CN103468991A - 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

Info

Publication number
CN103468991A
CN103468991A CN2013103326003A CN201310332600A CN103468991A CN 103468991 A CN103468991 A CN 103468991A CN 2013103326003 A CN2013103326003 A CN 2013103326003A CN 201310332600 A CN201310332600 A CN 201310332600A CN 103468991 A CN103468991 A CN 103468991A
Authority
CN
China
Prior art keywords
powder
sintering
compound
rare earth
high temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013103326003A
Other languages
Chinese (zh)
Other versions
CN103468991B (en
Inventor
皇志富
高义民
邢建东
马胜强
李烨飞
符寒光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201310332600.3A priority Critical patent/CN103468991B/en
Publication of CN103468991A publication Critical patent/CN103468991A/en
Application granted granted Critical
Publication of CN103468991B publication Critical patent/CN103468991B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 the high temperature oxidation resisting compound technical, relate to a kind of Cr of improvement 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 the high temperature oxidation condition.But the contriver prepares Cr in early stage 23c 6compound and carry out, when mechanical behavior under high temperature test, anti-oxidant test, after discovery adds appropriate rare earth element, it is due to Cr 23c 6generate Cr 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 its antioxygen, anti-carburetting ability are significantly improved, and compound is when being used higher than 1100 ℃, and its high temperature creep and creep rupture strength performance obviously improve.In sum, this is undoubtedly to improving Cr 23c 6compound high-temperature oxidation resistant, anti-carburetting coking behavior have important engineering application value.In addition, after finding to add appropriate rare earth element, Cr 23c 6the sintering temperature of compound can obviously reduce (approximately reducing by 100 ℃).Obviously, this is for realizing that its suitability for industrialized production has important energy-conservation, consumption reduction meaning.
In addition, by density functional theory the first performance principle, calculate known: rare-earth element cerium, lanthanum, yttrium displacement solid solution are in Cr 7c 3gibbs free energy respectively approximately :-111.6J/mol ,-106.1J/mol and 132.5J/mol; And by calculating (Cr, RE) 23c 6the thermodynamics enthalpy change value that (RE means rare-earth element cerium, lanthanum or yttrium) forms is negative value, further shows that this compound belongs to rock steady structure.
In a word, preparation (Cr, RE) from the thermodynamic argument angle 23c 6feasible.This material, for the high temperature resistant oxygen layer on the parts such as the High Temperature Furnaces Heating Apparatus base plate that uses under high temperature oxidation atmosphere, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray, will be had to important engineering using value.
Summary of the invention
The object of the invention is to further improve Cr 23c 6the performance of compound, provide a kind of raising Cr 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, it adopts rare earth to improve Cr 23c 6compound, can significantly improve antioxidant property, can be for the high temperature resistant oxygen layer on the parts such as the High Temperature Furnaces Heating Apparatus base plate that uses under high temperature oxidation atmosphere, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray.
The objective 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 piece material is crushed to granularity below 200 μ m, carries out ball-milling processing and obtain the rare earth powder that particle diameter is 30-50 μ m under the vacuum argon filling condition, after shutdown by the airtight preservation under vacuum condition of rare earth powder;
2) Cr powder and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, first Cr powder and Graphite Powder 99 are packed in ball grinder, vacuumized, 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 in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight, is again vacuumized that to make vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after ball milling completes, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould;
The graphite jig that 4) will hold rare earth powder, Cr powder, Graphite Powder 99 mixture is put into sintering oven and is carried out sintering, and sintering is to carry 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 ℃/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 ℃～1300 ℃; Soaking time is: 60～120 minutes, and together cooling with sintering oven after sintering, the Cr after being processed 23c 6compound.
Further, above-mentioned steps 1) in, rare earth is any of cerium, lanthanum or yttrium piece material.
The purity of above-mentioned rare earth >=99.5%.
Further, above-mentioned steps 2) in, the vacuum tightness while vacuumizing is 10 -1pa.
Further, above-mentioned steps 2) in, Cr powder purity and granularity are respectively: 99.9% and be less than 100 μ m.
Further, above-mentioned steps 2) in, Graphite Powder 99 purity and granularity are respectively: 99.99% and be less than 100 μ m.
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 three kinds of powders of Graphite Powder 99, and mechanical milling process adopts two steps, by controlling suitable ball-milling technology and sintering schedule, can successfully prepare the Cr after any doping in cerium, lanthanum, yttrium 23c 6compound, obviously improve its toughness raising, particularly antioxidant property and mechanical behavior under high temperature, simultaneously, 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 for using under high temperature oxidation atmosphere, kiln-opening-protecting plate, kiln quarter badge, retort, charging basket, charging tray.Concrete technical scheme of the present invention is:
1) rare earth piece material is crushed to granularity below 200 μ m, carries out ball-milling processing and obtain the rare earth powder that particle diameter is 30-50 μ m under the vacuum argon filling condition, after shutdown by the airtight preservation under vacuum condition of rare earth powder; Rare earth of the present invention can be for cerium, lanthanum or yttrium piece material any.The purity of rare earth >=99.5%.
2) Cr powder and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, first Cr powder and Graphite Powder 99 are packed in ball grinder, vacuumized, and ball milling 10-30 hour, vacuum degree control is 10 -1pa; The Cr powder purity and the granularity that wherein adopt are respectively: 99.9% and be less than 100 μ m; Graphite Powder 99 purity and granularity are respectively: 99.99% and be less than 100 μ m.
3) stop after ball mill after 2-3 hour, the rare earth powder after ball milling is good adds in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight, is again vacuumized that to make vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after ball milling completes, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
The graphite jig that 4) will hold rare earth powder, Cr powder, Graphite Powder 99 mixture is put into sintering oven and is carried out sintering, and sintering is to carry 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 ℃/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 ℃～1300 ℃; Soaking time is: 60～120 minutes, and together cooling with sintering oven after sintering, the Cr after being processed 23c 6compound.
Cr in the cerium proposed in the present invention, lanthanum, yttrium after any doping 23c 6compound, its toughness raising, particularly antioxidant property and mechanical behavior under high temperature obviously improve, simultaneously, 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
At first; commercial cerium piece material (purity >=99.5%) is crushed to granularity below 200 μ m; carry out ball-milling processing (increase its surface activity and further refinement) while obtaining 30 μ m left and right under the vacuum argon filling condition, after shutdown by cerium airtight preservation under vacuum condition.
Secondly, the pure Cr powder of commercialization and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, in the ball grinder of first Cr powder and Graphite Powder 99 being packed into, vacuumized that (vacuum tightness is 10 -1and ball milling 30 hours Pa).
Then, stop after ball mill after 2.5 hours, the cerium powder after ball milling is good (its addition be Cr powder and Graphite Powder 99 gross weight 0.01%) adds in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed, and is again vacuumized that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 50 hours, after ball milling completes, by the cerium powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, the graphite jig that holds cerium powder, Cr powder, Graphite Powder 99 mixture is put into to sintering oven and carry out sintering, sintering is to carry 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 ℃/secs; Pressure is: 50MPa; Sintering temperature is: 1300 ℃; Soaking time is: 120 minutes, together cooling with sintering oven after sintering.
The Cr prepared in the present invention 23c 6after the doped with rare-earth elements cerium, its toughness improves approximately 0.34 times, and under 1100 ℃ of lower high temperature oxidation atmosphere under anti-oxidant atmosphere approximately 0.67 times, at this temperature, high temperature creep property and creep rupture strength improve minute other and improve approximately more than 21.3% and 25.9%.
Embodiment 2
At first, commercial Rare Earth Lanthanum piece material (purity >=99.5%) is crushed to granularity below 200 μ m, carries out ball-milling processing while obtaining 40 μ m left and right under the vacuum argon filling condition, after shutdown by Rare Earth Lanthanum airtight preservation under vacuum condition.
Secondly, the pure Cr powder of commercialization and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, in the ball grinder of first Cr powder and Graphite Powder 99 being packed into, vacuumized that (vacuum tightness is 10 -1and ball milling 20 hours Pa).
Then, stop after ball mill after 2 hours, the lanthanum powder after ball milling is good (its addition be Cr powder and Graphite Powder 99 gross weight 0.1%) adds in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed, and is again vacuumized that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 40 hours, after ball milling completes, by the lanthanum powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, the graphite jig that holds lanthanum powder, Cr powder, Graphite Powder 99 mixture is put into to sintering oven and carry out sintering, sintering is to carry 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 ℃/secs; Pressure is: 35MPa; Sintering temperature is: 1250 ℃; Soaking time is: 90 minutes, together cooling with sintering oven after sintering.
The Cr prepared in the present invention 23c 6after the doped with rare-earth elements lanthanum, its toughness improves approximately 0.74 times, and under 1100 ℃ of lower high temperature oxidation atmosphere under anti-oxidant atmosphere approximately 0.96 times, at this temperature, high temperature creep property and creep rupture strength improve minute other and improve approximately more than 28.9% and 29.1%.
Embodiment 3
At first, commercial rare-earth yttrium piece material (purity >=99.5%) is crushed to granularity below 200 μ m, carries out ball-milling processing while obtaining 50 μ m left and right under the vacuum argon filling condition, after shutdown by rare-earth yttrium airtight preservation under vacuum condition.
Secondly, the pure Cr powder of commercialization and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, in the ball grinder of first Cr powder and Graphite Powder 99 being packed into, vacuumized that (vacuum tightness is 10 -1and ball milling 10 hours Pa).
Then, stop after ball mill after 2.5 hours, the yttrium powder after ball milling is good (its addition be Cr powder and Graphite Powder 99 gross weight 0.5%) adds in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed, and is again vacuumized that (vacuum tightness is 10 -1pa) and open ball mill, ball milling 30 hours, after ball milling completes, by the yttrium powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould.
Finally, the graphite jig that holds yttrium powder, Cr powder, Graphite Powder 99 mixture is put into to sintering oven and carry out sintering, sintering is to carry 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 ℃/secs; Pressure is: 5MPa; Sintering temperature is: 900 ℃; Soaking time is: 60 minutes, together cooling with sintering oven after sintering.
The Cr prepared in the present invention 23c 6after the doped with rare-earth elements yttrium, its toughness improves approximately 1.12 times, and under 1100 ℃ of lower high temperature oxidation atmosphere under anti-oxidant atmosphere approximately 1.26 times, at this temperature, high temperature creep property and creep rupture strength improve minute other and improve approximately more than 24.9% and 25.7%.

Claims (6)

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 piece material is crushed to granularity below 200 μ m, carries out ball-milling processing and obtain the rare earth powder that particle diameter is 30-50 μ m under the vacuum argon filling condition, after shutdown by the airtight preservation under vacuum condition of rare earth powder;
2) Cr powder and Graphite Powder 99 are pressed to carbide Cr 23c 6the molecular formula Atom than and after the nucleidic mass of each element is converted into weight ratio and weighs respectively, first Cr powder and Graphite Powder 99 are packed in ball grinder, vacuumized, 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 in the ball grinder that the Cr powder that mixed and Graphite Powder 99 are housed according to the 0.01-0.5% of Cr powder and Graphite Powder 99 gross weight, is again vacuumized that to make vacuum tightness be 10 -1pa, and open ball mill, ball milling 30-50 hour, after ball milling completes, by the rare earth powder, Cr powder and the Graphite Powder 99 mixture Fast Filling that mix in mould;
The graphite jig that 4) will hold rare earth powder, Cr powder, Graphite Powder 99 mixture is put into sintering oven and is carried out sintering, and sintering is to carry 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 ℃/sec; Pressure is: 5-50MPa; Sintering temperature is: 900 ℃～1300 ℃; Soaking time is: 60～120 minutes, and together cooling with sintering oven after sintering, the Cr after being processed 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, in step 1), rare earth is any of cerium, lanthanum or yttrium piece material.
3. raising Cr according to claim 2 23c 6the method of compound with oxidation resistance and mechanical behavior under high temperature, is characterized in that, the purity of described rare earth>=99.5%.
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, the vacuum tightness while vacuumizing is 10 -1pa.
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, Cr powder purity and granularity are respectively: 99.9% and be less than 100 μ m.
6. 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 μ m.
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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310332600.3A CN103468991B (en) 2013-08-01 2013-08-01 Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310332600.3A CN103468991B (en) 2013-08-01 2013-08-01 Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound

Publications (2)

Publication Number Publication Date
CN103468991A true CN103468991A (en) 2013-12-25
CN103468991B CN103468991B (en) 2015-07-01

Family

ID=49794029

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310332600.3A Expired - Fee Related CN103468991B (en) 2013-08-01 2013-08-01 Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound

Country Status (1)

Country Link
CN (1) CN103468991B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113501714A (en) * 2021-08-05 2021-10-15 沈阳新橡树磁性材料有限公司 MAX phase material with high hardness and high wear resistance and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846084A (en) * 1973-08-15 1974-11-05 Union Carbide Corp Chromium-chromium carbide powder and article made therefrom
US3881910A (en) * 1973-08-15 1975-05-06 Union Carbide Corp Chromium-chromium carbide powder
CN102219215A (en) * 2011-03-23 2011-10-19 北京矿冶研究总院 Preparation method of high-stability chromium carbide powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846084A (en) * 1973-08-15 1974-11-05 Union Carbide Corp Chromium-chromium carbide powder and article made therefrom
US3881910A (en) * 1973-08-15 1975-05-06 Union Carbide Corp Chromium-chromium carbide powder
CA1036390A (en) * 1973-08-15 1978-08-15 John F. Pelton Chromium-chromium carbide powder method for producing same and articles made therefrom
CN102219215A (en) * 2011-03-23 2011-10-19 北京矿冶研究总院 Preparation method of high-stability chromium carbide powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KEN HIROTA ET AL: "Simultaneous synthesis and consolidation of chromium carbides (Cr3C2，Cr7C3 and Cr23C6) by pulsed electric-current pressure sintering", 《MATERIALS SCIENCE AND ENGINEERING A》, vol. 399, no. 12, 30 June 2005 (2005-06-30), pages 154 - 160 *
S.SHARAFI ET AL: "Effects of milling and subsequent consolidation treatment on the microstructural properties and hardness of the nanocrystalline chromium carbide powders", 《INTERNATIONAL JOURNAL OF REFRACTORY METALS AND HARD MATERIALS》, vol. 30, no. 1, 31 January 2012 (2012-01-31), pages 57 - 63, XP028310726, DOI: doi:10.1016/j.ijrmhm.2011.07.004 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113501714A (en) * 2021-08-05 2021-10-15 沈阳新橡树磁性材料有限公司 MAX phase material with high hardness and high wear resistance and preparation method thereof

Also Published As

Publication number Publication date
CN103468991B (en) 2015-07-01

Similar Documents

Publication Publication Date Title
CN101736173B (en) Method for preparing AgSbTe2 thermoelectric material by combining melt rotatable swinging and spark plasma sintering
CN102277508A (en) Preparation method of magnesium-based hydrogen storage alloy
CN105895795A (en) Method for preparing composite tin selenide based thermoelectric material
CN107500767A (en) Uranium carbide pellet and preparation method thereof, fuel rod
CN108103337A (en) The preparation method of magnesium-base hydrogen storage material
CN111647773A (en) Rare earth hydrogen storage material and preparation method thereof
CN106854715B (en) A kind of lanthanum-magnesium containing yttrium-nickel system AB3Type hydrogen storage alloy and its preparation process
CN104073771A (en) Method for preparing sodium-doped molybdenum sputtering target material
CN103938005A (en) Method for preparing ultra-fine grained titanium and titanium alloy from jet-milled titanium hydride powder
CN108950347B (en) Preparation method of MgAgSb thermoelectric material
CN104388817A (en) High-strength-toughness sintered iron nickel alloy and preparation method thereof
CN101956110A (en) Method for preparing Mg2BIV-based thermoelectric material by low-temperature solid-phase reaction
CN103468991B (en) Method for increasing oxidation resistance and high-temperature mechanical performance of Cr23C6 compound
CN101719406B (en) Method for preparing Nd-Fe-B permanent magnet material by adding Gd-Fe alloy
CN104831352B (en) A kind of high purity high dense（LaxSm1‑x）B6Polycrystalline cathode material and preparation method thereof
CN109087987B (en) α -MgAgSb based nano composite thermoelectric material and preparation method thereof
CN102392149B (en) Method for microwave sintering preparation of nano-metric rare earth modified steel-bonded hard alloy
CN108002839B (en) ZrC1-xPreparation method of-SiC complex phase ceramic
CN107359232B (en) Cubic phase Cu 3 SbS 3 -based thermoelectric material and method for preparing thermoelectric material through element replacement
CN104909337A (en) Lithium metaborate hydrogen storage composite material adulterated with lithium hydride and preparation method thereof
CN105755381A (en) Ultrahigh pressure metal hydride hydrogen compression material
CN103451462B (en) A kind of rare earth improves block Cr 7c 3the method of anti-erosion performance
CN109608197B (en) SnS2Single-phase block and preparation method thereof
KR101500657B1 (en) Method of preparing the Nickel-Aluminum alloy powder in low temperature
CN105861897A (en) Method for designing long-service-life Nd-Mg-Ni hydrogen storage alloy through phase diagram

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150701

Termination date: 20190801

CF01 Termination of patent right due to non-payment of annual fee