0 → T2; ··· T0 → Tn). The formation of α-Al2O3-nano oxide occurs during three parallel reactions: dehydration, phase transition γ → α-Al2O3-nano and growth of α-Al2O3-nano particles. The samples were measured using chemical analysis methods (elemental and chemical phase composition), X-ray phase analysis (phase composition), X-ray diffractometric of the coherent scattering region hkl012 α-Al2O3-nano at 1470K (average size of α-Al2O3 crystallites), thermal desorption method nitrogen (Sspecific, BET) and X-ray fluorescence analysis (mass fraction of product and impurities). At 570–720 K, the activation energy of the dehydration of the two OH groups are EaAl(OH)3→AlO(OH), H2O ↑ = 59,4 ± 0,5 kJ · mol-1. At 820—1070 K, the last OH-group decomposes at a rate of 2,13 · 10–4— 4,93 ·10–4 mol · s-1  and an activation energy with in EaAlO(OH) →Al2O3, 0,5H2O ↑ = 13,2 ± 0,8 kJ · mol- 1. At 770—970 K (first), the activation energy of the phase transition is Ea, γ → Α-Al2O3 = 23,9 ± 1,0 kJ · mol-1. At 1070—1170 K Ea, γ → Α-Al2O3 = 83,5 ± 0,8 kJ · mol-1. It agrees with the known heat of transformation ΔН γ →Α-Al2O3 = 86,2 kJ · mol-1. Dimensional characteristics of crystallites (10,4—48 nm); specific surface area of powders (213—8,6 m2· · g-1, BET); thermokinetic parameters of thermal growth of α-Al2O3-nano crystallites (V α-Al2O3 =  1,44 · 10-3—6,67 · 10-3 nm · s-1; E α-Al2O3 = 38,7 ±2,1 kJ · mol-1; A0, α-Al2O3 = 0,80  ± 0,02 s-1 at 1220 –1370 K) along the temperature scale 570—1470 K were determined and calculated. When SAT ~ 1170 K for ~2 hours, the phase ratio γ-Al2O3 / α-Al2O3 ≈ 1 : 1. This ratio causes a high content of surface 5-coordinated ionic polyhedral27Al3+, as places for attachment of catalytically active atoms, such as Pt.

Keywords: thermal kinetics, phase transition, powders, γ → α-Al2O3-nano, dehydration, thermal growth of crystallites.


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