CN109970454A - A kind of transition metal oxide inhibit silicon nitride phase transformation method and its silicon nitride ceramics obtained - Google Patents

A kind of transition metal oxide inhibit silicon nitride phase transformation method and its silicon nitride ceramics obtained Download PDF

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CN109970454A
CN109970454A CN201910213957.7A CN201910213957A CN109970454A CN 109970454 A CN109970454 A CN 109970454A CN 201910213957 A CN201910213957 A CN 201910213957A CN 109970454 A CN109970454 A CN 109970454A
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silicon nitride
mgo
powder
phase transformation
metal oxide
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于俊杰
魏万鑫
郭伟明
林华泰
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The present invention provides a kind of method of transition metal oxide inhibition silicon nitride phase transformation and its silicon nitride ceramics obtained.This method is by α-Si3N4Transition metal oxide MO (ZrO is introduced in powder2、TiO2、HfO2、Ta2O5Or Cr2O3) and sintering aid MgO-Re2O3Through mixing, α-Si is obtained after dry3N4‑MO‑MgO‑Re2O3Mixed powder under the argon atmosphere of 1atm, be warming up to 1450~1550 DEG C by mixed powder after cold isostatic compaction and keep the temperature, obtain silicon nitride ceramics after pressureless sintering or hot pressed sintering.The present invention is by α-Si3N4MO is introduced in powder, it is suppressed that α-Si3N4At high temperature to β-Si3N4Phase transformation.Compared with prior art, the present invention is by inhibiting α-Si3N4To β-Si3N4Phase transformation, realize silicon nitride phase transformation controllability.

Description

A kind of transition metal oxide inhibits the method and its nitridation obtained of silicon nitride phase transformation Silicon ceramics
Technical field
The invention belongs to non-oxidized substance sill technical fields, inhibit more particularly, to a kind of transition metal oxide The method of silicon nitride phase transformation and its silicon nitride ceramics obtained.
Background technique
Si3N4It is a kind of strong covalent bond compound, is difficult to reach fine and close by solid-phase sintering, it is generally real using liquid-phase sintering Now densify.Usually with α → β-Si in liquid sintering process3N4Phase transformation, α-Si3N4Belong to low-temperature stabilization crystal form, have etc. Shaft-like crystal morphology, hardness is higher, but toughness is low；β-Si3N4Belong to high-temperature stable crystal form, there is long rodlike or acicular crystal pattern, Bending strength and fracture toughness are higher, but hardness is low.Currently, the research in relation to silicon nitride phase transformation, which is concentrated mainly on, promotes phase transformation side Face such as improves sintering temperature, introduces β-Si3N4Crystal seed or low-temperature sintering auxiliary agent Li2O-Y2O3Etc. realizing [Lei Fan, Meng Zhou,Hongjie Wang,Zhongqi Shi,Xuefeng Lu,Chao Wang,Low-Temperature Preparation ofβ-Si3N4Porous Ceramics with a Small Amount ofLi2O–Y2O3, J.Am.Ceram.Soc.97(2014)1371–1374.].And it is less and main in relation to control/inhibition silicon nitride phase transformation research Concentrate on reducing sintering temperature, introduce low content sintering aid or nano particle, using discharge plasma sintering (SPS) or other Field assisted sintering technology.Such as, Yu etc. obtains α-Si by SPS sintering technology3N4Content is the Si of 75.5wt%3N4Ceramics [J.J.Yu,W.M.Guo,W.X.Wei,H.T.Lin,C.Y.Wang,Fabrication and wear behaviors of graded Si3N4ceramics by the combination of two-step sintering and β- Si3N4seeds,J.Eur.Ceram.Soc.38(2018)3457–3462.].Based on this, if can control Si3N4In high temperature sintering Phase transformation in the process can prepare high α-Si3N4The silicon nitride ceramics of phase, to improve its hardness.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art and disadvantage, the primary purpose of the present invention is that providing a kind of mistake Cross the method that metal oxide inhibits silicon nitride phase transformation.This method is by introducing MO powder (ZrO2、TiO2、HfO2、Ta2O5Or Cr2O5) realize silicon nitride phase transformation controllability.
Another object of the present invention is to provide silicon nitride ceramics made from the above method.
A further object of the present invention is to provide the applications of above-mentioned silicon nitride ceramics.
The purpose of the present invention is realized by following technical proposals:
A kind of method that transition metal oxide inhibits silicon nitride phase transformation, comprises the following specific steps that:
S1. by α-Si3N4, MO, MgO and Re2O3Through mixing, Si is obtained after dry3N4-MO-MgO-Re2O3Mixed powder, The MO is ZrO2、TiO2、HfO2、Ta2O5Or Cr2O3；
S2. by Si3N4-MO-MgO-Re2O3Mixed powder is after cold isostatic compaction, under the argon atmosphere of 1atm, rises I to 1100~1200 DEG C of temperature, then heating up again and keeps the temperature by II to 1450~1550 DEG C, is 30MPa's through pressureless sintering or pressure Silicon nitride ceramics is obtained after hot pressed sintering, α-Si in the silicon nitride ceramics3N4The mass fraction of phase is 80~95%.
Preferably, α-Si described in step S13N4: MO:MgO-Re2O3Volume ratio be (97~89): (1~5): (2~ 6)；The MgO-Re2O3Middle MgO:Re2O3Volume ratio be (1~99): (1~99).
It is further preferable that α-the Si3N4: MO:MgO-Re2O3Volume ratio be 37:1:2, the MgO-Re2O3Middle MgO: Re2O3Volume ratio be 3:2.
Preferably, Re described in step S12O3Middle Re be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
Preferably, the α-Si3N4The purity of powder is 98~100wt%, α-Si3N4The partial size of powder is 0.3~1 μm；It is described The purity of MO powder is 99~99.99wt%, and the partial size of MO powder is 20~100nm；The purity of the MgO powder be 99.8~ The partial size of 99.99wt%, MgO powder is 50~100nm；The Re2O3The purity of powder is 99.9~99.99wt%, Re2O3Powder Partial size is 50~100nm.
Preferably, the diameter of cold isostatic compaction described in step S2 is 10~50mm, with a thickness of 3~6mm, briquetting pressure For 50~200MPa.
Preferably, the rate of heating I described in step S2 is 10~25 DEG C/min, and the rate of the heating II is 8~12 DEG C/min, the time of the heat preservation is 0.5~4h.
A kind of silicon nitride ceramics, the ceramics are that the method is made.
Preferably, α-Si in the silicon nitride ceramics3N4The mass fraction of phase is 80~95%.
Application of the silicon nitride ceramics in high speed cutting tool field.
Compared with prior art, the invention has the following advantages:
1. the present invention is by α-Si3N4The MO powder introduced in powder, wherein MO ZrO2、TiO2、HfO2、Ta2O5Or Cr2O5, can inhibit α-Si3N4To β-Si3N4Phase transformation；
2. α-Si in silicon nitride ceramics obtained in the present invention3N4Phase content is higher, it can be achieved that high rigidity.
Detailed description of the invention
Fig. 1 is the XRD spectrum of 1 silicon nitride ceramics of embodiment.
Fig. 2 is the XRD spectrum of 1 silicon nitride ceramics of comparative example.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention. Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. preparation:
(1) with α-Si3N4Powder is matrix material, with ZrO2Powder, MgO powder and Yb2O3Powder is sintering aid, according to Si3N4: ZrO2: MgO:Yb2O3Volume ratio be 90:2.5:3:2 through mixing, it is dry after obtain uniformly mixed Si3N4-ZrO2-MgO- Yb2O3Powder.
(2) by Si3N4-ZrO2-MgO-Yb2O3It is 50mm that mixed powder, which is placed on diameter through the cold isostatic compaction of 50MPa, In hot pressing furnace mold, under the argon gas of 1atm, 1200 DEG C are warming up to the rate of 15 DEG C/min, then with the rate of 10 DEG C/min 1500 DEG C are warming up to, and keeps the temperature 1h, obtains silicon nitride ceramics after pressure is the hot pressed sintering of 30MPa.
2. performance test: the resulting Si of the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 89%.Comparative example 1
1. being with 1 difference of embodiment: not adding ZrO in step (1)2Powder, and Si3N4: MgO:Yb2O3Volume ratio be 95:3:2.
2. performance test: the resulting Si of this comparative example3N4α-Si in ceramics3N4The mass fraction of phase is 78%.
Compared with comparative example 1, α-Si in embodiment 13N4The mass fraction of phase is higher, ZrO2The addition of powder can inhibit α- Si3N4To β-Si3N4Phase transformation.Fig. 1 is the XRD spectrum of 1 silicon nitride ceramics of embodiment.As can be known from Fig. 1, the silicon nitride ceramics With α-Si3N4For main phase, β-Si3N4Phase peak intensity is lower.Fig. 2 is the XRD spectrum of 1 silicon nitride ceramics of comparative example.As can be known from Fig. 2, The silicon nitride ceramics is also with α-Si3N4For main phase, but β-Si3N4Peak intensity corresponding to phase is especially being compared compared with embodiment the last 1 β-Si in example 1 (Fig. 2)3N4[110], [200] and [210] peak intensity of phase is higher.In conjunction with the embodiments 1 with comparative example 1 in α- Si3N4The mass fraction of phase is also it will be evident that in embodiment 1 by introducing micro ZrO2Powder inhibits α-Si3N4To β- Si3N4Phase transformation.
Embodiment 2
1. preparation: according to α-Si3N4Powder fraction is 91.5%, TiO2The volume fraction of powder is 2.5%, MgO volume point Number is 3%, Yb2O3Volume fraction is 2% progress ingredient, is heated up according to the method for embodiment 1, cold isostatic compaction pressure is 200MPa, blank diameter 30mm, obtain silicon nitride ceramics after pressureless sintering.
2. performance test: Si made from the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 90%.
Embodiment 3
1. preparation: according to α-Si3N4Powder fraction is 93.5%, HfO2The volume fraction of powder is 2.5%, MgO volume point Number is 2%, Gd2O3Volume fraction is 2% progress ingredient, prepares Si according to 1 method of embodiment3N4Ceramics.
2. performance test: Si made from the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 87%.
Embodiment 4
1. preparation: according to α-Si3N4Powder fraction is 92.5%, Ta2O5The volume fraction of powder is 2.5%, MgO volume Score is 3%, La2O3Volume fraction is 2% progress ingredient, prepares Si according to 2 method of embodiment3N4Ceramics.
2. performance test: Si made from the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 92%.
Embodiment 5
1. preparation: according to α-Si3N4Powder fraction is 96%, Cr2O3The volume fraction of powder is 1%, MgO volume fraction For 2%, Y2O3Volume fraction is 2% progress ingredient, prepares Si according to 1 method of embodiment3N4Ceramics.
2. performance test: Si made from the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 86%.
Embodiment 6
1. preparation: according to Si3N4Powder fraction is 90%, ZrO2The volume fraction of powder is 2%, Al2O3Volume fraction is 3%, CeO2Volume fraction is 2% progress ingredient, prepares Si according to 2 method of embodiment3N4Ceramics.
2. performance test: Si made from the present embodiment3N4α-Si in ceramics3N4The mass fraction of phase is 84%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of method that transition metal oxide inhibits silicon nitride phase transformation, which is characterized in that comprise the following specific steps that:
S1. by α-Si3N4, MO, MgO and Re2O3Through mixing, Si is obtained after dry3N4-MO-MgO-Re2O3Mixed powder, it is described MO is ZrO2、TiO2、HfO2、Ta2O5Or Cr2O3；
S2. by Si3N4-MO-MgO-Re2O3Mixed powder is after cold isostatic compaction, under the argon atmosphere of 1atm, heating I to 1100~1200 DEG C, then heating up again and keeps the temperature by II to 1450~1550 DEG C, burns through the hot pressing that pressureless sintering or pressure are 30MPa Silicon nitride ceramics is obtained after knot, α-Si in the silicon nitride ceramics3N4The mass fraction of phase is 80~95%.
2. the method that transition metal oxide according to claim 1 inhibits silicon nitride phase transformation, which is characterized in that step S1 Described in α-Si3N4: MO:MgO-Re2O3Volume ratio be (97~89): (1~5): (2~6)；The MgO-Re2O3Middle MgO: Re2O3Volume ratio be (1~99): (1~99).
3. the method that transition metal oxide according to claim 2 inhibits silicon nitride phase transformation, which is characterized in that the α- Si3N4: MO:MgO-Re2O3Volume ratio be 37:1:2, the MgO-Re2O3Middle MgO:Re2O3Volume ratio be 3:2.
4. the method that transition metal oxide according to claim 1 inhibits silicon nitride phase transformation, which is characterized in that step S1 Described in Re2O3Middle Re is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
5. the method that transition metal oxide according to claim 1 inhibits silicon nitride phase transformation, which is characterized in that the α- Si3N4The purity of powder is 98~100wt%, α-Si3N4The partial size of powder is 0.3~1 μm；The purity of the MO powder be 99~ The partial size of 99.99wt%, MO powder is 20~100nm；The purity of the MgO powder is 99.8~99.99wt%, the partial size of MgO powder For 50~100nm；The Re2O3The purity of powder is 99.9~99.99wt%, Re2O3The partial size of powder is 50~100nm.
6. the method that transition metal oxide according to claim 1 inhibits silicon nitride phase transformation, which is characterized in that step S2 Described in the diameter of cold isostatic compaction be 10~50mm, with a thickness of 3~6mm, briquetting pressure is 50~200MPa.
7. the method that transition metal oxide according to claim 1 inhibits silicon nitride phase transformation, which is characterized in that step S2 Described in heating I rate be 10~25 DEG C/min, it is described heating II rate be 8~12 DEG C/min, the time of the heat preservation For 0.5~4h.
8. a kind of silicon nitride ceramics, which is characterized in that the silicon nitride ceramics is described in any item according to claim 1~7 Method is made.
9. silicon nitride ceramics according to claim 8, which is characterized in that α-Si in the silicon nitride ceramics3N4The quality of phase point Number is 80~95%.
10. application of the silicon nitride ceramics described in claim 8 or 9 in high speed cutting tool field.
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