CN111139374A - Multilayer annular element for absorbing and desorbing hydrogen and absorbing impurity gas and preparation method thereof - Google Patents

Multilayer annular element for absorbing and desorbing hydrogen and absorbing impurity gas and preparation method thereof Download PDF

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Publication number
CN111139374A
CN111139374A CN202010010429.4A CN202010010429A CN111139374A CN 111139374 A CN111139374 A CN 111139374A CN 202010010429 A CN202010010429 A CN 202010010429A CN 111139374 A CN111139374 A CN 111139374A
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alloy
absorbing
hydrogen
powder
impurity gas
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CN111139374B (en
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卢淼
李志念
郭秀梅
袁宝龙
武媛方
叶建华
蒋利军
王树茂
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GRIMN Engineering Technology Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02Compacting only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01TSPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T1/00Details of spark gaps
    • H01T1/20Means for starting arc or facilitating ignition of spark gap
    • H01T1/22Means for starting arc or facilitating ignition of spark gap by the shape or the composition of the electrodes

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a multilayer annular element with hydrogen absorption and desorption functions and impurity gas absorption functions and a preparation method thereof. The element is formed by pressing a titanium-molybdenum alloy as a hydrogen absorbing and releasing alloy, a titanium-zirconium-manganese-iron alloy as an impurity gas absorbing alloy and copper powder as a separating layer in a mold layer by layer to form a blank and then sintering the blank. The element is used for absorbing and discharging hydrogen and removing impurity gas of a pseudo spark switch. The preparation method comprises the following steps: (1) smelting titanium and molybdenum to obtain hydrogen absorbing and releasing alloy cast ingots; (2) smelting titanium, zirconium, manganese and iron to obtain an impurity gas adsorption alloy ingot; (3) respectively crushing the two alloy cast ingots into powder, and respectively grinding the two alloy powder and the copper powder into powder; (4) putting different powders into a mould layer by layer in sequence under the argon protective atmosphere to be pressed into a multilayer annular element blank; (5) sintering the annular blank to form the element.

Description

Multilayer annular element for absorbing and desorbing hydrogen and absorbing impurity gas and preparation method thereof
Technical Field
The invention relates to a multilayer annular element with hydrogen absorption and desorption functions and impurity gas absorption functions and a preparation method thereof, in particular to a design and preparation method of a hydrogen absorption and desorption impurity gas removing multilayer annular element for a pseudo spark switch.
Background
Pseudo spark switches are the most important development in the field of pulse power technology after the eighties of the last century and can be used for fast closing switches which generate steep-wave-head large pulse currents with high repetition frequencies. The hydrogen storage device is an important part in the pseudo spark switch and is composed of a plurality of annular hydrogen storage material elements and a heating resistance wire, and when the switch works, the hydrogen storage material quickly releases hydrogen under the heating of the resistance wire to ensure the normal work of the pseudo spark switch. Meanwhile, in the working process of the pseudo spark switch, due to the fact that the current transferred by the electric charges is increased, the impurity gases released by different assemblies in the cavity are greatly increased, the impurity gases can deteriorate the working environment of the switch, the performance of the switch is reduced, even the switch is out of work, and therefore an element with the function of absorbing the impurity gases in the cavity is needed.
The existing hydrogen storage element is mainly made by mixing and sintering hydrogen absorbing and releasing metal powder, such as titanium hydride and impurity gas absorbing alloy powder, such as titanium ferrovanadium and the like. Practical tests show that after mixed sintering, different metal components have diffusion phenomena, so that the slope change of respective platform pressure of hydrogen absorption and desorption and impurity gas absorption is easily caused, powder is easily dropped or fragmentation is generated in the process of repeatedly absorbing and desorbing hydrogen, and fault factors are additionally increased; in addition, the titanium-vanadium-iron alloy still has large hydrogen absorption amount at 600 ℃, a large amount of hydrogen can be absorbed in the application range of the pseudo spark switch, and the reversibility of hydrogen absorption and desorption is poor, so that the capacity of absorbing impurity gas and the absorption rate are not high. Therefore, a new hydrogen absorption and desorption element capable of absorbing impurity gases and a preparation method thereof are urgently needed, and the problem of mutual diffusion of different functional metal components in the element preparation process is solved.
Disclosure of Invention
The invention aims to provide a multilayer annular element with functions of absorbing and releasing hydrogen and adsorbing impurity gases, which can absorb and release hydrogen and adsorb impurity gases without mutual interference under the conditions of specific temperature range and pressure of the operation of a pseudo spark switch.
It is another object of the invention to provide a method for the preparation of said element.
In order to achieve the purpose, the invention adopts the following technical scheme:
an element with the functions of absorbing and desorbing hydrogen and impurity adsorbate gas uses a titanium-molybdenum alloy as an absorbing and desorbing hydrogen alloy, uses a titanium-zirconium-manganese-iron alloy as an impurity gas absorbing alloy, and is formed by sintering a blank pressed by layering an absorbing and desorbing hydrogen alloy material and an impurity gas absorbing alloy material, wherein the absorbing and desorbing hydrogen alloy contains 75-95 atomic percent of titanium and 5-25 atomic percent of molybdenum; the impurity gas adsorption alloy contains 35-50 atomic percent of titanium, 5-10 atomic percent of zirconium, 35-50 atomic percent of manganese and 10-25 atomic percent of iron; in the blank, the mass percent of the hydrogen absorbing and releasing alloy is 80-90%, the mass percent of the impurity gas absorbing alloy is 8-18%, the mass percent of the pure copper for separation is 2%, and the pure copper is 300-mesh powder.
In the element of the invention, the hydrogen absorbing and releasing platform of the hydrogen absorbing and releasing alloy conforms to the working environment of the pseudo spark switch, and can absorb and release a large amount of hydrogen reversibly between the temperature of 500 ℃ and 800 ℃ and the pressure of 30Pa to 200PaAnd (3) hydrogen. The hydrogen absorbing and releasing platform for adsorbing impurity gas alloy is far higher than that of pseudo spark switch, and can adsorb O2 and CO in great amount and fast without absorbing hydrogen at 500-800 deg.c and 30-200 Pa2、N2、NO2And the layered structure ensures that the component diffusion phenomenon cannot occur in the sintering process of the two alloys, ensures that the respective components of the two alloys are stable, and the air suction pressure platform cannot deviate and change due to the sintering process.
The preparation method of the element comprises the following steps:
(1) smelting molybdenum and titanium which are used as hydrogen absorbing and releasing alloy components in a vacuum suspension furnace or medium-frequency induction smelting to obtain hydrogen absorbing and releasing alloy ingots; the smelting temperature is 1400-1600 ℃;
(2) performing suspension induction melting or medium-frequency induction melting on titanium, zirconium, manganese and iron which are used as alloy components for adsorbing impurity gases to obtain impurity gas adsorption alloy ingots;
(3) respectively crushing and pulverizing the hydrogen absorbing titanium molybdenum alloy cast ingot and the impurity gas absorbing titanium zirconium manganese iron alloy cast ingot to 20 meshes, and respectively grinding alloy particles into powder by using an air flow mill;
(4) under the protection of argon, putting the powder into an annular die for compression molding according to the sequence of impurity gas absorbing alloy-copper-hydrogen absorbing and releasing alloy-copper-impurity gas absorbing alloy, wherein the impurity gas absorbing alloy and the copper of the upper layer and the lower layer have the same dosage, and pressing the mixture into element blanks one by using a hydraulic machine at the pressure of 60 MPa;
(5) and putting the obtained element blank into a protective gas or vacuum environment, and sintering the blank to prepare the hydrogen absorption element by adopting the temperature, time and steps which are suitable for the sintering conditions of the components of the blank and the application requirements of the pseudo spark switch.
In the step (3), when the jet mill is adopted for grinding, argon or nitrogen is adopted as grinding gas, the working pressure is 0.3-0.7 MPa, the sorting frequency is 10-60 Hz, and the average particle size of the obtained powder is less than or equal to 50 mu m; the purity of the argon or the nitrogen is more than or equal to 99.99 percent.
In the step (4), the shrinkage proportion of the element blank in the sintering process is considered in the design of a die for preparing the element blank, and a shrinkage space is reserved, so that the appearance and the size of the sintered element meet the application requirements, and the element blank is pressed by a hydraulic press at the pressure of 60 MPa.
In the step (5), the sintering temperature of the sintering element blank is 800-850 ℃, and the sintering time is 15-30 min.
In the step (5), an aluminum oxide cylindrical supporting die is inserted into the circular holes of the multi-layer annular green body of the sintered element, so that the shrinkage rate of each layer of metal is consistent in the sintering process of the element; the same aluminum oxide cylinder can be sleeved into a plurality of blanks, and the blanks are not bonded through experimental verification; the diameter of the aluminum oxide cylinder is 0.01 mm-0.15 mm smaller than the inner diameter of the blank, and the length of the aluminum oxide cylinder is 10 mm-30 mm longer than the total length of the blanks;
the invention has the advantages that:
the component of the invention adopts titanium molybdenum alloy to improve the toughness of the component, and the titanium zirconium manganese cobalt alloy which is suitable for the temperature of 500-800 ℃ and the pressure range of 30-200 Pa is taken as a material for adsorbing impurity gas; the method for preparing the multilayer green body by separating copper powder in the preparation process solves the problem of alloy component diffusion in the sintering process; and controlling the sintering process, and adding an aluminum oxide cylindrical lining to ensure that the shrinkage proportion of each layer of the element is the same in the sintering process. The following points are embodied:
1. by using the sintering process of the titanium-molybdenum alloy, the slope of the pressure plateau of the hydrogen absorbing and releasing alloy under the working condition of the pseudo spark switch is further reduced, and the effective hydrogen storage capacity and the cycle life are further improved.
2. The element of the invention solves the problem of the change of the pressure and the slope of the hydrogen absorption platform caused by the diffusion of components of different alloys in the sintering process by using a copper powder separated layered sintering process for the hydrogen absorption alloy and the impurity gas absorption alloy.
3. According to the invention, the aluminum oxide cylinder is used as a supporting die in the sintering process, so that the problem of structural deformation caused by different shrinkage rates of alloys with different components in the sintering process is solved.
4. The elements of the present invention may also be used in the more demanding operating environments of pulsed discharge electronics where conventional elements are not suitable.
Drawings
FIG. 1 is a schematic view of a multilayer annular element according to the present invention.
FIG. 2 is a PCT plot of hydrogen absorption at 500 ℃ and hydrogen desorption at 800 ℃ for the elements of the invention, respectively.
FIG. 3 is a CO uptake capacity-rate curve at 500 ℃ for the elements of the invention using TiZrMnFe alloy.
FIG. 4 shows the CO uptake at 500 ℃ of the element of the invention using TiZrMnFe alloy2Capacity-rate curve.
FIG. 5 shows the N absorption at 500 ℃ of the element of the invention using TiZrMnFe alloy2Capacity-rate curve.
FIG. 6 shows NO absorption at 500 ℃ of the element of the invention using TiZrMnFe alloy2Capacity-rate curve.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
In the multilayer annular element with the functions of absorbing and desorbing hydrogen and adsorbing impurity gases, the titanium-molybdenum alloy is used as the hydrogen absorbing and desorbing alloy, the titanium-zirconium-manganese-iron alloy is used as the impurity gas adsorbing alloy, and the copper is used as a separating layer, wherein the copper is 300-mesh powder.
Example 2
The multilayer annular element with the functions of hydrogen storage and impurity gas adsorption, which is prepared by the invention, is characterized in that a hydrogen absorbing and releasing alloy component, namely TiMo alloy, is smelted in a vacuum suspension furnace at 1600 ℃, an alloy ingot obtained after the furnace cooling is crushed into 20 meshes in an argon protective atmosphere by crushing and ball milling, the powder enters a jet mill, the grinding gas is argon (the purity is more than or equal to 99.999%), the pressure is 0.50MPa, and the sorting frequency is 60 Hz. Collecting the powder to obtain TiMo powder with diameter not more than 50 μm.
Example 3
The element with the functions of absorbing and releasing hydrogen and adsorbing impurity gases prepared by the method has the advantages that the impurity gas adsorption alloy component, namely TiZrMnFe alloy, is smelted in a vacuum suspension furnace at 1400 ℃, an alloy ingot obtained after the furnace is cooled is crushed into 20 meshes in an argon protective atmosphere through crushing and ball milling, the powder enters a jet mill, the grinding gas is argon (the purity is more than or equal to 99.999%), the pressure is 0.50MPa, and the sorting frequency is 20 Hz. The diameter of the collected powder particles is less than or equal to 100 mu m.
Example 4
The element with the functions of absorbing and desorbing hydrogen and adsorbing impurity gas is prepared by adopting the method, under the argon protective atmosphere, powder is put into an annular die according to the sequence of impurity gas adsorption alloy-copper-hydrogen absorption and desorption alloy-copper-impurity gas adsorption alloy, the impurity gas adsorption alloy and the copper dosage on the upper layer and the lower layer are the same, and are pressed into element blanks one by a hydraulic machine at the pressure of 60MPa, the blanks are multilayer annular porous hydrogen storage element blanks with the outer diameter of 9mm and the inner diameter of 6.1mm and the thickness of 5.5mm, and the shapes of the element blanks are shown in figure 1.
Example 5
Repeating the embodiment 4, inserting an aluminum oxide cylinder with the diameter of 6mmd into the middle of the element blank pressed into the multilayer annular shape, putting the element blank into a vacuum tube furnace for sintering, vacuumizing the vacuum tube furnace until the pressure in the furnace is less than or equal to 1 x 10 < -4 > Pa, then heating to 850 ℃, preserving the temperature for 60 minutes, then naturally cooling to room temperature, and extracting the aluminum oxide cylinder to obtain the sintered multilayer annular porous hydrogen storage element.
Example 6
And testing the hydrogen absorption performance of the hydrogen absorption element according to a hydride reversible hydrogen absorption and desorption pressure-composition-isotherm (P-C-T) test method described in GB/T33291-2016. Under the condition that the hydrogen pressure is less than or equal to 1 multiplied by 10-4And (3) under the condition of Pa, heating by adopting a thermocouple and vacuumizing at the same time to activate the sample, wherein the activation condition is heating for 60min at 500 ℃. Keeping the temperature at 500 ℃, filling a test gas, wherein the test gas is hydrogen, the test pressure is gradually increased to 150Pa, and performing a hydrogen absorption test, wherein a PCT curve of hydrogen absorption and desorption is shown in figure 2; heating to 800 deg.C, reducing pressure to 50Pa to release hydrogen, and performing hydrogen release test, wherein PCT curve of hydrogen release is shown in FIG. 2.
Example 7
According to the method for testing the air suction performance of the hydrogen absorption element by the constant pressure method in GB/T25497-2010, the impurity gas adsorption of the hydrogen absorption element is realizedAnd (5) testing the performance. Under the condition that the vacuum degree is superior to 1 x 10 < -4 > Pa, a high-frequency generator and an induction coil are adopted to perform induction heating and vacuumizing on a sample simultaneously to realize sample activation, and the activation condition is heating at 500 ℃ for 60 min. Cooling to test temperature, vacuumizing to 1 × 10-6Pa, and testing with test gas N2O2, NO2 and CO2 at a test pressure of 2.7X 10-3Pa, and the gas adsorption test was carried out at 500 ℃ respectively, and the curves of the suction rate-capacity are shown in FIGS. 3, 4, 5 and 6 respectively.
The technical solution of the present invention is explained in detail above. It is obvious that the invention is not limited to the above. Many variations will be apparent to those skilled in the art in light of this disclosure, but any variations that are equivalent or similar to the present invention are within the scope of the present invention.

Claims (10)

1. The multilayer annular element with the functions of absorbing and releasing hydrogen and adsorbing impurity gases is characterized in that a titanium-molybdenum alloy is used as an absorbing and releasing hydrogen alloy, a titanium-zirconium-manganese-iron alloy is used as an impurity gas adsorbing alloy, copper is used as a separating layer, a hydrogen absorbing and releasing alloy material and an impurity gas adsorbing alloy material are pressed layer by layer to form a multilayer green body, and then the multilayer green body is sintered.
2. The element according to claim 1, wherein said hydrogen-absorbing and-releasing alloy contains 75-95 atomic% of titanium and 5-25 atomic% of molybdenum; the impurity gas adsorption alloy contains 35-50 atomic percent of titanium, 5-10 atomic percent of zirconium, 35-50 atomic percent of manganese and 10-25 atomic percent of iron; in the multilayer blank, the mass percent of hydrogen absorbing and releasing alloy is 80-90%, the mass percent of impurity gas absorbing alloy is 8-18%, the mass percent of pure copper used for the separating layer is 2%, and the pure copper is powder of 300 meshes.
3. A method for the production of a component according to claim 1 or 2, characterized in that it comprises the following steps:
(1) smelting titanium molybdenum serving as a hydrogen absorption and desorption alloy component in a vacuum suspension furnace or medium-frequency induction smelting to obtain a hydrogen absorption and desorption alloy ingot;
(2) performing suspension induction melting or medium-frequency induction melting on the titanium-zirconium-ferromanganese serving as the alloy component for adsorbing the impurity gas to obtain an alloy ingot for adsorbing the impurity gas;
(3) respectively crushing the hydrogen absorbing and releasing alloy cast ingots and the impurity gas absorbing alloy cast ingots, grinding the crushed ingots into powder by using an air flow mill, and respectively taking two kinds of alloy powder and high-purity copper powder according to the target component proportion;
(4) under the protection of argon, putting the alloy powder for adsorbing impurity gases, copper powder, hydrogen absorbing and releasing alloy powder, copper powder and alloy powder for adsorbing impurity gases into a die one by one for compression molding, wherein the dosage of the alloy powder for adsorbing impurity gases on the upper layer and the dosage of the copper powder are the same, and preparing the powder into an element blank;
(5) and (4) placing the element blank obtained in the step (4) into a protective gas or vacuum environment, and sintering to prepare the hydrogen absorbing element.
4. The method as claimed in claim 3, wherein the temperature of the smelting in step (1) is 1400-1600 ℃.
5. The method according to claim 3, wherein in the step (3), the ingot is crushed to 20 meshes, when a jet mill is used for grinding, argon or nitrogen is used as grinding gas, the working pressure is 0.3-0.7 MPa, the sorting frequency is 10-60 Hz, and the average particle size of the obtained powder is less than or equal to 50 μm.
6. The method as claimed in claim 3, wherein in the step (4), the mold reserves a shrinkage space, and the pressing is performed at a pressure of 60MPa by using a hydraulic press.
7. The method according to claim 3, wherein in the step (5), the sintering temperature of the sintered element blank is 800-850 ℃ and the sintering time is 15-30 min.
8. The method according to claim 3, wherein in the step (5), an alumina cylindrical supporting die is inserted into the circular hole of the element green body.
9. The method of claim 5, wherein the purity of the argon or nitrogen is 99.99% or more.
10. The method according to claim 8, wherein the alumina cylinders have a diameter of 0.01 to 0.15mm smaller than the inner diameter of the element body and a length of 10 to 30mm longer than the total length of the plurality of element bodies.
CN202010010429.4A 2020-01-06 2020-01-06 Multilayer annular element for absorbing and desorbing hydrogen and absorbing impurity gas and preparation method thereof Active CN111139374B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686716A (en) * 2020-12-29 2022-07-01 有研工程技术研究院有限公司 Method for rapidly preparing hydrogen storage element by secondary sintering

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1094377A (en) * 1993-04-29 1994-11-02 工程吸气公司 From hydrogen stream, remove the improvement technology of gaseous impurities
JP2018009202A (en) * 2016-07-11 2018-01-18 日本パーカライジング株式会社 Carbon steel before heat treatment having excellent scale removal property, carbon steel after heat treatment, manufacturing method of the same, scale removing method, and agent for easily forming descaling film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1094377A (en) * 1993-04-29 1994-11-02 工程吸气公司 From hydrogen stream, remove the improvement technology of gaseous impurities
JP2018009202A (en) * 2016-07-11 2018-01-18 日本パーカライジング株式会社 Carbon steel before heat treatment having excellent scale removal property, carbon steel after heat treatment, manufacturing method of the same, scale removing method, and agent for easily forming descaling film

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Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686716A (en) * 2020-12-29 2022-07-01 有研工程技术研究院有限公司 Method for rapidly preparing hydrogen storage element by secondary sintering

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