CN110530690A - A kind of electrochemical cathode hydrogen filling method of metal and alloy sample - Google Patents
A kind of electrochemical cathode hydrogen filling method of metal and alloy sample Download PDFInfo
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- CN110530690A CN110530690A CN201910672900.3A CN201910672900A CN110530690A CN 110530690 A CN110530690 A CN 110530690A CN 201910672900 A CN201910672900 A CN 201910672900A CN 110530690 A CN110530690 A CN 110530690A
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Abstract
The invention discloses a kind of metal and the electrochemical cathode hydrogen filling methods of alloy sample, include the following steps: 1) to dry after being flushed with hydrogen sample and carrying out acid-wash activation, the aqueous sulfuric acid containing thiocarbamide is configured simultaneously, the aqueous sulfuric acid containing thiocarbamide is poured into electrolytic cell again, and electrolytic cell is put into oil bath heating magnetic stirring apparatus, while the holding temperature and stirring rate of oil bath heating magnetic stirring apparatus are set；2) anode and sample to be flushed with hydrogen are fixed in electrolytic cell, DC power supply is connected with anode and sample to be flushed with hydrogen again, area and the preset output electric current for being flushed with hydrogen current density and adjusting DC power supply are flushed with hydrogen according to sample to be flushed with hydrogen, to realize being flushed with hydrogen for sample to be flushed with hydrogen, this method can obtain the metal and alloy sample of different hydrogen contents, and it is highly-safe, it operates relatively simple.
Description
Technical field
The invention belongs to the metal of different hydrogen contents and alloy sample preparation field, it is related to a kind of metal and alloy sample
Electrochemical cathode hydrogen filling method.
Background technique
With the continuous development of human society, fossil energy will face depleted, and problem of environmental pollution constantly deteriorates,
Searching cleaning, reproducible new energy are extremely urgent.Wherein, Hydrogen Energy because its combustion process in " zero carbon emission " and gradually at
For a kind of important new cleaning fuel, therefore, the hydrogen storage material that can store hydrogen energy releasing is gradually widely used
And research, people begin to focus on these hydrogen storage materials (such as pure titanium, pure vanadium, pure tantalum and its alloy) in storage and hydrogen energy releasing process
The hydride of middle formation；Meanwhile metal and alloy (such as pure zirconium, zircaloy, titanium alloy) are during use due to the hydrogen in environment
The metal hydride that matrix forms brittlement phase is penetrated into, workpiece is caused phenomena such as serious hydrogen embrittlement or hydrogen cause ductile fracture occur.Cause
This, people start to study metal hydride, the metal hydride mainly studied include TiHx/VHx/TaHx/ZrHx (0 <
X≤3) etc..In previous experiment, the hydrogenation of these metals and alloy sample (pure titanium, pure vanadium, pure tantalum, pure zirconium and its alloy)
Method mostly uses greatly atmosphere to seep hydrogen, but this method needs carry out under the circular environment of high-temperature vacuum and hydrogen, danger coefficient height,
It is complicated for operation, it is unfavorable for laboratory preparation.Therefore, it is necessary to a kind of method of safety economy environmental protection to sample be flushed with hydrogen experiment with
The metal and alloy sample of different hydrogen contents are obtained, while being met subsequent to sample progress tissue topography's characterization and mechanical property survey
The demand of examination.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, the electrification of a kind of metal and alloy sample is provided
Cathodic hydrogen charging method is learned, this method can obtain the metal and alloy sample of different hydrogen contents, and highly-safe, and operation is more simple
It is single.
In order to achieve the above objectives, the electrochemical cathode hydrogen filling method of metal and alloy sample of the present invention includes as follows
Step:
1) it will be dried after being flushed with hydrogen sample and carrying out acid-wash activation, while configure the aqueous sulfuric acid containing thiocarbamide, then by sulfur-bearing
The aqueous sulfuric acid of urea pours into electrolytic cell, and electrolytic cell is put into oil bath heating magnetic stirring apparatus, while oil bath is arranged
Heat the holding temperature and stirring rate of magnetic stirring apparatus；
2) anode and sample to be flushed with hydrogen are fixed in electrolytic cell, then DC power supply is connected with anode and sample to be flushed with hydrogen
It connects, area and the preset output electric current for being flushed with hydrogen current density and adjusting DC power supply is flushed with hydrogen according to sample to be flushed with hydrogen, to realize
Sample to be flushed with hydrogen is flushed with hydrogen.
During being flushed with hydrogen, by controlling the time being flushed with hydrogen, to control the hydrogen content of sample to be flushed with hydrogen.
Being flushed with hydrogen current density is 0.2A/cm2；
The concentration of aqueous sulfuric acid is 0.5mol/L；
Temperature during being flushed with hydrogen is 30 DEG C.
Sample to be flushed with hydrogen is subjected to acid-wash activation, to remove the oxidation film of sample to be flushed with hydrogen, while making sample to be flushed with hydrogen
Surface-brightening is smooth, completely removes the stressor layers of specimen surface to be flushed with hydrogen.
The content of thiocarbamide is 2g/L in aqueous sulfuric acid containing thiocarbamide, and thiocarbamide is as poisonous agent, to promote the infiltration of hydrogen atom
Permeability simultaneously inhibits hydrogen atom to combine generation hydrogen molecule.
It is offered on the top cover of electrolytic cell for the through-hole across anode and sample to be flushed with hydrogen and for the ventilation of ventilation
Hole.
Anode is platinized platinum.
The invention has the following advantages:
The electrochemical cathode hydrogen filling method of metal and alloy sample of the present invention is based on hydrogen atom when specific operation
It reacts with metal and generates MHXPrinciple, M can be Ti, V, Ta and Zr, using electrolysis method, using metal and alloy as negative
Pole generates and penetrates into so that hydrogen atom is constantly flushed with hydrogen face in sample, while is molten in sulfuric acid by being electrolysed the sulfuric acid solution of low concentration
Thiocarbamide is added in liquid as poisonous agent, to improve the permeability of hydrogen atom, and inhibits hydrogen atom to combine and generates hydrogen molecule, operation side
Just, simply, can be operated at room temperature, at a normal, safety is higher, while during being flushed with hydrogen, by control be flushed with hydrogen when
Between, to obtain the metal and alloy sample of different hydrogen contents.
Detailed description of the invention
Fig. 1 a is the structural schematic diagram of electrolytic cell in the present invention；
Fig. 1 b is the structural schematic diagram of electrolytic cell top cover in the present invention；
Fig. 2 is the light microscopic phenogram after sample acid-wash activation；
Fig. 3 is the XRD diffraction peak figure after pure zirconium electrochemistry is flushed with hydrogen；
Fig. 4 is to be flushed with hydrogen rear pure zirconium surface EBSD to detect Surface Hydrogen compound formation schematic diagram.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
The electrochemical cathode hydrogen filling method of metal and alloy sample of the present invention includes the following steps:
1) it will be dried after being flushed with hydrogen sample and carrying out acid-wash activation, while configure the aqueous sulfuric acid containing thiocarbamide, then by sulfur-bearing
The aqueous sulfuric acid of urea pours into electrolytic cell, and electrolytic cell is put into oil bath heating magnetic stirring apparatus, while oil bath is arranged
Heat the holding temperature and stirring rate of magnetic stirring apparatus, wherein exist by the hydrogen atom that electromagnetic agitation guarantees that electrolysis generates
The lower regions that sample is flushed with hydrogen face are evenly distributed；
2) anode and sample to be flushed with hydrogen are fixed in electrolytic cell, then DC power supply is connected with anode and sample to be flushed with hydrogen
It connects, area and the preset output electric current for being flushed with hydrogen current density and adjusting DC power supply is flushed with hydrogen according to sample to be flushed with hydrogen, to realize
Sample to be flushed with hydrogen is flushed with hydrogen.
During being flushed with hydrogen, by controlling the time being flushed with hydrogen, to control the hydrogen content of sample to be flushed with hydrogen.
Sample to be flushed with hydrogen is subjected to acid-wash activation, to remove the oxidation film of sample to be flushed with hydrogen, while making sample to be flushed with hydrogen
Surface-brightening is smooth, completely removes the stressor layers of specimen surface to be flushed with hydrogen, and carries out tissue topography's characterization to sample to reach subsequent
With the purpose of Mechanics Performance Testing.
The content of thiocarbamide is 2g/L in aqueous sulfuric acid containing thiocarbamide, and thiocarbamide is as poisonous agent, to promote the infiltration of hydrogen atom
Permeability simultaneously inhibits hydrogen atom to combine generation hydrogen molecule.
It is offered on the top cover of electrolytic cell for the through-hole across anode and sample to be flushed with hydrogen and for the ventilation of ventilation
Hole, cathode and the anode face always during being flushed with hydrogen, guarantee that the numerical value of current density is true and reliable.
Embodiment one
Sample used in this experimental example is pure zirconium, is carried out the following processing to the pure zirconium sample that wire cutting obtains:
Acid-wash activation is carried out to the pure zirconium sample for grinding polishing, is dried for standby, the light microscopic of sample is characterized such as Fig. 2 institute after pickling
Show；
Compound concentration is the aqueous sulfuric acid of 0.5mol/L, wherein thiourea concentration 2g/L, then pour into electrolytic cell, it will
Electrolytic cell, which is put into oil bath heating magnetic stirring apparatus, keeps constant temperature, and setting charging temperature is 30 DEG C, and stirring rate is arranged；
Use platinized platinum as anode, sample to be flushed with hydrogen is fixed on Fig. 1 a and figure as cathode, by platinized platinum and sample to be flushed with hydrogen
In electrolytic cell shown in 1b, meanwhile, DC power supply is connected, area is flushed with hydrogen according to sample and preset is flushed with hydrogen current density 0.2A/
cm2, adjust and be flushed with hydrogen electric current, sample is flushed with hydrogen；
The XRD of pure zirconium sample obtained by the time is flushed with hydrogen as shown in figure 3, as can be known from Fig. 3, there is δ-ZrH by 12h1.66With ε-
ZrH2Generation, characterize by the EBSD that 1h is flushed with hydrogen pure zirconium sample obtained by the time as shown in figure 4, as can be known from Fig. 4, zirconium base body exists
Still there is high verification and measurement ratio after being flushed with hydrogen.
Claims (7)
1. the electrochemical cathode hydrogen filling method of a kind of metal and alloy sample, which comprises the steps of:
1) it will be dried after being flushed with hydrogen sample and carrying out acid-wash activation, while configure the aqueous sulfuric acid containing thiocarbamide, then will be containing thiocarbamide
Aqueous sulfuric acid pours into electrolytic cell, and electrolytic cell is put into oil bath heating magnetic stirring apparatus, while oil bath heating is arranged
The holding temperature and stirring rate of magnetic stirring apparatus；
2) anode and sample to be flushed with hydrogen are fixed in electrolytic cell, then DC power supply are connected with anode and sample to be flushed with hydrogen,
It is flushed with hydrogen area and the preset output electric current for being flushed with hydrogen current density and adjusting DC power supply according to sample to be flushed with hydrogen, to realize wait fill
Hydrogen sample is flushed with hydrogen.
2. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that be flushed with hydrogen
In the process, by controlling the time being flushed with hydrogen, to control the hydrogen content of sample to be flushed with hydrogen.
3. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that be flushed with hydrogen electricity
Current density is 0.2A/cm2；
The concentration of aqueous sulfuric acid is 0.5mol/L；
Temperature during being flushed with hydrogen is 30 DEG C.
4. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that will be wait fill
Hydrogen sample carries out acid-wash activation, to remove the oxidation film of sample to be flushed with hydrogen, while making specimen surface light to be flushed with hydrogen smooth, complete
The stressor layers of specimen surface to be flushed with hydrogen are removed entirely.
5. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that contain thiocarbamide
Aqueous sulfuric acid in thiocarbamide content be 2g/L, thiocarbamide be used as poisonous agent, with promote the permeability of hydrogen atom and inhibit hydrogen original
Son, which combines, generates hydrogen molecule.
6. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that electrolytic cell
Top cover on offer through-hole for passing through anode and sample to be flushed with hydrogen and for the ventilation hole of ventilation.
7. the electrochemical cathode hydrogen filling method of metal according to claim 1 and alloy sample, which is characterized in that anode is
Platinized platinum.
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Cited By (3)
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| CN112858359A (en) * | 2020-12-29 | 2021-05-28 | 武汉科技大学 | Method for obtaining peritectic fracture in oriented silicon steel |
| CN115780940A (en) * | 2022-08-01 | 2023-03-14 | 西南交通大学 | Welding method of zirconium alloy |
| TWI845123B (en) * | 2023-01-16 | 2024-06-11 | 國立臺北科技大學 | Method for hydrogenating titanium alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112858359A (en) * | 2020-12-29 | 2021-05-28 | 武汉科技大学 | Method for obtaining peritectic fracture in oriented silicon steel |
| CN115780940A (en) * | 2022-08-01 | 2023-03-14 | 西南交通大学 | Welding method of zirconium alloy |
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