HfN Formation and Phase Relationships in the Hf-Si-La-O-N System

doi:10.15541/jim20200382

Abstract

Abstract:

In this study, the synthesis is feasibility and formulation design of HfN composite lanthanum silicate ceramics were explored. The feasibility of HfN synthesis by ternary reaction of HfO₂-Si₃N₄-La₂O₃ system was verified by experiments, and the relationship between reaction pathway of HfO₂-Si₃N₄ binary system and Hf-Si-La-O-N was studied. Considering that the lanthanum silicate salt in the reaction of HfO₂-SiO₂-La₂O₃ ternary system was contained in the Si₃N₄-SiO₂-La₂O₃ system, lanthanum silicate was extended to the HfO₂-Si₃N₄-La₂O₃-SiO₂-HfN (Hf-Si-La-O-N) system, which clarified the coexistence of HfN and the lanthanum salt phases in the system. Experimental phase diagrams of HfO₂-SiO₂-La₂O₃ ternary system and Hf-Si-La-O-N system at 1500 ℃ were proposed. The results show that intermediate product Hf₇O₈N₄ formed in the synthesis of HfN at high temperature in HfO₂-Si₃N₄ binary system. Introduction of La₂O₃ promoted the system to generate HfN which was beneficial to reduce the burning loss rate of ceramics. There existed HfN and La_4.67Si₃O₁₃, La₅Si₃NO₁₂, LaSiNO₂, La₄Si₂N₂O₇, La₂Hf₂O₇ five lanthanum salt phases in the Hf-Si-La-O-N system.

Key words: hafnium nitride, hafnium oxide-silicon nitride-lanthanum oxide, phase relationship, composite phase

CLC Number:

TQ174

LIU Yang, LU Youjun, LI Yanrui, LIN Liqun, YUAN Zhenxia, HUANG Zhenkun. HfN Formation and Phase Relationships in the Hf-Si-La-O-N System[J]. Journal of Inorganic Materials, 2021, 36(4): 443-448.

Figures/Tables 12

References 24

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Sample	n(Si₃N₄) : n(HfO₂)	T/℃	Phase composition by XRD	Mass loss/%
1Si1.5Hf	1 : 1.5	1400	HfO₂, Hf₇O₈N₄, Si₃N₄	8.1
		1600	HfO₂, Hf₇O₈N₄, Si₃N₄, HfN	18.3
		1800	HfO₂, HfN	26.4

Sample	n(Si₃N₄) : n(HfO₂)	T/℃	Phase composition by XRD	Mass loss/%
1Si1.5Hf	1 : 1.5	1400	HfO₂, Hf₇O₈N₄, Si₃N₄	8.1
		1600	HfO₂, Hf₇O₈N₄, Si₃N₄, HfN	18.3
		1800	HfO₂, HfN	26.4

Sample	n(HfO₂) : n(SiO₂) : n(La₂O₃)	Phase composition by XRD (1500 ℃)	Mass loss/%
a	6 : 5 : 14	La₂O₃, La₂Hf₂O₇, La₂SiO₅	1.30
b	12 : 45 : 43	La₂Hf₂O₇, La_4.67Si₃O₁₃, La₂SiO₅	1.60
c	12 : 3 : 5	HfO₂, La₂Hf₂O₇, La_4.67Si₃O₁₃	0.80
d	9 : 26 : 15	HfO₂, La₂Si₂O₇, La_4.67Si₃O₁₃	1.10
e	5 : 4 : 1	HfO₂, La₂Si₂O₇, HfSiO₄	1.90
f	15 : 73 : 12	SiO₂, La₂Si₂O₇, HfSiO₄	2.30
a′	2 : 1 : 2	La₂SiO₅, La₂Hf₂O₇	1.13
b′	2 : 3 : 3	La_4.67Si₃O₁₃, La₂Hf₂O₇	0.96
c′	5 : 3 : 2	La_4.67Si₃O₁₃, HfO₂	0.87
d′	1 : 2 : 1	La₂Si₂O₇, HfO₂	0.23
e′	1 : 3 : 1	La₂Si₂O₇, HfSiO₄	1.20

Sample	n(HfO₂) : n(SiO₂) : n(La₂O₃)	Phase composition by XRD (1500 ℃)	Mass loss/%
a	6 : 5 : 14	La₂O₃, La₂Hf₂O₇, La₂SiO₅	1.30
b	12 : 45 : 43	La₂Hf₂O₇, La_4.67Si₃O₁₃, La₂SiO₅	1.60
c	12 : 3 : 5	HfO₂, La₂Hf₂O₇, La_4.67Si₃O₁₃	0.80
d	9 : 26 : 15	HfO₂, La₂Si₂O₇, La_4.67Si₃O₁₃	1.10
e	5 : 4 : 1	HfO₂, La₂Si₂O₇, HfSiO₄	1.90
f	15 : 73 : 12	SiO₂, La₂Si₂O₇, HfSiO₄	2.30
a′	2 : 1 : 2	La₂SiO₅, La₂Hf₂O₇	1.13
b′	2 : 3 : 3	La_4.67Si₃O₁₃, La₂Hf₂O₇	0.96
c′	5 : 3 : 2	La_4.67Si₃O₁₃, HfO₂	0.87
d′	1 : 2 : 1	La₂Si₂O₇, HfO₂	0.23
e′	1 : 3 : 1	La₂Si₂O₇, HfSiO₄	1.20

Sample	n(HfO₂) : n(Si₃N₄) : n(La₂O₃)	Expected product	Phase composition by XRD (1500 ℃)	Mass loss/%
1	1 : 1/3 : 1	HfN, La₂SiO₅	HfN(w), La₂Hf₂O₇(s), La₅Si₃NO₁₂(vs)	3.20
2	2 : 2/3 : 1	HfN, La₂Si₂O₇	HfN(vs), La₂Hf₂O₇(s), La_4.67Si₃O₁₃(w), Si₃N₄(vw)	2.40
3	3 : 1 : 7/3	HfN, La_4.67Si₃O₁₃	HfN(vs), La₂Hf₂O₇(s), La_4.67Si₃O₁₃(s)	4.70
4	9/4 : 1 : 5/2	HfN, La₅Si₃NO₁₂	HfN(s), La₅Si₃NO₁₂(vs), La₂Hf₂O₇(w)	4.20
5	1/4 : 1/3 : 1/2	HfN, LaSiNO₂	HfN(w), LaSiNO₂(vs)	3.70
6	1/2 : 2/3 : 2	HfN, La₄Si₂N₂O₇	HfN(w), La₅Si₃NO₁₂ (vw), La₄Si₂N₂O₇(s)	4.40