CN1330607C - Prepn process of conductive TiN/O'-Sialon ceramic material with titanium-containing furnace slag - Google Patents
Prepn process of conductive TiN/O'-Sialon ceramic material with titanium-containing furnace slag Download PDFInfo
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- CN1330607C CN1330607C CNB200510047293XA CN200510047293A CN1330607C CN 1330607 C CN1330607 C CN 1330607C CN B200510047293X A CNB200510047293X A CN B200510047293XA CN 200510047293 A CN200510047293 A CN 200510047293A CN 1330607 C CN1330607 C CN 1330607C
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- sialon
- tin
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Abstract
The present invention relates to a method for preparing a TiN/O'-Sialon conductive ceramic material by titaniferous slag, which comprises two steps: step 1, TiN/O'-Sialon conductive ceramic powder synthesis: (1) ball milling, (2) sieving, (3) proportioning: 25.29 to 41.00 of titaniferous slag, 33.91 to 47.85 of silica ash, 4.44 to 6.93 of bauxite and 19.93 to 20.65 of carbon black, (4) wet mixing: the materials are mixed by using anhydrous alcohol as a medium, (5) drying: the materials are dried at the temperature of 60 DEG C, (6) dry mixing for 4 hours; (7) molding by pressing the materials in a single shaft direction, (8) high-temperature firing: the TiN/O'-Sialon conductive ceramic material is formed by firing the materials under the nitrogen protection by one high atmospheric pressure at the temperature of 1350 to 1400 DEG C, and (9) residual carbon is burnt off; step 2, the synthetized TiN/O'-Sialon powder in step one is sintered under the powder burying condition in a high-temperature furnace to obtain the TiN/O'-Sialon conductive ceramic material after molding by mould pressing, and the product has good mechanical performance and conductive performance. The present invention has the advantages of simple process and low manufacture cost, opens up a novel path for the integral and comprehensive utilization of titaniferous slag in China, and is beneficial to improve social environment.
Description
Technical field
The present invention relates to a kind of preparation method of electro-conductive material, be specifically related to utilize Ti-containing slag to prepare the method for TiN/O '-Sialon conducting ceramic material for main raw material.
Background technology
Adopt the reaction in sintering process to prepare the existing report of the compound O ' of TiN-Sialon material, but do not see as yet both at home and abroad at present and utilize Ti-containing slag to be equipped with any report of TiN/O '-Sialon electro-conductive material for raw material adopts the carbothermal reduction-nitridation legal system.Purity is higher though the reaction in sintering process can prepare, the TiN/O ' of better performances-Sialon electro-conductive material, because its raw material is pure reagent, costs an arm and a leg, and production cost is high and be not suitable for industrial-scale production and its application is restricted.And, it is carried out very necessity of rational Application because China's Ti-containing slag output is big.
Summary of the invention
At the defective of prior art, the purpose of this invention is to provide a kind of low-cost method for preparing TiN/O '-Sialon conducting ceramic material of Ti-containing slag of utilizing.Just utilize output Ti-containing slag big, with low cost to be main raw material, adjust composition, adopt the carbothermal reduction-nitridation legal system to be equipped with the material that this existing structure character of TiN/O '-Sialon has fine electroconductibility again with silicon ash and bauxitic clay.Reach simple for process and be fit to the industrialization continuous production again.Reduce the preparation cost of TiN/O '-Sialon conducting ceramic material greatly, do not provide a new way for China's Ti-containing slag has new integral body utilization discarded and pollution and ecology.
Realize the technical scheme of the object of the invention: with the Ti-containing slag is main raw material, uses SiO
2Content is the silicon ash of 82～90wt%, A1
2O
3Content is that 79～85wt% bauxitic clay is adjusted composition, and carbon black is a reductive agent, produces TiN/O '-Sialon conducting ceramic material in two steps:
The first step is synthesized TiN/O '-Sialon conducting ceramic material powder
(1) ball milling: the raw material Ti-containing slag bigger to granularity carries out fine grinding;
(2) sieve: sieve with the raw material powder of 200 mesh standard sieves after to above-mentioned ball milling;
(3) batching: choose that synthetic O '-the Sialon chemical formula is Si
2xAl
xO
1+xN
2-x, x=0.3 in the formula determines prescription, and is raw materials used by following mass percent preparation:
Ti-containing slag is 25.29～41.00%, and the silicon ash is 33.91～47.85%, and bauxitic clay is 4.44～6.93%, and carbon black is 19.93～20.65%;
(4) wet mixing: with the compound for preparing is that medium is mixed into slip with the dehydrated alcohol, and the wet mixing time is 24 hours;
(5) drying: the slip after the wet mixing is put into baking oven in 60 ℃ of oven dry down;
(6) dried mixing: the compound after will drying is done and was mixed 4 hours, and places moisture eliminator to preserve the gained blank;
(7) compression molding: to compression moulding, forming pressure is 25MPa, pressurize 1min with the blank single shaft;
(8) high temperature burns till: with the blank of above-mentioned compression moulding, place in the plumbago crucible, use MoSi
2The high temperature resistance furnace heating, at a normal atmosphere, firing temperature is 1350～1400 ℃, and constant temperature 7～8 hours heats up and cooling rate is 3～5 ℃/min, in the sintering process, feed in the process furnace under the flowing nitrogen condition that flow is 400～800ml/min and burn till;
(9) burning-off carbon residue: for preventing to burn till TiN phase oxidation in the powder, the above-mentioned product that burns till is placed on grind into powder in the agate mortar, is placed on then in the retort furnace, constant temperature was heat-treated in 6 hours in 580 ℃ of air, removed remaining uncombined carbon;
Second step: the preparation of TiN/O '-Sialon conducting ceramic material
Adopt two kinds of preparation of raw material: a kind of is with the first step synthetic TiN/O '-Sialon powder and the Sm that accounts for raw material gross weight 3%
2O
3Additive mixes; Another kind is to be raw material with the first step synthetic TiN/O '-Sialon powder directly, does not add any additives; With above-mentioned first kind of preparing or the moulding of second kind of raw material powder single way stempressing, forming pressure 200MPa, pressurize 1min.The green compact of above-mentioned compression molding are put into plumbago crucible, bury Si
3N
4+ SiO
2Powder, wherein Si
3N
4With SiO
2Mol ratio be 1: 1, firing furnace is selected MoSi for use
2High temperature resistance furnace is 1450～1500 ℃ at normal pressure, firing temperature, soaking time 2 hours; intensification and cooling rate are 3～5 ℃/min; adopt under logical high pure nitrogen (with the burying the powder protection) condition, burn till, produce TiN/O '-Sialon conducting ceramic material.The high-purity nitrogen flow control of being adopted in system to external world environment be malleation.
Advantage of the present invention and positively effect are:
1, having made full use of output Ti-containing slag big, with low cost is main raw material, and therefore not only production cost can reduce greatly, and has opened up new way for the utilization of a large amount of Ti-containing slags of China, has reduced environmental pollution simultaneously;
2, the present invention utilizes Ti-containing slag to synthesize TiN/O '-Sialon electro-conductive material, not only technology is simple, the product that is obtained, conductive phase TiN particle is tiny, disperse is at the crystal boundary place of basic phase O '-Sialon, good with basic consistency mutually, have various good performances: (1) belongs to high-density, high rigidity, high-strength material.Volume density can reach 2.8～3.2g/cm
3, Vickers' hardness 8～12GPa, folding strength reaches 110～200MPa; (2) TiO in initial raw material
2Add-on was greater than 25% o'clock, and the TiN of generation is continuous net-shaped distribution in matrix, formed conductive network, caused resistivity of material sharply to reduce, and resistivity at room temperature is 10
-2～10
-3Ω cm, (3) have lower thermal expansivity: 4.2 * 10
-6～5.9 * 10
-6K
-1(4) has higher anti-atmospheric oxidation performance.Take place in air " passive oxidation ", sample is outer to form " protective membrane ", stops further carrying out of oxidizing reaction.
Embodiment
Embodiment 1: the first step is synthesized TiN/O '-Sialon conductivity ceramics powder.Get the depleted Ti-containing slag, place the urethane ball grinder to grind, sieve with 200 purpose standard sieves; Proportioning raw materials is: Ti-containing slag 30.46g, silicon ash 43.26g, bauxitic clay 6.11g, carbon black 20.17g.Prepared mixture is placed the urethane ball grinder, is medium wet mixing 24h with the dehydrated alcohol, then slip is put into baking oven in 60 ℃ of oven dry down.The dried again 4h that mixes is full and uniform to guarantee compound after the material thorough drying to be mixed, and blank is put into punching block, is pressed into the roundlet base of Φ 15mm under 25MPa pressure to machine with single shaft.The blank that is pressed into is packed in the plumbago crucible, place vertical MoSi
2In the resistance furnace zone of constant temperature, feed nitrogen (N%＞99%) continuously by furnace bottom, under the normal pressure, (Asia-Pacific, Shanghai precision meter factory) carries out temperature control with XMTA-1 type temperature controller, the about 5 ℃/min of heat-up rate, the about 4 ℃/min of cooling rate, sintering temperature is 1400 ℃, constant temperature 7h, nitrogen flow carry out sintering under the 400ml/min condition.Sample after burning till is placed on grind into powder in the agate mortar, is placed on then in the retort furnace, constant temperature was heat-treated in 6 hours in 580 ℃ of air, to remove remaining uncombined carbon.Detected result shows: main thing is O '-Sialon and TiN mutually in the synthetic powder, and sum of the two accounts for more than 70% of product total amount, also has a small amount of B '-Sialon and unreacted TiO in addition
2
Second step preparation TiN/O '-Sialon conducting ceramic material.Above-mentioned synthetic TiN/O '-Sialon powder is put into punching block, and placing an order in 200MPa, to become diameter be the bar-shaped sample of 5.7mm * 5.7mm * 40mm in axial dry-pressing.The sample bar is packed in the plumbago crucible, place vertical MoSi
2In the resistance furnace zone of constant temperature, under normal pressure, carry out sintering.Feed high pure nitrogen continuously by furnace bottom in the sintering process, N%＞99.999%, N
2Flow 20ml/min also buries Si
3N
4+ SiO
2Powder, Si
3N
4: SiO
2=1: 1 (mol ratio).Sintering temperature is 1500 ℃, heat-up rate is 5 ℃/min, soaking time 2h, and cooling rate is 3 ℃/min, detected result shows: main thing does not contain beta '-Sialon and TiO mutually for O '-Sialon and TiN in synthetic TiN/O '-Sialon conducting ceramic material
2Phase.This material volume density is 3.1g/cm
3, Vickers' hardness reaches 10GPa, and folding strength reaches 170MPa, and resistivity at room temperature is 5.32 * 10
-3Ω cm; Thermal expansivity 5.5 * 10
-6K
-1Behind 1260 ℃ of oxidation 1h, the unit surface oxidation weight gain is 5.95mg/cm
2
Embodiment 2: the first step is synthesized TiN/O '-Sialon conductivity ceramics powder.Proportioning raw materials is: get Ti-containing slag 25.29g, silicon ash 47.85g, bauxitic clay 6.93g, carbon black 19.93g.1375 ℃ of sintering temperatures, constant temperature 8h, nitrogen flow are 600ml/min.Second step preparation TiN/O '-Sialon conducting ceramic material.1450 ℃ of sintering temperatures, heat-up rate are 3 ℃/min, insulation 2h, cooling rate is 5 ℃/min, more than other technological process in two steps and processing condition with embodiment 1.Detected result shows: main thing also has a small amount of beta '-Sialon and unreacted TiO in addition mutually for O '-Sialon and TiN in the synthetic powder
2Main thing is O '-Sialon and TiN mutually in synthetic TiN/O '-Sialon conducting ceramic material, does not contain beta '-Sialon and TiO
2Phase.This material volume density is 2.9g/cm
3, Vickers' hardness reaches 9GPa, and folding strength reaches 1 50MPa; Resistivity at room temperature is 1.80 * 10
-2Ω cm; Thermal expansivity 5.4 * 10
-6K
-1Behind 1260 ℃ of oxidation 1h, the unit surface oxidation weight gain is 5.23 mg/cm
2
Embodiment 3: the first step is synthesized TiN/O '-Sialon conductivity ceramics powder.Proportioning raw materials is: get Ti-containing slag 41.00g, silicon ash 33.91g, bauxitic clay 4.44g, carbon black 20.65g.1350 ℃ of sintering temperatures, constant temperature 8h, nitrogen flow are 800ml/min.Second step preparation TiN/O '-Sialon conducting ceramic material, 1475 ℃ of sintering temperatures, insulation 2h.More than other technological processs of two steps and processing condition with embodiment 1.Detected result shows: main thing also has a small amount of beta '-Sialon and unreacted TiO in addition mutually for O '-Sialon and TiN in the synthetic powder
2Main thing is O '-Sialon and TiN mutually in synthetic TiN/O '-Sialon conducting ceramic material, does not contain beta '-Sialon and TiO
2Phase.This material volume density is 2.8g/cm
3, Vickers' hardness reaches 8GPa, and folding strength reaches 110MPa; Resistivity at room temperature is 1.33 * 10
-3Ω cm; Thermal expansivity 5.6 * 10
-6K
-1Behind 1260 ℃ of oxidation 1h, the unit surface oxidation weight gain is 7.19 mg/cm
2
Embodiment 4: the first step is synthesized the proportioning raw materials of TiN/O '-Sialon conductivity ceramics powder and specific embodiment and processing condition with embodiment 1.Second step preparation TiN/O '-Sialon conducting ceramic material.With the first step synthetic powder is raw material, and adds the Sm that accounts for raw material total amount 3%
2O
3As additive, sintering temperature is 1500 ℃, and heat-up rate is 4 ℃/min, soaking time 2h, and cooling rate is 4 ℃/min, other processing condition are with embodiment 1.Main thing is O '-Sialon and TiN mutually in synthetic TiN/O '-Sialon conducting ceramic material, does not contain beta '-Sialon and TiO
2Phase.This material volume density is 3.2g/cm
3, Vickers' hardness reaches 12GPa, and folding strength reaches 200MPa; Resistivity at room temperature is 1.12 * 10
-3Ω cm; Thermal expansivity 5.9 * 10
-6K
-1Behind 1260 ℃ of oxidation 1h, the unit surface oxidation weight gain is 5.11mg/cm
2
Claims (2)
1, a kind of method of utilizing Ti-containing slag to prepare TiN/O '-Sialon conducting ceramic material, it is characterized in that: with the Ti-containing slag is main raw material, uses SiO
2Content is silicon ash and the Al of 82～90wt%
2O
3Content is that the bauxitic clay of 79～85wt% is adjusted composition, and carbon black is a reductive agent, produces TiN/O '-Sialon conducting ceramic material in two steps:
The first step is synthesized TiN/O '-Sialon conducting ceramic material powder
(1) ball milling: the raw material Ti-containing slag bigger to granularity carries out fine grinding;
(2) sieve: sieve with the raw material powder of 200 mesh standard sieves after to above-mentioned ball milling;
(3) batching: select that synthetic O '-the Sialon chemical formula is Si for use
2xAl
xO
1+xN
2-x, x=0.3 in the formula determines prescription, and is raw materials used by following mass percent preparation:
Ti-containing slag is 25.29～41.00%, and the silicon ash is 33.91～47.85%, and bauxitic clay is 4.44～6.93%, and carbon black is 19.93～20.65%;
(4) wet mixing: with the compound for preparing is that medium is mixed into slip with the dehydrated alcohol, and the wet mixing time is 24 hours;
(5) drying: the slip after the wet mixing is put into baking oven in 60 ℃ of oven dry down;
(6) dried mixing: the compound after will drying is done and was mixed 4 hours, and places moisture eliminator to preserve the gained blank;
(7) compression molding: to compression moulding, forming pressure is 25MPa, pressurize 1min with the blank single shaft;
(8) high temperature burns till: with the blank of above-mentioned compression moulding, place in the plumbago crucible, use MoSi
2The high temperature resistance furnace heating, at a normal atmosphere, firing temperature is 1350～1400 ℃, and constant temperature 7～8 hours heats up and cooling rate is 3～5 ℃/min, in the sintering process, feed in the process furnace under the flowing nitrogen condition that flow is 400～800ml/min and burn till;
(9) burning-off carbon residue: the product after will burning till is placed on grind into powder in the agate mortar, is placed on then in the retort furnace, and constant temperature was heat-treated in 6 hours in 580 ℃ of air, removes remaining uncombined carbon;
Second step: the preparation of TiN/O '-Sialon conducting ceramic material
Adopt two kinds of preparation of raw material: a kind of is with the first step synthetic TiN/O '-Sialon powder and the Sm that accounts for raw material gross weight 3%
2O
3Additive mixes; Another kind is to be raw material with the first step synthetic TiN/O '-Sialon powder directly, does not add any additives; With above-mentioned first kind of preparing or the moulding of second kind of raw material powder single way stempressing, forming pressure 200MPa, pressurize 1min; The green compact of compression molding are put into plumbago crucible, and firing furnace is MoSi
2High temperature resistance furnace buries Si
3N
4+ SiO
2Powder, Si
3N
4With SiO
2Mol ratio be 1: 1, be 1450～1500 ℃ at normal pressure, firing temperature, soaking time 2 hours heats up and cooling rate is 3～5 ℃/min, burns till under the feeding high pure nitrogen condition, produces TiN/O '-Sialon conducting ceramic material.
2, according to the described method of utilizing Ti-containing slag to prepare TiN/O '-Sialon conducting ceramic material of claim 1, it is characterized in that feeding in the second step firing furnace flow of high-purity nitrogen, being controlled in the system to external world, environment is a malleation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510047293XA CN1330607C (en) | 2005-09-29 | 2005-09-29 | Prepn process of conductive TiN/O'-Sialon ceramic material with titanium-containing furnace slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510047293XA CN1330607C (en) | 2005-09-29 | 2005-09-29 | Prepn process of conductive TiN/O'-Sialon ceramic material with titanium-containing furnace slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772704A CN1772704A (en) | 2006-05-17 |
| CN1330607C true CN1330607C (en) | 2007-08-08 |
Family
ID=36759867
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510047293XA Expired - Fee Related CN1330607C (en) | 2005-09-29 | 2005-09-29 | Prepn process of conductive TiN/O'-Sialon ceramic material with titanium-containing furnace slag |
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| Country | Link |
|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273227A (en) * | 2000-05-22 | 2000-11-15 | 东北大学 | In-situ synthesis process for preparing complex-phase TiN/O'-sialon material |
-
2005
- 2005-09-29 CN CNB200510047293XA patent/CN1330607C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273227A (en) * | 2000-05-22 | 2000-11-15 | 东北大学 | In-situ synthesis process for preparing complex-phase TiN/O'-sialon material |
Non-Patent Citations (1)
| Title |
|---|
| 配料组成对含钛高炉渣合成TiN/(Ca,Mg)α′- Sialon粉的影响 姜涛、薛向欣，硅酸盐学报，第33卷第4期 2005 * |
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|---|---|
| CN1772704A (en) | 2006-05-17 |
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