CN106045525B - A kind of silicon nitride sinter and preparation method thereof - Google Patents

A kind of silicon nitride sinter and preparation method thereof Download PDF

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CN106045525B
CN106045525B CN201610381662.7A CN201610381662A CN106045525B CN 106045525 B CN106045525 B CN 106045525B CN 201610381662 A CN201610381662 A CN 201610381662A CN 106045525 B CN106045525 B CN 106045525B
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metal
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silicon nitride
nitride
silicon
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CN106045525A (en
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刘学建
王鲁杰
杨晓
姚秀敏
黄政仁
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to a kind of silicon nitride sinters and preparation method thereof, the silicon nitride sinter includes silicon nitride phase and Grain-Boundary Phase, the Grain-Boundary Phase includes metal silicide and metal nitride, wherein metal silicide and metal nitride are at least partly with form that is adjacent or/and mutually wrapping up presence, the metal silicide and metal nitride gross mass account for the 0.1~10wt%, preferably 0.1~5wt% of the gross mass of the silicon nitride and sintering aid.Nitride sintering plastid provided by the invention has good bending strength, fracture toughness, thermal shock resistance, can be used for the fields such as machinery, metallurgy, aviation.

Description

A kind of silicon nitride sinter and preparation method thereof
Technical field
The present invention relates to a kind of silicon nitride sinters and preparation method thereof, belong to Material Field.
Background technique
Silicon nitride is widely used in the fields such as machinery, metallurgy, aviation with performances such as high intensity, high tenacity, anti-thermal shocks.Its Performance depends on consistency, grain size distribution and the draw ratio of silicon nitride, the property of reinforced phase etc..
The silicide of Fe, Mn, Cu, Ni, Co, Cr etc. have lower fusing point, can promote silicon nitride mass transfer, accelerate fine and close The advantages that changing, increasing grain aspect ratio, conducive to the raising of silicon nitride plastid performance.But these silicides itself, which often have, to be compared High thermal expansion coefficient is easy to crack because contraction is excessive in cooling procedure after the sintering of silicon nitride plastid, and it possesses Relatively low elasticity modulus, be easy to cause stress concentration effect, and micro-crack and stress concentration are be easy to cause under the intensity of silicon nitride Drop, excessively high thermal expansion coefficient are also unfavorable for the thermal shock resistance of silicon nitride sinter.
W, the nitride of Mo, Ti, V etc. often have the characteristics that thermal expansion coefficient is low, elasticity modulus is high, are separately added to The fracture toughness of silicon nitride can be improved in silicon nitride in a certain range, but high elastic modulus also be easy to cause stress to concentrate, It is unfavorable for the promotion of silicon nitride bending strength.
Summary of the invention
In view of the above-mentioned problems, the present invention combines the silicide and W, Mo, Ti, V etc. of Fe, Mn, Cu, Ni, Co, Cr etc. for the first time The advantages of nitride, its purpose is to provide a kind of, and the silicon nitride with good bending strength, fracture toughness, thermal shock resistance is burnt Knot body.
On the one hand, the present invention provides a kind of silicon nitride sinter, the silicon nitride sinter includes silicon nitride phase and crystalline substance Boundary's phase, the Grain-Boundary Phase include metal silicide and metal nitride, and wherein metal silicide and metal nitride be at least partly With form that is adjacent or/and mutually wrapping up presence, the metal silicide and metal nitride gross mass account for the silicon nitride with 0.1~10wt% of the gross mass of sintering aid, preferably 0.1~5wt%.Metal silicide and metal nitrogen in the Grain-Boundary Phase Compound is more than 30% presence in the form of phase that is adjacent or mutually wrapping up.
The silicide of Fe, Mn, Cu, Ni, Co, Cr etc. in conjunction with the Nitride Phase of W, Mo, Ti, V etc., are passed through gold by the present invention Category silicide is adjacent or wraps up the presence of metal nitride form, and metal silicide can effectively promote effect of mass transmitting, improves The pattern of silicon nitride, and metal nitride plays the high thermal expansion coefficient of metal silicide, low elastic modulus and delays well Punching effect, stress concentration effect and thermal expansion mismatch effect and are controlled effectively.
Preferably, the diameter of adjacent phase and/or mutually package phase that the metal silicide is formed with metal nitride is 0.2~200 μm.
Preferably, the mass ratio of the metal silicide and metal nitride is 1:10~10:1, preferably 1:5~5:1.
Preferably, the metal silicide is at least one of the silicide of Fe, Mn, Cu, Ni, Co, Cr.
Preferably, the metal nitride is at least one of the nitride of W, Mo, Ti, V.
On the other hand, the present invention also provides a kind of preparation methods of silicon nitride sinter, comprising:
(1) at least one of first metal-powder W, Mo, Ti, V and silicon powder are mixed according to atomic ratio 1:2~3:1 ball milling It dried, be sieved after conjunction, be heat-treated 1-2 hours at 1300-1700 DEG C in argon atmosphere, obtain the first metal silicide Powder；
(2) by least one of second metal-powder Fe, Mn, Cu, Ni, Co, Cr and silicon powder according to atomic ratio 1:2~3: After 1 weighs, dried, be sieved after adding the first metal silication powder ball milling mixing of gained, in argon atmosphere It is heat-treated 1-2 hours at 1100-1300 DEG C, obtains more metal silication powders；
(3) by much after metal silicide powder, beta-silicon nitride powder, sintering aid ball milling mixing through drying, sieving, at Type is sintered 1~5 hour at 1700~1900 DEG C in the atmosphere containing nitrogen, obtains the silicon nitride sinter.
The method comprises the steps of firstly, preparing more metal silication powders, wherein more metal silication powders are mostly mutually to wrap up or adjacent Structure exists, and is bonded to each other close.Then beta-silicon nitride powder, more metal silication powders, sintering aid are uniformly mixed, at Type is sintered under the atmosphere containing nitrogen, made in sintered body by reaction in-situ the first metal silicide (for example, W, Mo, At least one of silicide of Ti, V) in-situ preparation metal nitride, and the second metal silicide of formation (for example, Fe, Mn, At least one of silicide of Cu, Ni, Co, Cr) or package phase adjacent with the first metal nitride.So many metal silicide It is not easy in mixing process to be broken up, is easy to make metal nitride and the second metal silicide is adjacent or mutual package.
Preferably, at least one of second metal-powder Fe, Mn, Cu, Ni, Co, Cr described in step (2) and silicon powder The mass ratio of gross mass and the first metal silication powder is 1:10~10:1, preferably 1:5~5:1.
Preferably, sintering aid described in step (3) is metal oxide or/and rare earth oxide, the sintering aid Quality be beta-silicon nitride powder and sintering aid gross mass 3~15wt%, wherein metal oxide be Al2O3, in MgO extremely Few one or more, rare earth oxide Y2O3、Yb2O3、Sm2O3、La2O3One of or it is a variety of.
Preferably, the solvent of the ball milling mixing can be dehydrated alcohol.
Preferably, the drying is 2-8 hours dry at 40-80 DEG C.
Preferably, the quality of more metal silication powders described in step (3) is beta-silicon nitride powder and the total matter of sintering aid 0.1~10wt% of amount, preferably 0.1~5%.
Preferably, the average grain diameter of more metal silication powders is no more than 15 μm.
Preferably, the first isostatic cool pressing at 120-200MPa again after 10-80MPa dry-pressing is shaped to described in step (3), Or the cold isostatic compaction directly at 120-200MPa.
Nitride sintering plastid provided by the invention has good bending strength, fracture toughness, thermal shock resistance, can be used for The fields such as machinery, metallurgy, aviation.
Detailed description of the invention
Fig. 1 is the XRD spectrum of more metal silication powders prepared by embodiment 1；
Fig. 2 is the SEM backscattered electron figure of more metal silication powders prepared by embodiment 1；
Fig. 3 is the EDS elemental analysis energy spectrum diagram of more metal silication powders prepared by embodiment 1；
Fig. 4 is the EDS elemental analysis energy spectrum diagram of silicon nitride sinter section prepared by embodiment 1；
Fig. 5 is the SEM figure of silicon nitride sinter burnishing surface prepared by embodiment 1；
Fig. 6 is the EDS element line with adjacent or package structure Grain-Boundary Phase of silicon nitride sinter prepared by embodiment 1 Scanning spectra；
Fig. 7 is in silicon nitride sinter burnishing surface prepared by embodiment 1 with adjacent or package structure Grain-Boundary Phase EBSD energy spectrum diagram.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this Invention, is not intended to limit the present invention.
The present invention uniformly mixes beta-silicon nitride powder, more metal silication powders, sintering aid, and molding is containing nitrogen Atmosphere under be sintered, the silicon nitride sinter comprising silicon nitride phase and Grain-Boundary Phase can be formed.Wherein Grain-Boundary Phase includes by mostly golden Belong to silication powder generate at least partly with metal silicide and metal nitride adjacent or/and mutually wrap up.Wherein burn Knot auxiliary agent largely exists in Grain-Boundary Phase.The content of metal silicide described in Grain-Boundary Phase and metal nitride depends on adding The more metal silication powder amounts entered, can account for 0.1~10wt% of beta-silicon nitride powder and sintering aid gross mass, preferably 0.1~ 5wt%.The present invention can also be by the ratio of adjusting metal silicide and metal nitride, wherein the metal silicide and metal The mass ratio of nitride can be 1:10~10:1, preferably 1:5~5:1, can make silicon nitride body bending strength, fracture toughness with And thermal shock resistance reaches different degrees of raising.Illustrate to following exemplary that silicon nitride sinter provided by the invention obtains the side of preparation Method.
The present invention weighs at least one of first metal-powder W, Mo, Ti, V and silicon powder according to atomic ratio 1:2~3:1 Mixing adds solvent (for example, dehydrated alcohol etc.) and carries out ball milling mixing, obtains a slurry.
By a slurry drying, sieving, it is heat-treated 1-2 hours, obtains at 1300-1700 DEG C in argon atmosphere First metal silication powder.
At least one of second metal-powder Fe, Mn, Cu, Ni, Co, Cr and silicon powder are claimed according to atomic ratio 1:2~3:1 After amount, after adding the first metal silication powder of gained, solvent (for example, dehydrated alcohol etc.) progress ball milling mixing, two are obtained Secondary slurry.The wherein gross mass and first of at least one of described second metal-powder Fe, Mn, Cu, Ni, Co, Cr with silicon powder The mass ratio of metal silication powder can be 1:10~10:1, preferably 1:5~5:1.
By secondary slurry drying, sieving, it is heat-treated 1-2 hours, obtains at 1100-1300 DEG C in argon atmosphere More metal silication powders.This time heat treatment is so that silicide different in more metal silication powders is closely combined one It rises, different silicides is also difficult to be dispersed by ball milling mixing in the mixing process being added in beta-silicon nitride powder.
By the more metal silication powders, beta-silicon nitride powder, sintering aid of preparation (for example, metal oxide and rare earth oxygen Compound), solvent (for example, dehydrated alcohol etc.), and ball milling mixing is carried out, wherein the quality of more metal silication powders can be 0.1~10wt% of beta-silicon nitride powder and sintering aid gross mass, preferably 0.1~5wt%.The quality of the sintering aid can be 3~15wt% of beta-silicon nitride powder and sintering aid gross mass.Then by dry, sieving, molding, then at the gas containing nitrogen It is sintered 1~5 hour at 1700~1900 DEG C in atmosphere (such as nitrogen pressure can be 1MPa), obtains the silicon nitride sinter. Make the first metal silicide in more metal silication powders partially or completely through reaction in-situ in this sintering process Metal nitride is generated in sintered body, wherein the second metal silicide and metal silicide portion form metal silicide and gold Category nitride is adjacent or wraps up phase.Wherein, the average grain diameter of more metal silication powders is no more than 15 μm, and particle crosses conference Cause difficulties in dispersion.
It is dried described in the above method generally 2-8 hours dry at 40-80 DEG C using baking oven.
Molding described in the above method can be the first isostatic cool pressing at 120-200MPa again after 10-80MPa dry-pressing.Or it is straight Connect the cold isostatic compaction at 120-200MPa.
The present invention uses the three-point bending resistance intensity of universal testing machine test sample.The present invention is using fluting method test sample Fracture toughness.
The present invention reduces by 50% temperature difference using water cooling test intensity, with the thermal shock resistance of test sample.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
Phase tungsten powder and the total 100g of silicon powder are weighed according to W:Si=1:2 (atomic ratio), is placed in silicon nitride ball grinding jar；
100g silicon nitride mill ball, 150g dehydrated alcohol are added, planetary ball mill (rpm=300) mixes 1h；
Slurry crosses 80 meshes, obtains powder through 80 DEG C of oven drying 5h；
Powder 1400 DEG C of heat treatment 2h under an argon atmosphere, obtain WSi2Powder；
Corresponding iron powder and the total 100g of silicon powder, WSi obtained by the above method are weighed according to Fe:Si=1:2 (atomic ratio)2Powder 100g is placed in silicon nitride ball grinding jar；
200g silicon nitride mill ball, 300g dehydrated alcohol are added, planetary ball mill (rpm=300) mixes 2h；
Slurry crosses 80 meshes, obtains powder through 60 DEG C of oven drying 5h；
Powder 1200 DEG C of heat treatment 3h under an argon atmosphere, obtain FeSi2:WSi2More metal silications of=1:1 (mass ratio) Powder；Weigh FeSi2:WSi2More metal silication powder 1.5g of=1:1 (mass ratio), alumina powder 3g, oxidation yttrium powder Body 9g, beta-silicon nitride powder 88g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material；
Powder molding after under 1MPa nitrogen pressure 1800 DEG C of sintering 2h.
Fig. 1 is the XRD spectrum of more metal silication powders prepared by embodiment 1, the results showed that W powder, Fe powder and Si powder can To react completely, preparing main group becomes WSi2、FeSi2With the object phase of FeSi, other miscellaneous phases are not found.
Fig. 2 is the SEM backscattered electron figure of more metal silication powders prepared by embodiment 1, the results showed that prepared Metal silicide grain is tiny, uniform.
Fig. 3 is the EDS elemental analysis energy spectrum diagram of more metal silication powders prepared by embodiment 1, the results showed that prepared More metal silication powders mostly mutually to wrap up or adjacent structure exists, be bonded to each other close.
Fig. 4 is the EDS elemental analysis energy spectrum diagram of silicon nitride sinter section prepared by embodiment 1, the results showed that made In standby silicon nitride ceramics sintered body, phase containing Fe and phase containing W are largely combined together, and form adjacent or/and package phase.
Fig. 5 is the SEM figure of silicon nitride sinter burnishing surface prepared by embodiment 1；Fig. 6 is silicon nitride prepared by embodiment 1 With the EDS elemental line scan map of adjacent or package structure Grain-Boundary Phase in sintered body burnishing surface.In conjunction with Fig. 5 and Fig. 6 result Show: phase containing Fe and phase containing W are combined together in the form mutually wrapped up, the effectively package phase containing W of phase containing Fe.
Fig. 7 is in silicon nitride sinter burnishing surface prepared by embodiment 1 with adjacent or package structure Grain-Boundary Phase EBSD energy spectrum diagram, the results showed that form the microstructure of the effectively package phase containing W of phase containing Fe；And phase containing Fe is Fe5Si3Phase, Phase containing W is WN phase.
Embodiment 2
CuSi is prepared referring to embodiment 12/WSi2More metal silication powders of=1:1 (mass ratio)；
Weigh CuSi2/WSi2More metal silication powder 5g of=1:1 (mass ratio), magnesium oxide powder 3g, oxidation yttrium powder Body 5g, beta-silicon nitride powder 92g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 5MPa nitrogen pressure 1860 DEG C of sintering 3h.
Embodiment 3
FeSi is prepared referring to embodiment 12/MoSi2More metal silication powders of=10:1 (mass ratio)；
Weigh FeSi2/MoSi2More metal silication powder 1g, the alumina powder 4g, lanthana of=10:1 (mass ratio) Powder 11g, beta-silicon nitride powder 85g are placed in silicon nitride ball grinding jar, add 150g dehydrated alcohol, 200g silicon nitride mill ball, warp Ball milling, drying, sieving obtain powder material.Powder molding after under 0.2MPa nitrogen pressure 1750 DEG C of sintering 5h.
Embodiment 4
FeSi is prepared referring to embodiment 12/MoSi2More metal silication powders of=10:1 (mass ratio)；
Weigh FeSi2/MoSi2More metal silication powder 0.5g of=10:1 (mass ratio), alumina powder 3g, oxidation Cerium powder 5g, beta-silicon nitride powder 92g are placed in silicon nitride ball grinding jar, add 150g dehydrated alcohol, 200g silicon nitride mill ball, warp Ball milling, drying, sieving obtain powder material.Powder molding after under 3MPa nitrogen pressure 1850 DEG C of sintering 1h.
Embodiment 5
MnSi is prepared referring to embodiment 12/MoSi2More metal silication powders of=1:10 (mass ratio)；
Weigh MnSi2/MoSi2More metal silication powder 3g, the alumina powder 4g, samarium oxide of=1:10 (mass ratio) Powder 4g, beta-silicon nitride powder 92g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 0.5MPa nitrogen pressure 1820 DEG C of sintering 3h.
Embodiment 6
Fe is prepared referring to embodiment 15Si3/MoSi2More metal silication powders of=10:1 (mass ratio)；
Weigh Fe5Si3/MoSi2More metal silication powder 2g, the alumina powder 5g, erbium oxide of=10:1 (mass ratio) Powder 6g, beta-silicon nitride powder 89g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 0.1MPa nitrogen pressure 1800 DEG C of sintering 2h.
Embodiment 7
FeSi is prepared referring to embodiment 12/WSi2More metal silication powders of=1:10 (mass ratio)；
Weigh FeSi2/WSi2More metal silication powder 0.1g, the alumina powder 2g, ytterbium oxide of=1:10 (mass ratio) Powder 8g, beta-silicon nitride powder 90g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 3MPa nitrogen pressure 1800 DEG C of sintering 2h.
Embodiment 8
FeSi is prepared referring to embodiment 12/WSi2More metal silication powders of=1:5 (mass ratio)；
Weigh FeSi2/WSi2More metal silication powder 0.6g, the alumina powder 9g, luteium oxide of=1:5 (mass ratio) Powder 6g, beta-silicon nitride powder 85g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 0.1MPa nitrogen pressure 1700 DEG C of sintering 5h.
Embodiment 9
Cu is prepared referring to embodiment 13Si/WSi2More metal silication powders of=5:1 (mass ratio)；
Weigh Cu3Si/WSi2More metal silication powder 1g of=5:1 (mass ratio), alumina powder 5g, oxidation yttrium powder Body 5g, beta-silicon nitride powder 90g are placed in silicon nitride ball grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, through ball Mill, dry, sieving obtain powder material.Powder molding after under 1MPa nitrogen pressure 1750 DEG C of sintering 2h.
Embodiment 10
FeSi is prepared referring to embodiment 12/WSi2More metal silication powders of=1:1 (mass ratio)；
Weigh FeSi2/WSi2More metal silication powder 10g, the magnesium oxide powder 2.5g, ytterbium oxide of=1:1 (mass ratio) Powder 0.5g, beta-silicon nitride powder 97g are placed in silicon nitride ball grinding jar, add 150g dehydrated alcohol, 200g silicon nitride mill ball, warp Ball milling, drying, sieving obtain powder material.Powder molding after under 6MPa nitrogen pressure 1900 DEG C of sintering 5h.
Embodiment 2~10 is using variety classes and the metal-powder of content and silicon powder raw material, by same as Example 1 Or similar preparation process, prepare various other silicon nitride sinters；Result of study shows: being sintered in prepared silicon nitride The microstructure that respective metal silicide is adjacent with metal nitride or wraps up is similarly formed in body, the bending resistance of sintered body is strong Degree, fracture toughness and thermal shock resistance etc. are excellent in, reference table 1.
Comparative example 1
It weighs alumina powder 3g, yttrium oxide powder 9g, beta-silicon nitride powder 88g to be placed in silicon nitride ball grinding jar, add 150g dehydrated alcohol, 200g silicon nitride mill ball, obtain powder material through ball milling, drying, sieving.In 1MPa nitrogen after powder molding The lower 1800 DEG C of sintering 2h of gas air pressure.
Comparative example 2
MoSi is prepared referring to embodiment 12Powder；
Weigh MoSi2Powder 0.5g, alumina powder 3g, yttrium oxide powder 9g, beta-silicon nitride powder 88g are placed in silicon nitride ball In grinding jar, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, obtains powder material through ball milling, drying, sieving.Powder at After type under 1MPa nitrogen pressure 1800 DEG C of sintering 2h.
Comparative example 3
FeSi is prepared referring to embodiment 12Powder；
Weigh FeSi2Powder 2g, alumina powder 3g, yttrium oxide powder 9g, beta-silicon nitride powder 88g are placed in silicon nitride ball milling In tank, 150g dehydrated alcohol, 200g silicon nitride mill ball are added, obtains powder material through ball milling, drying, sieving.Powder molding 1800 DEG C of sintering 2h under 1MPa nitrogen pressure afterwards.
Comparative example 1~3 is using same as Example 1 or similar preparation process, (the comparison when not introducing metal silicide Example 1), bending strength, fracture toughness and thermal shock resistance of prepared sintered material etc. decrease；When only introducing one kind When metal silicide (comparative example 2 and 3), the property such as bending strength, fracture toughness and thermal shock resistance of prepared sintered material It can not can get a promotion simultaneously, reference table 1.
1 metal silicide of table adds type, content and respective intensities, toughness, thermal shock resistance

Claims (10)

1. a kind of silicon nitride sinter, which is characterized in that the silicon nitride sinter includes silicon nitride phase and Grain-Boundary Phase, the crystalline substance Boundary mutually includes metal silicide and metal nitride, wherein metal silicide and metal nitride at least partly with adjacent or/and The form mutually wrapped up exists, and the metal silicide and metal nitride gross mass account for the beta-silicon nitride powder and sintering aid Gross mass 0.1~10wt%；
The metal silicide be Fe, Mn, Cu, Ni, Co, Cr at least one of silicide, the metal nitride be W, At least one of nitride of Mo, Ti, V；
The preparation method of the silicon nitride sinter includes:
(1) after by least one of first metal-powder W, Mo, Ti, V and silicon powder according to atomic ratio 1:2~3:1 ball milling mixing Drying, sieving are heat-treated 1~2 hour at 1300-1700 DEG C in argon atmosphere, obtain the first metal silicide powder Body；
(2) at least one of second metal-powder Fe, Mn, Cu, Ni, Co, Cr and silicon powder are claimed according to atomic ratio 1:2~3:1 After amount, dried, be sieved after adding the first metal silication powder ball milling mixing of gained, in argon atmosphere 1100~ It is heat-treated 1~2 hour at 1300 DEG C, obtains more metal silication powders；
(3) by much after metal silicide powder, beta-silicon nitride powder, sintering aid ball milling mixing through drying, sieving, molding, It is sintered 1~5 hour at 1700~1900 DEG C in the atmosphere containing nitrogen, obtains the silicon nitride sinter.
2. silicon nitride sinter according to claim 1, which is characterized in that the metal silicide and metal nitride are total Quality accounts for 0.1~5wt% of the gross mass of the silicon nitride and sintering aid.
3. silicon nitride sinter according to claim 1, which is characterized in that the metal silicide and metal nitride shape At adjacent phase and/or mutually package phase diameter be 0.2~200 μm.
4. silicon nitride sinter according to any one of claim 1-3, which is characterized in that the metal silicide and gold The mass ratio for belonging to nitride is 1:10~10:1.
5. a kind of preparation method for preparing silicon nitride sinter, which is characterized in that the silicon nitride sinter includes silicon nitride phase And Grain-Boundary Phase, the Grain-Boundary Phase include metal silicide and metal nitride, wherein metal silicide and metal nitride be at least Part accounts for the nitridation with form that is adjacent or/and mutually wrapping up presence, the metal silicide and metal nitride gross mass 0.1~10wt% of the gross mass of silicon powder and sintering aid；The preparation method includes:
(1) after by least one of first metal-powder W, Mo, Ti, V and silicon powder according to atomic ratio 1:2~3:1 ball milling mixing Drying, sieving are heat-treated 1~2 hour at 1300-1700 DEG C in argon atmosphere, obtain the first metal silicide powder Body；
(2) at least one of second metal-powder Fe, Mn, Cu, Ni, Co, Cr and silicon powder are claimed according to atomic ratio 1:2~3:1 After amount, dried, be sieved after adding the first metal silication powder ball milling mixing of gained, in argon atmosphere 1100~ It is heat-treated 1~2 hour at 1300 DEG C, obtains more metal silication powders；
(3) by much after metal silicide powder, beta-silicon nitride powder, sintering aid ball milling mixing through drying, sieving, molding, It is sintered 1~5 hour at 1700~1900 DEG C in the atmosphere containing nitrogen, obtains the silicon nitride sinter.
6. preparation method according to claim 5, which is characterized in that the second metal-powder Fe, Mn, Cu, Ni, Co, At least one of Cr is 1:10~10:1 with the gross mass of silicon powder and the mass ratio of the first metal silication powder.
7. preparation method according to claim 5, which is characterized in that the sintering aid is metal oxide or/and dilute Native oxide, the quality of the sintering aid are 3 ~ 15wt% of beta-silicon nitride powder and sintering aid gross mass, and wherein metal aoxidizes Object is Al2O3, at least one of MgO or a variety of, rare earth oxide Y2O3、Yb2O3、Sm2O3、La2O3One of or it is more Kind.
8. preparation method according to claim 5, which is characterized in that the average grain diameter of more metal silication powders is not More than 15 μm.
9. the preparation method according to any one of claim 5-8, which is characterized in that more metal silication powders Quality is 0.1~10wt% of beta-silicon nitride powder and sintering aid gross mass.
10. according to preparation method as claimed in claim 9, which is characterized in that the quality of more metal silication powders is nitridation 0.1~5wt% of silicon powder and sintering aid gross mass.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1842507A (en) * 2003-08-26 2006-10-04 京瓷株式会社 Silicon nitride based sintered material and method for producing the same, and molten-metal-resistant member and wear-resistant member using the same
CN104817327A (en) * 2015-03-27 2015-08-05 冷水江市明玉陶瓷工具有限责任公司 Silicon nitride composite ceramic die material, and preparation method and application thereof
CN105541337A (en) * 2015-12-25 2016-05-04 中国科学院上海硅酸盐研究所 Multi-metal silicide powder and preparing method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH064515B2 (en) * 1985-04-10 1994-01-19 株式会社日立製作所 High toughness silicon nitride sintered body and manufacturing method thereof
JP3694583B2 (en) * 1998-03-24 2005-09-14 京セラ株式会社 Crusher parts
FR2934854B1 (en) * 2008-08-08 2011-04-22 Beatrice Drazenovic SEMICONDUCTOR CERAMIC

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1842507A (en) * 2003-08-26 2006-10-04 京瓷株式会社 Silicon nitride based sintered material and method for producing the same, and molten-metal-resistant member and wear-resistant member using the same
CN104817327A (en) * 2015-03-27 2015-08-05 冷水江市明玉陶瓷工具有限责任公司 Silicon nitride composite ceramic die material, and preparation method and application thereof
CN105541337A (en) * 2015-12-25 2016-05-04 中国科学院上海硅酸盐研究所 Multi-metal silicide powder and preparing method thereof

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