CN103274695A - Burning, synthesizing and casting method of non-oxide eutectic ceramics - Google Patents
Burning, synthesizing and casting method of non-oxide eutectic ceramics Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000919 ceramic Substances 0.000 title claims abstract description 48
- 238000005266 casting Methods 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 58
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 230000035939 shock Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000005049 combustion synthesis Methods 0.000 description 3
- 238000004093 laser heating Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 238000012795 verification Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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Abstract
The invention relates to a method for preparing eutectic ceramics and in particular relates to a burning, synthesizing and casting method of non-oxide eutectic ceramics. The invention aims to solve the technical problems of the conventional method that the prepared non-oxide eutectic ceramics have small size and the preparation period is long. According to the method, the reactant is metal powder and nitrate, the diluent is eutectic granulation powder, the raw materials are ignited, the reaction is carried out through the combustion heat release of the metal powder and nitrate, excessive metal powder is added into the raw materials so as to neutralize nitrogen in the reaction and reduce air holes in the product, so that the reaction is performed under normal pressure or extremely low pressure, the reaction pressure is 0.1-10MPa, the reaction pressure is low, and the safety is high; and moreover, the experimental process is rapid, the reaction time is less than 10 minutes, the preparation period is short, the product purity is high, and the method can be applied to the field of preparation of non-oxide eutectic ceramics.
Description
Technical field
The present invention relates to a kind of preparation method of eutectic ceramic, particularly the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning.
Background technology
The non-oxidized substance eutectic ceramic can be applicable to the material under hot environment or the high temperature oxidation stability condition with its good oxidation-resistance, heat-shock resistance and fracture toughness property etc.
The preparation method commonly used of eutectic ceramic mainly contains following several: Bridgman method, LASER HEATING Fu Liu district method, little daraf(reciprocal of farad), deckle are fed embrane method and combustion synthesis method.
The principle of Bridgman method (falling crucible method) is that reactant is put into crucible, crucible is put into the burner hearth that ruhmkorff coil is housed again.By ruhmkorff coil burner hearth is heated to more than the reactant fusing point, allows crucible in burner hearth, slowly descend, make the material melting in the crucible.Then, along with the decline of crucible, the bottom takes the lead in breaking away from the heating zone, drop to below the fusing point of material when temperature after, the beginning crystallization.For different materials, can adopt resistance furnace or induction heating.The advantage of Bridgman method is: (1) can prepare large-sized block materials; (2) can prepare the sample with complicated shape.Shortcoming has: (1) speed of growth is slow; (2) production cost is higher; (3) thermograde is less, and distance is bigger between each eutectic phase, the performance of influence tissue.
As thermal source, concentrate, and produces high temperature molten ceramic material by energy height with laser for LASER HEATING Fu Liu district method (claiming the LZF method again).Compare with traditional technology of preparing, the LASER HEATING method has higher thermograde, can reach (10
4K/cm).The advantage of this method is: the thermograde height, pollution-free, need not crucible, fast growth etc.The higher material of fusing point also can melt and cool off fast, and the material structure that obtains is thinner, is that the performance of material is significantly improved.According to the scanning speed difference of laser, the micromechanism of melting range eutectic structure can be very different, and can control the performance of material whereby.But the influence of Stimulated Light spot diameter, its product size is also restricted.
Little daraf(reciprocal of farad) (μ-PD method) is the same with Bridgman method to be to heat in crucible, and the crucible bottom of little daraf(reciprocal of farad) that different is has a hole.After the material melts in the crucible, melt is grown downwards along aperture under the crucible.This method can the identical or closely spaced tissue in interface of preparation property, compares with additive method, is more suitable for preparing the less fibrous crystals of diameter.By the shape of change crucible, can prepare eutectic rod or the eutectic fiber of various size.The eutectic structure microtexture that this method obtains is better, so have excellent mechanical property, compares with the Bridgman method that can prepare the large size eutectic, and the intensity of eutectic fiber is higher.But the sample size of this method preparation is too small also to be its main drawback.
It is to immerse refractory metal type film in the crucible of eutectic melt is housed that deckle is fed embrane method (border epitaxial method), utilizes the wicking action of liquid, and melt rises along the pore in the type film.The thermograde on type film surface is 400～1600K/cm, can obtain the different sample of size according to the difference of pull rate, can prepare eutectic material continuously.The advantage of this method is: thermograde is big, and the material of producing has outstanding mechanical property.Shortcoming is: the sample size of preparation is little, and shape is single.
Combustion synthesis method (combustion synthesis) claims self propagating high temperature synthesis method (being called for short SHS) again, is proposed by USSR (Union of Soviet Socialist Republics) scientist Merzhanov.This method need not external heat source, is that liberated heat carries out the synthetic technology of inorganic refractory when relying on the raw material id reaction.The advantage of this method is: cost is low, power consumption is low, temperature of reaction is high, growth efficiency is high.Shortcoming is: because growth velocity is too high, can cause bigger residual thermal stress at material internal, may cause final product fracture phenomena to occur.
Existing one piece of title and author who was published in APPLIED SURFACE SCIENCE in 2011 is (" Microstructure and mechanism of Al
2O
3-ZrO
2Eutectic coating prepared by combustion-assisted thermal explosion spraying " author: Yongting Zheng, Hongbo Li, Tao Zhou) document, adopt detonation flame spraying to prepare Al in the document
2O
3/ ZrO
2The eutectic coating, other has one piece of title and author who was published in JOURNAL OF ALLOYS AND COMPOUNDS in 2012 is (" Microstructure and mechanical properties of Al
2O
3/ ZrO
2Eutectic ceramic composites prepared by explosion synthesis " author: Yongting Zheng, Hongbo Li, Tao Zhou, Jing Zhao, Pan Yang) document, adopt the synthetic Al that prepared of blast in the document
2O
3/ ZrO
2Eutectic ceramic, but aforesaid method all has following shortcoming: and (1) reaction pressure is big, in 30～100MPa scope, has the blast impulse effect simultaneously, and preparation technology's danger very big (2) product size is little, is Φ 20*40mm to the maximum
3
Summary of the invention
The present invention is the little technical problem long with preparation cycle of non-oxidized substance eutectic ceramic size that solves existing method preparation, and a kind of method of the synthetic founding of burning of non-oxidized substance eutectic ceramic is provided.
The method of the synthetic founding of the burning of a kind of non-oxidized substance eutectic ceramic of the present invention is carried out according to the following steps:
One, mixes after will meeting the non-oxidic powders drying of eutectic ratio, carry out the presintering granulation, obtain thinner;
Two, nitrate is placed on independent drying treatment in the loft drier, obtains the nitrate reaction agent;
Three, metal-powder is placed on drying treatment in the vacuum drying oven, obtains the metal-powder reagent;
Four, the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the thinner that step 1 is obtained, step 2 and step 3, mix by ball milling, pack into then in the reaction unit, light raw material, the thermopositive reaction of burning, reaction times＜10min, temperature of reaction＜4300K, reaction pressure＜10MPa gets rid of the gas in the reaction system in the reaction process, obtain the non-oxidized substance eutectic ceramic.Wherein the mol ratio of the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the step 2 described in the step 4 and step 3 is 3: (24～32), wherein the ratio of the thinner that the quality sum of metal-powder reagent and step 1 obtain in nitrate reaction agent and the step 3 in the step 2 described in the step 4 is 1: (0.553～2.367).
The reagent of the inventive method is metal-powder and nitrate, thinner is eutectic granulation powder, light raw material, burning heat release by metal-powder and nitrate is reacted, method of the present invention has the following advantages: (1) rapid heating systems temperature of burning heat release by metal-powder and nitrate is to more than the fusing point of all substances, by the percentage composition of strictness control thinner, hierarchy of control temperature remains on more than all substances fusing point, and this reaction is the combustion reactions of speed-controllable; (2) under no centrifugal, high temperature, large-sized condition, can pass through the gas that methods such as mechanical shock, ultrasonic vibration or induction stirring are got rid of systems, make ceramic dense; (3) under centrifugal condition, through cooling off fast, solidifying, obtain large size non-oxidized substance eutectic ceramic, size can reach Φ 500mm; (4) in raw material, add excessive metal powder, in reaction, can neutralize nitrogen, make be reflected under the normal pressure or very low pressure under carry out, reaction pressure is 0.1MPa～10MPa, reaction pressure is low, and is safe; (5) separate pore and oxide components by high speed centrifugation, obtain fine and close fully as cast condition eutectic structure, the speed-controllable of synthesis process, but rapidly synthetic compared to traditional technology, the efficient height, the reaction times changes with the size of producing product, the difference of synthesis technique, be generally 1min～10min, preparation cycle is short, and the product purity height can be applicable to the preparation field of non-oxidized substance eutectic ceramic.
Embodiment
Technical scheme of the present invention is not limited to following embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for the synthetic founding of the burning of a kind of non-oxidized substance eutectic ceramic of present embodiment is carried out according to the following steps:
One, mixes after will meeting the non-oxidic powders drying of eutectic ratio, carry out the presintering granulation, obtain thinner;
Two, nitrate is placed on independent drying treatment in the loft drier, obtains the nitrate reaction agent;
Three, metal-powder is placed on drying treatment in the vacuum drying oven, obtains the metal-powder reagent;
Four, the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the thinner that step 1 is obtained, step 2 and step 3, mix by ball milling, pack into then in the reaction unit, light raw material, the thermopositive reaction of burning, reaction times＜10min, temperature of reaction＜4300K, reaction pressure＜10MPa gets rid of the gas in the reaction system in the reaction process, obtain the non-oxidized substance eutectic ceramic.Wherein the mol ratio of the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the step 2 described in the step 4 and step 3 is 3: (24～32), wherein the ratio of the thinner that the quality sum of metal-powder reagent and step 1 obtain in nitrate reaction agent and the step 3 in the step 2 described in the step 4 is 1: (0.553～2.367).
Presintering granulation described in the present embodiment is known prior art.
The reagent of the method for embodiment is metal-powder and nitrate, thinner is eutectic granulation powder, light raw material, burning heat release by metal-powder and nitrate is reacted, the method of present embodiment has the following advantages: (1) rapid heating systems temperature of burning heat release by metal-powder and nitrate is to more than the fusing point of all substances, percentage composition by strictness control thinner, hierarchy of control temperature remains on more than all substances fusing point, and this reaction is the combustion reactions of speed-controllable; (2) under no centrifugal, high temperature, large-sized condition, can pass through the gas that methods such as mechanical shock, ultrasonic vibration or induction stirring are got rid of systems, make ceramic dense; (3) under centrifugal condition, through cooling off fast, solidifying, obtain large size non-oxidized substance eutectic ceramic, size can reach Φ 500mm; 4) in raw material, add excessive metal powder, in reaction, can neutralize nitrogen, make be reflected under the normal pressure or very low pressure under carry out, reaction pressure is 0.1MPa～10MPa, reaction pressure is low, and is safe; (5) separate pore and oxide components by high speed centrifugation, obtain fine and close fully as cast condition eutectic structure, the speed-controllable of synthesis process, but rapidly synthetic compared to traditional technology, the efficient height, the reaction times changes with the size of producing product, the difference of synthesis technique, be generally 1min～10min, preparation cycle is short, and the product purity height can be applicable to the preparation field of non-oxidized substance eutectic ceramic.
Embodiment two: what present embodiment and embodiment one were different is that the non-oxidic powders that meets the eutectic ratio described in the step 1 is for forming the non-oxidic powders of eutectic structure.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is: the non-oxidic powders that meets the eutectic ratio described in the step 1 is ZrB
2The combination of powder and SiC powder, ZrB
2The combination of powder and WC powder, ZrB
2Powder and LaB
6The combination of powder or HfB
2Powder and LaB
6The combination of powder.Other step and parameter are identical with embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the nitrate reaction agent described in the step 2 is metal nitrate.Other step and parameter are identical with one of embodiment one to three.
When the metal nitrate of present embodiment was mixture, each component was pressed arbitrary proportion and is mixed.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the nitrate reaction agent described in the step 2 is Zr (NO
3)
4, Al (NO
3)
3, Mg (NO
3)
2, Y (NO
3)
3In one or more mixture.Other step and parameter are identical with one of embodiment one to four.
When the metal nitrate of present embodiment was mixture, each component was pressed arbitrary proportion and is mixed.
Embodiment six: what present embodiment was different with one of embodiment one to five is: the drying treatment described in the step 2 is by being under 50～70 ℃ the condition in temperature, and be that 8h～12h realizes time of drying.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: the metal-powder reagent described in the step 3 is reactive metal.Other step and parameter are identical with one of embodiment one to six.
When the described metal-powder reagent of present embodiment is mixture, presses arbitrary proportion between each component and mix.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: the metal-powder reagent described in the step 3 is one or more the mixture among Al, Ti, Fe, Mg, Si, K, the Ca.Other step and parameter are identical with one of embodiment one to seven.
When the described metal-powder reagent of present embodiment is mixture, presses arbitrary proportion between each component and mix.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: the drying treatment described in the step 3 is by being under 70～90 ℃ the condition in temperature, and be that 8h～12h realizes time of drying.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different with one of embodiment one to nine is: the ball milling described in the step 4 is by being under 3: 1 the condition at ball material mass ratio, and ball milling mixing 4h～6h realizes.Other step and parameter are identical with one of embodiment one to nine.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is: temperature of reaction is 3000K～4300K in the step 4, and reaction pressure is 0.1MPa～10MPa in the step 4.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: what present embodiment was different with one of embodiment one to 11 is: the gas of getting rid of in the reaction system in the reaction process described in the step 4 is by under no centrifugal condition, adopts mechanical shock, ultrasonic vibration or induction stirring to realize.Other step and parameter are identical with one of embodiment one to 11.
Present embodiment has realized separating of gas and eutectic liquid, obtains the composite ceramics that non-oxidized substance eutectic and oxide eutectic coexist.
Embodiment 13: what present embodiment was different with one of embodiment one to 12 is: the gas of getting rid of in the reaction system in the reaction process described in the step 4 is by under centrifugal condition, reaction unit is installed in the centrifugation systems, and setting centrifugal force is that 100g～1000g realizes; Described centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.Other step and parameter are identical with one of embodiment one to 12.
With following verification experimental verification beneficial effect of the present invention:
The method of the synthetic founding of the burning of embodiment 1, a kind of non-oxidized substance eutectic ceramic is carried out according to the following steps:
One, takes by weighing the ZrB that amounts to 200g
2Powder and SiC powder (ZrB
2Satisfy the eutectic ratio with SiC), mix after the drying, be 20MP at pressure then, temperature is to carry out the presintering granulation under 1200 ℃, obtains thinner;
Two, with Zr (NO
3)
45H
2O is placed in the loft drier dry separately, and drying temperature is 60 ℃, and be 10h time of drying, obtains Zr (NO
3)
4
Three, Al is placed on drying in the vacuum drying oven, drying temperature is 80 ℃, and be 10h time of drying;
Four, take by weighing the 160.6g step 1 and obtain the Zr (NO that thinner, 75.4g step 2 obtain
3)
4And the Al that obtains of 64.0g step 3, by ball milling mixing 5h, ball material mass ratio is 3: 1, in the reaction unit of packing into then, reaction unit is installed in the centrifugation systems, setting centrifugal force is 200g, lights raw material then, the thermopositive reaction of burning, reaction times is 10min, temperature of reaction is 3400K, and reaction pressure is 3MPa, obtains being of a size of the ZrB of Φ 100mm
2/ SiC eutectic ceramic; Wherein said centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.
The method of the synthetic founding of the burning of embodiment 2, a kind of non-oxidized substance eutectic ceramic eutectic ceramic is carried out according to the following steps:
One, takes by weighing the ZrB that amounts to 200g
2Powder and LaB
6Powder (ZrB
2And LaB
6Satisfy the eutectic ratio), mix after the drying, be 20MP at pressure then, temperature is to carry out the presintering granulation under 1200 ℃, obtains thinner;
Two, with Zr (NO
3)
45H
2O is placed in the loft drier dry separately, and drying temperature is 60 ℃, and be 10h time of drying, obtains Zr (NO
3)
4
Three, Al is placed on drying in the vacuum drying oven, drying temperature is 80 ℃, and be 10h time of drying;
Four, take by weighing the thinner that the 169.9g step 1 obtains, the Zr (NO that the 70.3g step 2 obtains
3)
4And the Al that obtains of 59.7g step 3, by ball milling mixing 5h, ball material mass ratio is 3: 1, in the reaction unit of packing into then, reaction unit is installed in the centrifugation systems, setting centrifugal force is 300g, lights raw material then, the thermopositive reaction of burning, reaction times is 10min, temperature of reaction is 3600K, and reaction pressure is 4MPa, obtains being of a size of the ZrB of Φ 150mm
2/ LaB
6Eutectic ceramic; Wherein said centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.
The method of the synthetic founding of the burning of embodiment 3, a kind of non-oxidized substance eutectic ceramic eutectic ceramic is carried out according to the following steps:
One, takes by weighing the ZrB that amounts to 250g
2Powder and WC powder (ZrB
2Satisfy the eutectic ratio with WC), mix after the drying, be 20MP at pressure then, temperature is to carry out the presintering granulation under 1200 ℃, obtains thinner;
Two, with Zr (NO
3)
45H
2O is placed in the loft drier dry separately, and drying temperature is 60 ℃, and be 10h time of drying, obtains Zr (NO
3)
4
Three, Al is placed on drying in the vacuum drying oven, drying temperature is 80 ℃, and be 10h time of drying;
Four, take by weighing the thinner that the 194.5g step 1 obtains, the Zr (NO that the 57.1g step 2 obtains
3)
4And the Al that obtains of 48.4g step 3, by ball milling mixing 5h, ball material mass ratio is 3: 1, in the reaction unit of packing into then, reaction unit is installed in the centrifugation systems, setting centrifugal force is 400g, lights raw material then, the thermopositive reaction of burning, reaction times is 10min, temperature of reaction is 3800K, and reaction pressure is 4MPa, obtains being of a size of the ZrB of Φ 200mm
2/ WC eutectic ceramic; Wherein said centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.
The method of the synthetic founding of the burning of embodiment 4, a kind of non-oxidized substance eutectic ceramic eutectic ceramic is carried out according to the following steps:
One, takes by weighing the ZrB that amounts to 200g
2Powder and LaB
6Powder (ZrB
2And LaB
6Satisfy the eutectic ratio), mix after the drying, be 20MP at pressure then, temperature is to carry out the presintering granulation under 1200 ℃, obtains thinner;
Two, with Zr (NO
3)
45H
2O is placed in the loft drier dry separately, and drying temperature is 60 ℃, and be 10h time of drying, obtains Zr (NO
3)
4
Three, Al is placed on drying in the vacuum drying oven, drying temperature is 80 ℃, and be 10h time of drying;
Four, take by weighing the thinner that the 168.3g step 1 obtains, the Zr (NO that the 71.3g step 2 obtains
3)
4And the Al that obtains of 60.5g step 3, by ball milling mixing 5h, ball material mass ratio is 3: 1, in the reaction unit of packing into then, reaction unit is installed in the centrifugation systems, setting centrifugal force is 500g, lights raw material then, the thermopositive reaction of burning, reaction times is 10min, temperature of reaction is 4000K, and reaction pressure is 5MPa, obtains being of a size of the HfB of Φ 300mm
2/ LaB
6Eutectic ceramic; Wherein said centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.
Claims (10)
1. a non-oxidized substance eutectic ceramic burns and synthesizes the method for founding, it is characterized in that the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning is carried out according to the following steps:
One, mix after will meeting the non-oxidic powders drying of eutectic ratio, carry out the presintering granulation, obtain thinner:
Two, nitrate is placed on independent drying treatment in the loft drier, obtains the nitrate reaction agent;
Three, metal-powder is placed on drying treatment in the vacuum drying oven, obtains the metal-powder reagent;
Four, the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the thinner that step 1 is obtained, step 2 and step 3, mix by ball milling, pack into then in the reaction unit, light raw material, the thermopositive reaction of burning, reaction times＜10min, temperature of reaction＜4300K, reaction pressure＜10MPa gets rid of the gas in the reaction system in the reaction process, obtain the non-oxidized substance eutectic ceramic.Wherein the mol ratio of the metal-powder reagent that obtains of the nitrate reaction agent that obtains of the step 2 described in the step 4 and step 3 is 3: (24～32), wherein the ratio of the thinner that the quality sum of metal-powder reagent and step 1 obtain in nitrate reaction agent and the step 3 in the step 2 described in the step 4 is 1: (0.553～2.367).
2. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 1 is characterized in that the non-oxidic powders that meets the eutectic ratio described in the step 1 is for forming the non-oxidic powders of eutectic structure.
3. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 1 and 2 is characterized in that the nitrate reaction agent described in the step 2 is metal nitrate.
4. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 3 is characterized in that the drying treatment described in the step 2 is by being that be that 8h～12h realizes time of drying under 50～70 ℃ the condition in temperature.
5. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 3 is characterized in that the metal-powder reagent described in the step 3 is reactive metal.
6. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 3 is characterized in that the drying treatment described in the step 3 is by being that be that 8h～12h realizes time of drying under 70～90 ℃ the condition in temperature.
7. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 3 is characterized in that the ball milling described in the step 4 is by being under 3: 1 the condition at ball material mass ratio, ball milling mixings 4h～6h realization.
8. the method for the synthetic founding of a kind of non-oxidized substance eutectic ceramic burning according to claim 3 is characterized in that temperature of reaction is 3000K～4300K in the step 4, and reaction pressure is 0.1MPa～10MPa in the step 4.
9. the method for founding is synthesized in a kind of non-oxidized substance eutectic ceramic burning according to claim 3, it is characterized in that the gas of getting rid of in the reaction system in the reaction process described in the step 4 is by under no centrifugal condition, adopt mechanical shock, ultrasonic vibration or induction stirring to realize.
10. the method for founding is synthesized in a kind of non-oxidized substance eutectic ceramic burning according to claim 3, the gas that its feature is got rid of in the reaction process described in the step 4 in the reaction system is by under centrifugal condition, reaction unit is installed in the centrifugation systems, and setting centrifugal force is that 100g～1000g realizes; Described centrifugation systems has circulating water cooling device, portfire, electric heater unit, temperature test device and pressure test device.
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