CN107986767A - A kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method - Google Patents

A kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method Download PDF

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CN107986767A
CN107986767A CN201711195837.6A CN201711195837A CN107986767A CN 107986767 A CN107986767 A CN 107986767A CN 201711195837 A CN201711195837 A CN 201711195837A CN 107986767 A CN107986767 A CN 107986767A
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sialon
raw material
content
column shape
long column
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黄军同
侯小龙
张梦
李喜宝
胡智辉
冯志军
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Nanchang Hangkong University
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Nanchang Hangkong University
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Abstract

It is an object of the invention to provide a kind of preparation method of the α Sialon fine grains of CRN method synthesis long column shape.The molecular formula of the α Sialon of the present invention is Mv+ xSi12‑(m+n)Al(m+n)OnN16‑n, M is metal cation in formula, and v is the chemical valence of metal cation M, and x is the solid solution capacity of metal cation M（x≤2）, and x=m/v.This method is to provide one kind from cheap quartz, aluminium oxide, aluminium nitride etc. as primary raw material, Re2O3For one of which cation raw material, another cation raw material is CaF2、MgF2、YF3, CaO, MgO or Y2O3In one kind, activated carbon or carbon black are reducing agent, the α Sialon fine powders prepared using conbustion synthesis is crystal seeds, by controlling the technological parameters such as raw material proportioning, synthesis temperature, soaking time, seed load, nitrogen flow and pressure, the long column shape α Sialon fine grains of high-purity, size uniform, good dispersion are prepared using carbothermal reduction-nitridation.

Description

A kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method
Technical field
The present invention relates to a kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method, belong to pottery Porcelain powder technology field.
Background technology
α-Sialon, it is considered to be α-Si3N4In there are m (Si-N keys are by m Al-N) keys to substitute, a (Si-N) keys of n are by n A (Al-O) key substitution, thus caused electricity price imbalance is compensated by metal M.Therefore the ratio between negative ions in α-Sialon Not equal to 3:4, its general formula is MxSi12-(m+n)Alm+nOnN16-n, x in formula<2.The gold of α-Sialon structures can be entered by having reported at present Category is Li, Ca, Mg, Y and rare earth element Re（Re=Nd, Sm, Gd, Dy, Er and Yb）Deng.α-Sialon ceramics are high, resistance to hardness The features such as corrosivity is good, thermal shock resistance is excellent and can reduce crystal boundary, however, since what is be usually formed is that equi-axed crystal pattern is led Cause relatively low fracture toughness and limit its extensive use.High performance ceramics are prepared, it is necessary to synthesize good crystal grain Powder.α-Sialon the crystal grain of long column shape how is prepared, is the key for obtaining high-fracture toughness α-Sialon ceramics.
Up to the present, related scholar by control nucleation and Growing Process of Crystal Particles progressively obtain the α of long column shape- Sialon crystal grain, main method concentrates on high-temperature solid phase reaction method and conbustion synthesis, but both approaches need expensive height Purity Si3N4, Si, AlN and rare earth oxide be raw material, the α-Sialon ceramics prices being prepared are relatively expensive.Carbon heat is also Former nitriding can utilize the cheap raw material method that directly synthesize Sialon as a kind of, using quartz, bauxite, clay, Zeolite, talcum etc. also synthesize and have obtained α-Sialon, but due to be concentrated mainly on the α of single cationic stabilized- Sialon, so as to obtain isometric short column crystal grain.It is reported that during solid phase method prepares α-Sialon, use（Li, Y）It is polynary α-the Sialon of cationic systems doping can obtain some fibre columnar grain, and polynary cation has than single cation more For the effect of the control nucleation of complexity.In addition, T. Li Ko etc. are reported, then using quartz as raw material, carbon it is that reducing agent passes through nitridation Reaction forms Si3N4Research in find, add some Si3N4Crystal seed is beneficial to improve Si3N4Nitriding rate and reduction Si3N4Production The crystallite dimension of thing.
Therefore, the selection of raw material and technique how is used to utilize quartz, aluminium oxide etc. to be gone back for primary raw material by carbon heat Former nitriding synthesizes to obtain long column shape α-Sialon crystal grain for preparing the α-Sialon ceramics of high-performance and low-cost with important Meaning.
The content of the invention
For in above-mentioned background technology synthesize α-Sialon there are the problem of, it is an object of the invention to provide a kind of raw material Cheap, the simple CRN method synthesis long column shape α-Sialon fine grains of technique method.This method is with cheap Quartz, aluminium oxide, aluminium nitride etc. are primary raw material, Re2O3For one of which cation raw material, another cation raw material is CaF2、MgF2、YF3, CaO, MgO or Y2O3In one kind, activated carbon or carbon black are reducing agent, with conbustion synthesis prepare α- Sialon fine powders are crystal seed, and high-purity is prepared using carbothermal reduction-nitridation in 1650 DEG C -1750 DEG C in a nitrogen atmosphere Long column shape α-Sialon fine grains.
In order to realize above-mentioned technical assignment, the present invention uses following technical scheme：
A kind of α-Sialon the fine grains and preparation method of CRN method synthesis long column shape, the raw material used, its feature It is：Quartz, SiO2Content >=98%, particle diameter≤300 μm, its content account for 40 ~ 60wt.% of total dispensing；Aluminium oxide, Al2O3Content >=98%, particle diameter≤74 μm, its content accounts for 0 ~ 10wt.% of total dispensing；Aluminium nitride, oxygen content≤2%, particle diameter≤74 μm, its content Account for 2 ~ 10 wt.% of total dispensing；Rare earth oxide Re2O3Micro mist, content >=99.5%, particle diameter≤74 μm, its content account for total dispensing 2 ~ 15wt.%；Addition of C aF2、MgF2、YF3、CaO、MgO、Y2O3It is to analyze pure, particle diameter≤30 μm Deng micro mist, its content Account for 0.1 ~ 10wt.% of total dispensing；Crystal seed α-Sialon fine powders, particle diameter≤10 μm, its content account for 0.1 ~ 10wt.% of total dispensing； For carbon black ,≤100nm, its content accounts for 18 ~ 28wt.% of total dispensing；High pure nitrogen, purity ＞ 99.99%.
A kind of preparation method of the α-Sialon fine grains of CRN method synthesis long column shape, it is characterised in that main Comprise the technical steps that：
Dispensing：By molecular formula Mv+ xSi12-(m+n)Al(m+n)OnN16-n, according to 0.5≤m≤3,0.2≤n≤1.5, v=m/x, claim Content of starting materials powder quartz, aluminium oxide, aluminium nitride, Re2O3For primary raw material, another cation chosen CaF2、MgF2、YF3、CaO、 MgO or Y2O3In one kind, its content accounts for 0 ~ 5wt.% of total dispensing.It is crystalline substance to add α-Sialon fine powders prepared by conbustion synthesis Kind, its content accounts for 0 ~ 10wt.% of total dispensing.
Ball milling：Using the method for wet ball grinding batch mixing, raw material is sufficiently mixed.Weigh raw material be put into ball milling In tank, while the agate ball of different-diameter is put into, using absolute ethyl alcohol as medium, material:Ball:Ethanol（Mass ratio）=1:1.5:2, With 10 ~ 24h of rotating speed ball milling mixing of 200 ~ 500r/min on planetary ball mill.
It is dry：The mixed powder that raw material is formed after ball milling first spontaneously dries 1h ~ 6h, absolute ethyl alcohol is greatly reduced Concentration, be then placed in baking oven and 3 ~ 15h dried below 60 DEG C.
Carbothermal reduction-nitridation：The mixed powder dried is placed in graphite crucible, it is placed in multifunctional furnace together Carry out vacuumize process so that vacuum≤10 in stove-2Pa, is then charged with N2, keep nitrogen pressure 0.12MPa, from room temperature with 20 ~ 50 DEG C of min of speed-11200 DEG C are warming up to, then with 2 ~ 10 DEG C of min-1Speed raise temperature to nitriding temperature 1650 DEG C ~ 1750 DEG C, 2 ~ 10h is kept the temperature, after nitridation reaction, naturally cools to room temperature.
Except carbon：Powder after synthesis is kept the temperature into 1 ~ 5h to exclude the carbon in powder at 650 ~ 750 DEG C, finally obtains this The invention long column shape α-Sialon fine grains.
α-the Sialon that the present invention is prepared using cheap raw material have purity height（Mass percent more than 95%）, crystal grain It is small（0.5-4 μm of diameter）, draw ratio is big（5-10）Outstanding advantages, can for prepare high quality alpha-Sialon ceramics provide it is high-quality The powder of amount ensures, can obtain great promotion and application in the industrial production.
Brief description of the drawings
Fig. 1 is the XRD spectrum that α-Sialon crystal grain is synthesized in embodiment one；
Fig. 2 is the SEM photograph that α-Sialon crystal grain is synthesized in embodiment one.
Embodiment
The raw material is carried out dispensing by the present invention by the matching principle first, mixes each raw material after wet ball grinding Uniformly, take out and successively dry in natural environment and baking oven；Dried mixed powder is placed in graphite crucible again, by one Rise to be placed in multifunctional furnace and carry out vacuumize process, reacted by the temperature, soaking time and reaction atmosphere condition；Complete Synthetic powder is subjected to insulation after the predetermined reaction time and removes carbon, finally obtains long column shape α-Sialon of the present invention Fine grain.
Below by specific embodiment, the more detailed description present invention, but these embodiments are only intended to help easily to manage The solution present invention, the present invention is not limited to these embodiments.
Embodiment 1
According to molecular formula Mv+ xSi12-(m+n)Al(m+n)OnN16-n, select m=2n, work as m=1.5, using quartz, aluminium oxide, aluminium nitride as Primary raw material, using carbon black as reducing agent, Dy is selected in the doping of dication system2O3And CaF2Two kinds of compounds, are according to molecular formula Ca0.3Dy0.3Si9.75Al2.25O0.75N15.25Material powder is weighed, and the Y- α-Sialon fine powders for adding conbustion synthesis preparation are crystalline substance Kind, its content accounts for the 10wt.% of total dispensing.
1. load weighted material powder is put into ball grinder, expect:Ball:Ethanol（Mass ratio）=1:1.5:2, planetary With the rotating speed ball milling mixing 20h of 350r/min on ball mill, so that material powder is sufficiently mixed.
2. the mixed powder formed after ball milling first spontaneously dries 5h, place into baking oven and dry 12h at 50 DEG C.
3. the mixed powder dried is placed in graphite crucible, then it is placed in multifunctional furnace, vacuum is kept in stove 10-2Pa, is filled with N2And keep nitrogen pressure 0.12MPa；With 35 DEG C of min-1Speed temperature is risen to 1200 DEG C from room temperature, then With 8 DEG C of min-1Speed be warming up to 1700 DEG C of nitriding temperature, when insulation 8 is small, after treating nitridation reaction, naturally cool to room Temperature.
4. the powder after reacted synthesis keeps the temperature 1h at 720 DEG C, it is thin to obtain long column shape α-Sialon of the present invention Crystal grain, purity 98wt.%, 2-4 μm of crystal grain diameter, draw ratio 5-10.
Embodiment 2
According to molecular formula Mv+ xSi12-(m+n)Al(m+n)OnN16-n, select m=2n, work as m=1.5, using quartz, aluminium oxide, aluminium nitride as Primary raw material, using carbon black as reducing agent, Nd is selected in the doping of dication system2O3With two kinds of compounds of MgO, it is according to molecular formula Mg0.3Nd0.3Si9.75Al2.25O0.75N15.25Material powder is weighed, and the Y- α-Sialon fine powders for adding conbustion synthesis preparation are crystalline substance Kind, its content accounts for the 8wt.% of total dispensing.
1. load weighted material powder is put into ball grinder, expect:Ball:Ethanol（Mass ratio）=1:1.5:2, planetary With the rotating speed ball milling mixing 18h of 400r/min on ball mill, so that material powder is sufficiently mixed.
2. the mixed powder formed after ball milling first spontaneously dries 4h, place into baking oven and dry 10h at 55 DEG C.
3. the mixed powder dried is placed in graphite crucible, then it is placed in multifunctional furnace, vacuum is kept in stove 10-2Pa, is filled with N2And keep nitrogen pressure 0.12MPa；With 40 DEG C of min-1Speed temperature is risen to 1200 DEG C from room temperature, then With 10 DEG C of min-1Speed be warming up to 1680 DEG C of nitriding temperature, when insulation 6 is small, after treating nitridation reaction, naturally cool to Room temperature.
4. the powder after reacted synthesis keeps the temperature 2h at 700 DEG C, it is thin to obtain long column shape α-Sialon of the present invention Crystal grain, purity 97wt.%, 1-3 μm of crystal grain diameter, draw ratio 5-8.
Embodiment 3
According to molecular formula Mv+ xSi12-(m+n)Al(m+n)OnN16-n, select m=2n, work as m=1.5, using quartz, aluminium oxide, aluminium nitride as Primary raw material, using carbon black as reducing agent, Eu is selected in the doping of dication system2O3And Y2O3Two kinds of compounds, are according to molecular formula Y0.2Nd0.3Si9.75Al2.25O0.75N15.25Material powder is weighed, and the Y- α-Sialon fine powders for adding conbustion synthesis preparation are crystalline substance Kind, its content accounts for the 5wt.% of total dispensing.
1. load weighted material powder is put into ball grinder, expect:Ball:Ethanol（Mass ratio）=1:1.5:2, planetary With the rotating speed ball milling mixing 20h of 450r/min on ball mill, so that material powder is sufficiently mixed.
2. the mixed powder formed after ball milling first spontaneously dries 5h, place into baking oven and dry 15h at 50 DEG C.
3. the mixed powder dried is placed in graphite crucible, then it is placed in multifunctional furnace, vacuum is kept in stove 10-2Pa, is filled with N2And keep nitrogen pressure 0.12MPa；With 45 DEG C of min-1Speed temperature is risen to 1200 DEG C from room temperature, then With 5 DEG C of min-1Speed be warming up to 1680 DEG C of nitriding temperature, when insulation 5 is small, after treating nitridation reaction, naturally cool to room Temperature.
4. the powder after reacted synthesis keeps the temperature 4h at 720 DEG C, it is thin to obtain long column shape α-Sialon of the present invention Crystal grain, purity 96wt.%, 2-4 μm of crystal grain diameter, draw ratio 5-9.

Claims (3)

  1. A kind of 1. α-Sialon fine grains of CRN method synthesis long column shape and preparation method thereof, it is characterised in that：α- The molecular formula of Sialon is Mv+ xSi12-(m+n)Al(m+n)OnN16-n, M is metal cation in formula, and v is the chemical combination of metal cation M Valency, x are the solid solution capacity of metal cation M（x≤2）, M Ca, Mg, Y and rare earth element Re（La、Ce、Pr、Nd、Sm、Eu、Dy、 Gd, Ho, Er and Yb）；There is provided it is a kind of from cheap quartz, aluminium oxide, aluminium nitride etc. be primary raw material, Re2O3For one of which sun from Sub- raw material, another cation raw material are CaF2、MgF2、YF3, CaO, MgO or Y2O3In one kind, activated carbon or carbon black are reduction Agent, the α-Sialon fine powders prepared using conbustion synthesis use carbon thermal reduction in 1650 DEG C -1750 DEG C in a nitrogen atmosphere as crystal seed Long column shape α-Sialon the fine grains of high-purity are prepared in nitridation.
  2. 2. α-Sialon fine grain the preparation methods of CRN method synthesis long column shape according to claim 1, its It is characterized in that, comprises the following steps that：Raw material through dispensing, wet ball grinding, drying, Nitration synthesis, except technical process such as carbon, its It is characterized in that mainly comprising the technical steps that：
    Dispensing：By molecular formula Mv+ xSi12-(m+n)Al(m+n)OnN16-n, according to 0.5≤m≤3,0.2≤n≤1.5, v=m/x, weigh Material powder quartz, aluminium oxide, aluminium nitride, Re2O3For primary raw material, another cation chosen CaF2、MgF2、YF3、CaO、 MgO or Y2O3In one kind, its content accounts for 0 ~ 5wt% of total dispensing；It is crystal seed to add α-Sialon fine powders prepared by conbustion synthesis, Its content accounts for the 0 ~ 10% of total dispensing；
    Ball milling：Using the method for wet ball grinding batch mixing, raw material is sufficiently mixed；Weigh raw material be put into ball grinder, The agate ball of different-diameter is put at the same time, using absolute ethyl alcohol as medium, material:Ball:Mass ratio=1 of ethanol:1.5:2, planetary With 10 ~ 24h of rotating speed ball milling mixing of 200 ~ 500r/min on ball mill；
    It is dry：The mixed powder that raw material is formed after ball milling first spontaneously dries 1h ~ 6h, the dense of absolute ethyl alcohol is greatly reduced Degree, is then placed in baking oven and 3 ~ 15h is dried below 60 DEG C；
    Carbothermal reduction-nitridation：The mixed powder dried is placed in graphite crucible, it is placed in multifunctional furnace together and is carried out Vacuumize process so that vacuum≤10 in stove-2Pa, is then charged with N2, nitrogen pressure 0.12MPa is kept, from room temperature with speed 20~50℃·min-11200 DEG C are warming up to, then with 2 ~ 10 DEG C of min-1Speed raise temperature to 1650 DEG C of nitriding temperature ~ 1750 DEG C, when insulation 2 ~ 10 is small, after nitridation reaction, naturally cool to room temperature；
    Except carbon：Powder after synthesis is kept the temperature into 1 ~ 5h to exclude the carbon in powder at 650 ~ 750 DEG C, finally obtains the present invention Long column shape α-Sialon the fine grains.
  3. 3. α-Sialon fine grain the preparation methods of the CRN method synthesis long column shape according to claim 1-2, It is characterized in that：Quartz, SiO2Content >=98%, particle diameter≤300 μm, its content account for 40 ~ 60wt.% of total dispensing；Aluminium oxide, Al2O3Content >=98%, particle diameter≤74 μm, its content account for 0 ~ 10wt.% of total dispensing；Aluminium nitride, oxygen content≤2%, particle diameter≤74 μm, its content accounts for 2 ~ 10wt.% of total dispensing；Rare earth oxide Re2O3Micro mist, content >=99.5%, particle diameter≤74 μm, its content Account for 2 ~ 15wt.% of total dispensing；Addition of C aF2、MgF2、YF3、CaO、MgO、Y2O3It is that analysis is pure Deng micro mist, the μ of particle diameter≤30 M, its content account for 0.1 ~ 10wt.% of total dispensing；Crystal seed α-Sialon fine powders, particle diameter≤10 μm, its content account for total dispensing 0.1 ~ 10wt.%；For carbon black ,≤100nm, its content accounts for 18 ~ 28wt.% of total dispensing；High pure nitrogen, purity ＞ 99.99%.
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