CN103468991B - Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound - Google Patents

Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound Download PDF

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Publication number
CN103468991B
CN103468991B CN201310332600.3A CN201310332600A CN103468991B CN 103468991 B CN103468991 B CN 103468991B CN 201310332600 A CN201310332600 A CN 201310332600A CN 103468991 B CN103468991 B CN 103468991B
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powder
compound
sintering
rare earth
oxidation resistance
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CN103468991A (en
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皇志富
高义民
邢建东
马胜强
李烨飞
符寒光
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a method for increasing oxidation resistance and high-temperature mechanical performance of a Cr23C6 compound. A Cr23C6 compound doped by any one of cerium, lanthanum and yttrium can be successfully prepared by controlling proper ball-milling process and sintering procedure, by using Cr powder and graphite powder and rare bulk material. The toughness of the prepared Cr23C6 compound is increased; particularly, the oxidation resistance and high-temperature mechanical performance of the prepared Cr23C6 compound are increased obviously; and at the same time, a sintering temperature of the Cr23C6 compound doped by the rare earth element is reduced significantly.

Description

A kind of raising Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature
Technical field
The invention belongs to high temperature oxidation resisting compound technical, relate to one and improve Cr 23c 6the method of compounds property, especially a kind of raising Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature.
Background technology
Block Cr 23c 6compound has face-centred cubic structure, although have the ability of excellent anti-oxidant, anti-carburetting coking under high temperature oxidizing conditions.But contriver prepares Cr in early stage 23c 6compound and carry out, mechanical behavior under high temperature test, Oxidation Resistance Test time, find add appropriate rare earth element after, it is due to Cr 23c 6cr is generated in oxidation 2o 3the density of oxide film is obviously improved, particularly Cr 2o 3with Cr 23c 6binding ability and Cr 2o 3the fragility of film reduces, and make its antioxygen, anti-carburetting ability significantly improves, and compound is when using higher than 1100 DEG C, its high temperature creep and creep rupture strength performance significantly improve.In sum, this is undoubtedly to raising Cr 23c 6compound high-temperature oxidation resistant, anti-carburetting coking behavior have important engineer applied meaning.In addition, after finding to add appropriate rare earth element, Cr 23c 6the sintering temperature of compound can obviously reduce (about reducing by 100 DEG C).Obviously, this has important energy-conservation, consumption reduction meaning for realizing its suitability for industrialized production.
In addition, calculate known by density functional theory first performance principle: the displacement of rare-earth element cerium, lanthanum, yttrium is solid-solution in Cr 7c 3gibbs free energy respectively about :-111.6J/mol ,-106.1J/mol and 132.5J/mol; And by calculating (Cr, RE) 23c 6the thermodynamic enthalpy variate that (RE represents rare-earth element cerium, lanthanum or yttrium) is formed is negative value, shows that this compound belongs to rock steady structure further.
In a word, from thermodynamic argument angle, (Cr, RE) is prepared 23c 6feasible.High temperature resistant oxygen layer on the parts such as the High Temperature Furnaces Heating Apparatus base plate used under high temperature oxidative atmosphere by this material, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray, is worth having important engineer applied.
Summary of the invention
The object of the invention is to improve Cr further 23c 6the performance of compound, provides a kind of and improves Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, it adopts rare earth to improve Cr 23c 6compound, significantly can improve antioxidant property, the high temperature resistant oxygen layer on the parts such as the High Temperature Furnaces Heating Apparatus base plate that can use under high temperature oxidative atmosphere, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray.
The object of the invention is to be achieved through the following technical solutions:
This raising Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, comprises the following steps:
1) rare earth block material is crushed to granularity below 200 μm, under vacuum argon filling condition, carries out ball-milling processing obtain the rare earth powder that particle diameter is 30-50 μm, by the airtight preservation under vacuum of rare earth powder after shutdown;
2) Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, vacuumize, and ball milling 10-30 hour;
3) stop after ball mill after 2-3 hour, the rare earth powder after ball milling is good adds according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing making vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after the milling is completed, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould;
4) by hold rare earth powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 3-10 DEG C/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 DEG C ~ 1300 DEG C; Soaking time is: 60 ~ 120 minutes, together cool after sintering with sintering oven, obtains the Cr after processing 23c 6compound.
Further, above-mentioned steps 1) in, rare earth is any one of cerium, lanthanum or yttrium block material.
Purity >=99.5% of above-mentioned rare earth.
Further, above-mentioned steps 2) in, vacuum tightness when vacuumizing is 10 -1pa.
Further, above-mentioned steps 2) in, Cr powder purity and granularity are respectively: 99.9% and be less than 100 μm.
Further, above-mentioned steps 2) in, Graphite Powder 99 purity and granularity are respectively: 99.99% and be less than 100 μm.
The present invention has following beneficial effect:
The present invention improves Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature utilizes rare earth to improve Cr 23c 6compound, adopt rare earth powder, Cr powder and Graphite Powder 99 three kinds of powders, mechanical milling process adopts two steps, by controlling suitable ball-milling technology and sintering schedule, successfully can prepare the Cr after any one doping in cerium, lanthanum, yttrium 23c 6compound, makes the raising of its toughness, particularly antioxidant property and mechanical behavior under high temperature significantly improve, meanwhile, and the Cr after doped with rare-earth elements 23c 6the sintering temperature of compound is significantly reduced.
Embodiment
The present invention proposes a kind of raising Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, the appearance of this material can be applicable to the high temperature resistant oxygen layer on the parts such as High Temperature Furnaces Heating Apparatus base plate, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray that use under high temperature oxidative atmosphere.Concrete technical scheme of the present invention is:
1) rare earth block material is crushed to granularity below 200 μm, under vacuum argon filling condition, carries out ball-milling processing obtain the rare earth powder that particle diameter is 30-50 μm, by the airtight preservation under vacuum of rare earth powder after shutdown; Rare earth of the present invention can be any one of cerium, lanthanum or yttrium block material.Purity >=99.5% of rare earth.
2) Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, vacuumize, and ball milling 10-30 hour, vacuum degree control is 10 -1pa; The Cr powder purity wherein adopted and granularity are respectively: 99.9% and be less than 100 μm; Graphite Powder 99 purity and granularity are respectively: 99.99% and be less than 100 μm.
3) stop after ball mill after 2-3 hour, the rare earth powder after ball milling is good adds according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing making vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after the milling is completed, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
4) by hold rare earth powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 3-10 DEG C/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 DEG C ~ 1300 DEG C; Soaking time is: 60 ~ 120 minutes, together cool after sintering with sintering oven, obtains the Cr after processing 23c 6compound.
Cr in the cerium proposed in the present invention, lanthanum, yttrium after any one doping 23c 6compound, the raising of its toughness, particularly antioxidant property and mechanical behavior under high temperature significantly improve, meanwhile, the Cr after doped with rare-earth elements 23c 6the sintering temperature of compound is significantly reduced.
Below specific embodiments of the invention are described:
Embodiment 1
First; commercial cerium block material (purity >=99.5%) is crushed to granularity below 200 μm; ball-milling processing (increasing its surface activity and further refinement) is carried out when obtaining about 30 μm, by cerium airtight preservation under vacuum after shutdown under vacuum argon filling condition.
Secondly, pure for commercialization Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, carry out vacuumizing that (vacuum tightness is 10 -1and ball milling 30 hours Pa).
Then, stop after ball mill after 2.5 hours, the cerium powder (its addition is 0.01% of Cr powder and Graphite Powder 99 gross weight) after ball milling is good adds and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 50 hours, after the milling is completed, by the cerium powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, by hold cerium powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 3 DEG C/sec; Pressure is: 50MPa; Sintering temperature is: 1300 DEG C; Soaking time is: 120 minutes, together cool after sintering with sintering oven.
The Cr prepared in the present invention 23c 6after doped with rare-earth elements cerium, its toughness improves about 0.34 times, at 1100 DEG C under high temperature oxidative atmosphere under anti-oxidant atmosphere about 0.67 times, and high temperature creep property and creep rupture strength improve and point else improve more than about 21.3% and 25.9% at such a temperature.
Embodiment 2
First, commercial Rare Earth Lanthanum block material (purity >=99.5%) is crushed to granularity below 200 μm, under vacuum argon filling condition, carries out ball-milling processing when obtaining about 40 μm, by Rare Earth Lanthanum airtight preservation under vacuum after shutdown.
Secondly, pure for commercialization Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, carry out vacuumizing that (vacuum tightness is 10 -1and ball milling 20 hours Pa).
Then, stop after ball mill after 2 hours, the lanthanum powder (its addition is 0.1% of Cr powder and Graphite Powder 99 gross weight) after ball milling is good adds and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 40 hours, after the milling is completed, by the lanthanum powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, by hold lanthanum powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 5 DEG C/sec; Pressure is: 35MPa; Sintering temperature is: 1250 DEG C; Soaking time is: 90 minutes, together cool after sintering with sintering oven.
The Cr prepared in the present invention 23c 6after doped with rare-earth elements lanthanum, its toughness improves about 0.74 times, at 1100 DEG C under high temperature oxidative atmosphere under anti-oxidant atmosphere about 0.96 times, and high temperature creep property and creep rupture strength improve and point else improve more than about 28.9% and 29.1% at such a temperature.
Embodiment 3
First, commercial rare-earth yttrium block material (purity >=99.5%) is crushed to granularity below 200 μm, under vacuum argon filling condition, carries out ball-milling processing when obtaining about 50 μm, by rare-earth yttrium airtight preservation under vacuum after shutdown.
Secondly, pure for commercialization Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, carry out vacuumizing that (vacuum tightness is 10 -1and ball milling 10 hours Pa).
Then, stop after ball mill after 2.5 hours, the yttrium powder (its addition is 0.5% of Cr powder and Graphite Powder 99 gross weight) after ball milling is good adds and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 30 hours, after the milling is completed, by the yttrium powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, by hold yttrium powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 10 DEG C/sec; Pressure is: 5MPa; Sintering temperature is: 900 DEG C; Soaking time is: 60 minutes, together cool after sintering with sintering oven.
The Cr prepared in the present invention 23c 6after doped with rare-earth elements yttrium, its toughness improves about 1.12 times, at 1100 DEG C under high temperature oxidative atmosphere under anti-oxidant atmosphere about 1.26 times, and high temperature creep property and creep rupture strength improve and point else improve more than about 24.9% and 25.7% at such a temperature.

Claims (5)

1. one kind is improved Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, comprises the following steps:
1) rare earth block material is crushed to granularity below 200 μm, under vacuum argon filling condition, carry out ball-milling processing obtain the rare earth powder that particle diameter is 30-50 μm, by the airtight preservation under vacuum of rare earth powder after shutdown, described rare earth is any one of cerium, lanthanum or yttrium block material;
2) Cr powder and Graphite Powder 99 are pressed carbide Cr 23c 6molecular formula Atom than and the nucleidic mass of each element be converted into weight ratio and after weighing respectively, first by Cr powder and Graphite Powder 99 loading ball grinder, vacuumize, and ball milling 10-30 hour;
3) stop after ball mill after 2-3 hour, the rare earth powder after ball milling is good adds according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight and is equipped with in the ball grinder of Cr powder and the Graphite Powder 99 mixed, and again carries out vacuumizing making vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after the milling is completed, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould;
4) by hold rare earth powder, Cr powder, Graphite Powder 99 mixture graphite jig put into sintering oven and sinter, sintering carries out in vacuum sintering funace, and during sintering, the vacuum tightness of vacuum oven is 10 -1pa; The heat-up rate of sintering oven is: 3-10 DEG C/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 DEG C ~ 1300 DEG C; Soaking time is: 60 ~ 120 minutes, together cool after sintering with sintering oven, obtains the Cr after processing 23c 6compound.
2. raising Cr according to claim 1 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, purity>=99.5% of described rare earth.
3. raising Cr according to claim 1 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, step 2) in, vacuum tightness when vacuumizing is 10 -1pa.
4. raising Cr according to claim 1 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, step 2) in, Cr powder purity and granularity are respectively: 99.9% and be less than 100 μm.
5. raising Cr according to claim 1 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, step 2) in, Graphite Powder 99 purity and granularity are respectively: 99.99% and be less than 100 μm.
CN201310332600.3A 2013-08-01 2013-08-01 Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound Expired - Fee Related CN103468991B (en)

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