CN104880400A - High pressure hydrogen penetration test device and method - Google Patents
High pressure hydrogen penetration test device and method Download PDFInfo
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- CN104880400A CN104880400A CN201410717532.7A CN201410717532A CN104880400A CN 104880400 A CN104880400 A CN 104880400A CN 201410717532 A CN201410717532 A CN 201410717532A CN 104880400 A CN104880400 A CN 104880400A
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Abstract
The invention discloses a high pressure hydrogen penetration test device and method. The method comprises measuring a hydrogen permeation amount in sample stretching, and carrying out on-line in-situ measurement on quantitative relationships between a fatigue load state and the hydrogen permeation amount in different high pressure hydrogen environments, wherein the quantitative relationships can visually show an internal relationship between stress and hydrogen segregation diffusion and through the quantitative relationships, a direct relationship of dislocation motion, and a hydrogen diffusion coefficient, an acceleration amount and a hydrogen acceleration amount under different conditions is indirectly analyzed so that a reliable data basis is provided for dislocation density determination. The high pressure hydrogen penetration test device and method reduce a test dose and test time of a single test.
Description
Technical field
The present invention relates to High Pressure Hydrogen penetration testing technical field, especially relate to a kind of can the critical fatigue load of test material at short notice, measure High Pressure Hydrogen pervasion test device and the method for testing of the hydrogen infiltration capacity under different temperatures, hydrogen pressure and fatigue load.
Background technology
Along with the fast development of China's economy, energy supply and demand contradiction, constitutes a serious threat to energy security and sustainable economic development.Hydrogen energy source develops and the processing and upgrading of conventional fossil fuel has become the important channel solving energy supply and environmental problem.The high pressure hydrogen-contacting equipments such as the hydrogenation reactor in oil hydrocracking, hydrofining, hydroforming, coal Hydrogenation liquefaction process and the UHV (ultra-high voltage) hydrogen storage vessel in hydrogen energy storage are the nucleus equipments in the pillars of the national economy fields such as the energy, oil, chemical industry.High-pressure hydro equipment has the weight equipment of the features such as Service Environment harshness, failure mechanism is complicated, damage sequence is serious.In high pressure hydrogen environment, the material of high-pressure hydro equipment often can keep good use at short notice, but along with the prolongation of time, often problem of Cracking occurs; Find through research, the cracking of above-mentioned material is the result due to fatigue load and hydrogen damage double action.
High pressure H
2in environment, H
2molecule can be adsorbed on metal surface and dissociate further and enter metal inside, and with material bearing load reciprocation, cause hydrogen induced cracking, stress corrosion crack, hydrogen to cause the hydrogen damage of the various ways such as fatigue crack, the safety of serious harm equipment is on active service.Hydrogen is immersed in the mechanical property that metal inside can reduce material on the one hand, especially the antifatigue failure performance of material is reduced, and on the other hand, material is under different load effects, the diffusion process of hydrogen to metal inside can be affected, the two is all subject to the impact of hydrogen pressure, the interphase interaction of three, forms a complicated coupling mechanism.Therefore, material is at high pressure H
2the emphasis that mechanical property degradation research under environment becomes hydrogen energy source utilization and extention is also difficult point.
Chinese invention mandate publication number: CN202693457U, authorize publication date on January 23rd, 2013, disclose a kind of High Temperature High Pressure hydrogen-sulfide environmental hydrogen Liquid penetrant testing device, described High Temperature High Pressure hydrogen-sulfide environmental hydrogen Liquid penetrant testing device includes: a High Temperature High Pressure cathode reaction still, the sidewall of its side is disposed radially a sealing shroud, one end of described sealing shroud is positioned at the reaction chamber place of described High Temperature High Pressure cathode reaction still, its other end then protrudes out the lateral wall of described High Temperature High Pressure cathode reaction still, and and formed between the lateral wall of described High Temperature High Pressure cathode reaction still and be tightly connected, the weak point of this invention is, can not detect hydrogen infiltration capacity while tensile sample.
Summary of the invention
Goal of the invention of the present invention is to overcome deficiency of the prior art, provide a kind of can the critical fatigue load of test material at short notice, measure High Pressure Hydrogen pervasion test device and the method for testing of the hydrogen infiltration capacity under different temperatures, hydrogen pressure and fatigue load.
To achieve these goals, the present invention is by the following technical solutions:
A kind of High Pressure Hydrogen pervasion test device, described High Pressure Hydrogen pervasion test device is connected with fatigue tester with electrochemical workstation, oil bath controller respectively, and fatigue tester is provided with upper fixture for connecting sample two ends and lower clamp; The reactor comprising controller, hydrogen gas tank, nitrogen pot, ionic pump, hydrogen buffering still and be located on fatigue tester; Described reactor comprise upper end open for the first kettle of holding alkaline conducting liquid and the first kettle cover be tightly connected with the first kettle, the first kettle outer peripheral face is provided with the heating chamber around the first kettle, and heating chamber is connected with oil bath controller; Described first kettle cover and the first kettle are respectively equipped with for carrying out the spacing upper hermetically-sealed construction of sealing and lower seal structure to the hollow rod-shape sample vertically running through reactor; Described nitrogen pot is connected with the first kettle by nitrogen inlet duct, and the first kettle is provided with gas outlet; Reactor is provided with the first tensimeter for detecting the nitrogen pressure in the first kettle; Sample two ends are connected with hydrogen buffering still respectively by snorkel, and ionic pump is connected with hydrogen buffering still;
First kettle cover is provided with the contrast electrode and impressed current anode that stretch into the first kettle inside; Electrochemical workstation is electrically connected with contrast electrode, impressed current anode and sample respectively;
The second kettle that described hydrogen buffering still comprises upper end open and the second kettle cover be tightly connected with the second kettle, described hydrogen gas tank is connected with the second kettle inside by two hydrogen conduction pipes; Hydrogen buffering still is provided with the second tensimeter for detecting the Hydrogen Vapor Pressure in the second kettle;
Described controller is electrically connected with electrochemical workstation, oil bath controller, fatigue tester, the first solenoid valve be located in hydrogen gas tank, the second solenoid valve be located on nitrogen pot, the 3rd solenoid valve, ionic pump, the first tensimeter and the second tensimeter be located on gas outlet respectively.
In traditional hydrogen environmental mechanics system, the indirect relation that external environment condition hydrogen pressure and material mechanical performance are degenerated can only be characterized, the intrusion volume of hydrogen and the inner link between the reciprocation of load and material mechanical performance can not be characterized to a deeper level, constrain high pressure H
2the Quantitative study that material mechanical performance in environment is degenerated.
And the measuring method of intrusion volume about hydrogen, the method be widely used now is D-S hydroxide method, the principle that the method measures hydrogen plates one deck nickel or palladium in metal surface, and apply an oxidizing potential to metal surface, this current potential is just the passivation potential of coating and is the oxidizing potential of hydrogen, when not having hydrogen to emerge from metal surface, metal surface is in passivation state, without Charger transfer, when hydrogen atom is diffused into this one end surperficial from the other end of metal, hydrogen atom is oxidized into hydrogen ion again, and there is Charger transfer, utilize the electric current that the collection of electro-chemical test equipment produces, the transfer of an electronics just represents the diffusion of a hydrogen atom, the electric current formed represents the diffusing capacity of hydrogen, can only measure under uncharged high pressure hydrogen environment at present, or measure under without the load of hyperbaric environment, lack a kind of can carry out Mechanical loading in high pressure hydrogen environment again can the equipment of infiltration capacity of in site measurement hydrogen.
Normal experiment method thinks that matrix material is 1 × 10
6still rupture after individual circulation, then think and then 2 × 10 are needed the fatigue limit of this load lower than material for weld metal
6individual circulation, measuring fatigue limit needs to carry out a large amount of experiments, the time of the frequent last from days of each experiment, needs 10 several samples, during laboratory fees, takes a lot of work, effort.As everyone knows, the essence of material generation fatigue break is the directed movement that fatigue load causes dislocation, thus causes the final fracture of material;
The present invention can online under the different high pressure hydrogen environment of in site measurement, quantitative relationship between fatigue load state and hydrogen infiltration capacity, set up the mutual relationship of several data, and the present invention can shorten fatigue limit load, and (material is when being subject to the load action changed in time and alternately, the stress produced also can act on alternately change in time, this alterante stress exceedes the destruction that namely a certain ultimate strength and prolonged and repeated effect can cause material, and this limit is called the fatigue limit of material) mensuration workload.
When the present invention carries out fatigue limit mensuration, under given hydrogen pressure condition, after hydrogen current stabilization for seep, to material applying phase step type fatigue load from small to large, then show that this load causes the dislocation motion of material internal when hydrogen infiltration electric current starts to increase along with the lifting of load, then think that this load is material fatigue limit in the present context.
Therefore, tool of the present invention has the following advantages:
(1) conventional test methodologies needs 10-12 sample, and the present invention only needs a sample, reduces experimental amount, and overcomes the impact of the performance inconsistency of commercial materials on experiment own;
(2) traditional means of experiment measures fatigue limit needs to be performed for more than 1x10 to material
6individual circulation, especially when low frequency cycle (frequency < 1Hz), sample (under a certain load) will be performed for more than the experiment of 270 hours, experimental result under utilizing the present invention then only to need two hours just can judge this load, shortens the test duration.
As preferably, described first kettle cover and the first autoclave body bottom are respectively equipped with upper through hole for penetrating sample and lower through-hole, and described upper hermetically-sealed construction is between upper through hole and sample; Described lower seal structure is between lower through-hole and sample; The ladder that described upper through hole presents cross section area large is poroid, and described upper hermetically-sealed construction comprises to be located at two O RunddichtringOs in through hole top and to be positioned at through hole and the gland nut of compression two O RunddichtringOs downwards;
It is poroid that described lower through-hole is the large ladder of lower cross section area, and described lower seal structure comprises to be located at two O RunddichtringOs in lower through-hole bottom and to be positioned at lower through-hole and the gland nut of upwards compression two O RunddichtringOs.
As preferably, described reactor is connected with fatigue tester by supporting construction, described supporting construction comprise around heating chamber support ring and be located at two horizontal support arms of support ring both sides, two horizontal support arms are connected with two montants be located on fatigue tester respectively.
Two montants are equipped with the semicircular pipe pair of horizontal-extending towards the inner side of supporting construction, semicircular pipe is to the semicircular pipe comprising about 2 correspondences, two horizontal support arms insert the semicircular pipe centering of two montants respectively, the degree of depth in two semicircular pipes is inserted according to two horizontal support arms, the right position of support ring can be regulated, thus regulate the right position of the reactor be placed on support ring, sample is located by connecting with upper and lower fixture.
As preferably, described support ring is provided with the vertical hole of several circle distribution along support ring, is equipped with internal thread in each vertical hole; Described support ring is also provided with the connecting hole for inserting the screw be connected with reactor of several circle distribution along support ring.
For penetrating horizontal adjustment screw in each vertical hole, horizontal adjustment screw upper end for pushing up the lower surface of reactor, thus makes reactor horizontal positioned, and makes the line of sample and upper lower clamp collinear.
As preferably, sample two ends are respectively equipped with the hollow ferrule fitting be connected with the cavity in sample, and two snorkels are connected with two ferrule fittings respectively; First autoclave body bottom is provided with liquid-leaking nozzle, and liquid-leaking nozzle is provided with sealing-plug.The setting of liquid-leaking nozzle is convenient to alkalescence conduction also be discharged from the first kettle after test terminates.
Be applicable to a method of testing for High Pressure Hydrogen pervasion test device, comprise the steps:
(6-1) utilize electrochemical operation to stand in sample outside surface and plate nickel dam; The bar samples of hollow to be inserted in the first kettle and to make sample lower end pass the first autoclave body bottom, between sample lower end and reactor, loading lower seal structure;
(6-2) contrast electrode and impressed current anode are arranged on the first kettle cover, alkaline conducting liquid is poured in the first kettle, first kettle cover is covered on the first kettle, sample upper end is passed from the first kettle cover, between sample upper end and the first kettle cover, installs hermetically-sealed construction; Contrast electrode and impressed current anode bottom are all stretched in alkaline conducting liquid;
(6-3) 2 soft stainless steel snorkels are utilized to be connected with hydrogen buffering still respectively in sample upper end, lower end;
(6-4) be installed on fatigue tester by reactor, and sample upper end is connected with upper fixture, sample lower end is connected with lower clamp;
(6-5) nitrogen inlet duct lower end is stretched in alkaline conduction liquid, and gas outlet lower end is near the first kettle cover lower surface; Controller controls the second solenoid valve and the 3rd solenoid valve is opened, and enters in the first kettle under making the effect of the pressure differential of nitrogen between nitrogen cylinder and the first kettle, and make nitrogen be alkaline conduction liquid deoxygenation after 10 to 20 minutes, controller controls the second closed electromagnetic valve;
(6-6) controller controls oil bath controller and pass into heating oil in heating chamber, makes the temperature stabilization of heating chamber at 45 DEG C in 55 DEG C;
(6-7) start electrochemical workstation, electrochemical workstation is arranged on potentiostatic mode, potential setting is on the current potential of relative saturation mercurous chloride electrode 0V; Treat that the current density that electrochemical workstation catches is less than 5 × 10
-7Atime, proceed to step (6-8);
(6-8) controller control ionic pump vacuumizes the hydrogen buffering still be communicated with and sample, after vacuum tightness reaches 0.5 Pascal, controls ionic pump and quits work;
Controller controls the first solenoid valve and opens, and under the effect of the pressure differential between hydrogen gas tank and hydrogen buffering still, hydrogen enters in hydrogen buffering still and sample;
While filling hydrogen to hydrogen buffering still and sample, controller controls the second solenoid valve and opens, and makes nitrogen enter the first kettle inner;
(6-9) Hydrogen Vapor Pressure detected when nitrogen pressure and second voltage table of the first voltage table detection is all positioned at the pressure limit preset in the controller, and when the specimen current of electrochemical workstation detection is stabilized in 10
-5during the order of magnitude of A, controller controls the phase step type fatigue load that fatigue tester applies from small to large to sample, and the time of often kind of load applying is M hour, till sample fracture; Electrochemical workstation obtains the hydrogen infiltration current curve along with time variations.
The present invention measures hydrogen infiltration capacity in the process of tensile sample, to the line sample in situ under different high pressure hydrogen environment, measure the quantitative relationship between fatigue load state and hydrogen infiltration capacity, inner link between the segregation that can show stress and hydrogen intuitively spreads, sets up the mutual relationship of several data.
As preferably, the upper fixture of described fatigue tester can move up and down, and sample top is provided with annular groove, and annular groove is provided with spacing ring.
The setting of spacing ring, when sample is pulled off, sample top can not fly out reactor under the position-limiting action of spacing ring.
As preferably, described conducting solution is the KOH solution of 0.19mol/L to 0.23mol/L.
As preferably, the pressure limit preset is 4.5 to 5.4MPa.
As preferably, sample is reduced gradually by two ends to middle part cross-sectional area; The thickness of nickel dam is 1 μm to 4 μm.
Therefore, the present invention has following beneficial effect:
(1) can online under the different high pressure hydrogen environment of in site measurement, the quantitative relationship between fatigue load state and hydrogen infiltration capacity, the inner link between the segregation that can show stress and hydrogen intuitively spreads, sets up the mutual relationship of several data;
(2) under different high pressure hydrogen environment can being measured, the quantitative relationship between temperature and hydrogen infiltration capacity, and High Pressure Hydrogen, temperature factor is on the impact of fatigue of materials performance;
(3) impact of environment hydrogen on the materials'use life-span can be shown clearly, except analysis list pure hydrogen environment is on except the impact of fatigue of materials performance, also can by adding other gases in reactor, the contention adsorption process of analytical gas is on the promotion of hydrogen damage or inhibiting impact;
(4) conventional test methodologies needs 10-12 sample, and the present invention only needs a sample, reduces experimental amount, and overcomes the impact of the performance inconsistency of commercial materials on experiment own;
(5) traditional means of experiment measures fatigue limit needs to be performed for more than 1x10 to material
6individual circulation, especially when low frequency cycle (frequency < 1Hz), sample (under a certain load) will be performed for more than the experiment of 270 hours, experimental result under utilizing the present invention then only to need two hours just can judge this load, which reduces the test duration.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of the present invention;
Fig. 2 is a kind of structural representation of hydrogen buffering still of the present invention;
Fig. 3 is a kind of structural representation of supporting construction of the present invention;
Fig. 4 is a kind of structural representation of reactor of the present invention;
Fig. 5 is the another kind of structural representation of reactor of the present invention;
Fig. 6 is a kind of process flow diagram of embodiments of the invention;
Fig. 7 is a kind of Hydrogen permeation curve figure of the present invention;
Fig. 8 is a kind of sample times of fatigue curve map of the prior art;
Fig. 9 is a kind of theory diagram of the present invention.
In figure: electrochemical workstation 1, oil bath controller 2, fatigue tester 3, upper fixture 4, lower clamp 5, hydrogen gas tank 6, hydrogen conduction pipe 7, hydrogen buffering still 8, reactor 9, first kettle 10, first kettle cover 11, heating chamber 12, oil inlet pipe 13, flowline 14, sample 15, upper hermetically-sealed construction 16, lower seal structure 17, snorkel 18, first tensimeter 19, contrast electrode 20, impressed current anode 21, second kettle 22, second kettle cover 23, second tensimeter 24, upper through hole 25, O RunddichtringO 26, gland nut 27, supporting construction 28, support ring 29, horizontal support arms 30, montant 31, vertical hole 32, connecting hole 33, nitrogen inlet duct 34, gas outlet 35, spacing ring 36, controller 37, first solenoid valve 38, second solenoid valve 39, ferrule fitting 40, liquid-leaking nozzle 41, sealing-plug 42, 3rd solenoid valve 44.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment is as shown in Figure 1, Figure 4, Figure 5 a kind of High Pressure Hydrogen pervasion test device, High Pressure Hydrogen pervasion test device is connected with fatigue tester 3 with electrochemical workstation 1, oil bath controller 2 respectively, and fatigue tester is provided with upper fixture 4 for connecting sample two ends and lower clamp 5; The reactor 9 comprising PLC 37, hydrogen gas tank 6, nitrogen pot, ionic pump, hydrogen buffering still 8 and be located on fatigue tester; Reactor comprise upper end open for the first kettle 10 of holding alkaline conducting liquid and the first kettle cover 11 be tightly connected with the first kettle, first kettle outer peripheral face is provided with the heating chamber 12 around the first kettle, and heating chamber is connected with oil bath controller with flowline 14 by oil inlet pipe 13; First kettle cover and the first kettle are respectively equipped with for carrying out the spacing upper hermetically-sealed construction 16 of sealing and lower seal structure 17 to the hollow rod-shape sample 15 vertically running through reactor; Nitrogen pot is connected with the first kettle by nitrogen inlet duct 34, and the first kettle is provided with gas outlet 35; Reactor is provided with the first tensimeter 19 for detecting the nitrogen pressure in the first kettle; Sample two ends are connected with hydrogen buffering still respectively by snorkel 18, and ionic pump is connected with hydrogen buffering still;
First kettle cover is provided with the contrast electrode 20 and impressed current anode 21 that stretch into the first kettle inside; As shown in Figure 9, electrochemical workstation is electrically connected with contrast electrode, impressed current anode and sample respectively;
As shown in Figure 2, the second kettle 22 that hydrogen buffering still comprises upper end open and the second kettle cover 23 be tightly connected with the second kettle, hydrogen gas tank is connected with the second kettle inside by two hydrogen conduction pipes 7; Hydrogen buffering still is provided with the second tensimeter 24 for detecting the Hydrogen Vapor Pressure in the second kettle.First, second tensimeter is digital voltmeter.
As shown in Figure 9, controller is electrically connected with electrochemical workstation, oil bath controller, fatigue tester, the first solenoid valve 38 be located in hydrogen gas tank, the second solenoid valve 39 be located on nitrogen pot, the 3rd solenoid valve 44, ionic pump, the first tensimeter and the second tensimeter be located on gas outlet respectively.
As shown in Figure 4, the first kettle cover and the first autoclave body bottom are respectively equipped with upper through hole 25 for penetrating sample and lower through-hole, and upper hermetically-sealed construction is between upper through hole and sample; Lower seal structure is between lower through-hole and sample.
As shown in Figure 5, the ladder that upper through hole presents cross section area large is poroid, and upper hermetically-sealed construction comprises to be located at two O RunddichtringOs in through hole top 26 and to be positioned at through hole and the gland nut 27 of compression two O RunddichtringOs downwards;
It is poroid that lower through-hole is the large ladder of lower cross section area, and lower seal structure comprises to be located at two O RunddichtringOs in lower through-hole bottom 26 and to be positioned at lower through-hole and the gland nut 27 of upwards compression two 0 RunddichtringOs.
As shown in Figure 1, reactor is connected with fatigue tester by supporting construction 28; As shown in Figure 3, the support ring 29 that supporting construction comprises around heating chamber is connected with two montants 31 be located on fatigue tester respectively with two horizontal support arms, 30, two horizontal support arms being located at support ring both sides.
Support ring is provided with the vertical hole 32 of 3 circle distribution along support ring, is equipped with internal thread in each vertical hole; Support ring is also provided with the connecting hole 33 for inserting the screw be connected with reactor of 3 circle distribution along support ring.
As shown in Figure 1, shown in Figure 5, sample two ends are respectively equipped with hollow ferrule fitting 40, two snorkels be connected with the cavity in sample and are connected with two ferrule fittings respectively; First autoclave body bottom is provided with liquid-leaking nozzle 41, and liquid-leaking nozzle is provided with sealing-plug 42.
The present invention utilizes the penetration theory of hydrogen to detect hydrogen infiltration electric current:
Hydrogen is positioned at sample and hydrogen buffering still, and sample outside surface and the first kettle form hydrogen trap room; Hydrogen molecule changes atom H at sample inside surface into by physisorption and chemisorption.Concrete steps are as follows:
(1) van der Waals interaction: molecular hydrogen random migration is to sample inside surface, and collision is adsorbed;
(2) physisorption: H
2+ M → H
2m;
(3) chemisorption: form covalent type atomic hydrogen by reaction: H
2m+M → 2H
altogetherm or H
2m → HM+M
(4) course of dissolution: become absorbing atomic hydrogen: H
altogetherm → MH
molten
(5) diffusion process: enter sample inside:
Hydrogen trap room, by connecting electrochemical workstation, is applied with a larger current potential, ensures that H once be all ionized into H immediately after sample inside surface diffuses to outside surface
+, namely
H→H
++e
Thus formation electric current I; Through after a period of time, electric current I reaches maximal value, is called steady-state current I
∞; The necessary nickel plating of outside surface of sample, to ensure the reliability of hydroxide electric current.Sample can use stainless steel, carbon steel, pipe line steel material to make.
As shown in Figure 6, a kind of method of testing of High Pressure Hydrogen pervasion test device, comprises the steps:
Step 100, to the sample pretreatment that carbon steel material is made, and sample is installed:
The pressure limit preset in controller is 5 ± 0.1MPa; Utilize electrochemical operation to stand in sample outside surface and plate nickel dam; The bar samples of hollow to be inserted in the first kettle and to make sample lower end pass the first autoclave body bottom, between sample lower end and reactor, loading lower seal structure;
Step 200, after installing sample, makes sample, contrast electrode and impressed current anode bottom all stretch in alkaline conducting liquid:
Contrast electrode and impressed current anode are arranged on the first kettle cover, in the first kettle, pour alkaline conducting liquid into, the first kettle cover is covered on the first kettle, sample upper end is passed from the first kettle cover, between sample upper end and the first kettle cover, installs hermetically-sealed construction; Contrast electrode and impressed current anode bottom are all stretched in alkaline conducting liquid;
Step 300, is communicated with sample and hydrogen buffering still:
2 soft stainless steel snorkels are utilized to be connected with hydrogen buffering still respectively in sample upper end, lower end;
Step 400, is installed to reactor on fatigue tester, and sample upper end is connected with upper fixture, and sample lower end is connected with lower clamp;
Step 500 is alkaline conduction liquid deoxygenation:
As shown in Figure 1, shown in Figure 5, nitrogen inlet duct lower end is stretched in alkaline conduction liquid, and gas outlet lower end is near the first kettle cover lower surface; Controller controls the second solenoid valve and the 3rd solenoid valve is opened, enter in the first kettle under making the effect of the pressure differential of nitrogen between nitrogen cylinder and the first kettle, gas outlet is connected with the exhaust gas processing device that supersaturation NaOH solution is housed, make nitrogen be alkaline conduction liquid deoxygenation after 20 minutes, controller controls the second solenoid valve and the 3rd closed electromagnetic valve;
Step 600, controller controls oil bath controller and pass into heating oil in heating chamber, makes the temperature stabilization of heating chamber in 50 ± 0.5 DEG C;
Step 700, start electrochemical workstation, electrochemical workstation is arranged on potentiostatic mode, and potential setting is on the current potential of relative saturation mercurous chloride electrode 0V; Treat that the current density that electrochemical workstation catches is less than 5 × 10
-7Atime, proceed to step 800;
Step 800, vacuumizes for sample and fills hydrogen:
Controller controls ionic pump and vacuumizes the hydrogen buffering still be communicated with and sample, after vacuum tightness reaches 0.5 Pascal, controls ionic pump and quits work;
Controller controls the first solenoid valve and opens, and under the effect of the pressure differential between hydrogen gas tank and hydrogen buffering still, hydrogen enters in hydrogen buffering still and sample;
While filling hydrogen to hydrogen buffering still and sample, controller controls the second solenoid valve and opens, and makes nitrogen enter the first kettle inner;
Step 900, tensile sample and obtain along with time variations hydrogen infiltration current curve:
The Hydrogen Vapor Pressure detected when nitrogen pressure and second voltage table of the first voltage table detection is all positioned at 5 ± 0.1MPa, and the specimen current that electrochemical workstation detects is stabilized in 5 × 10
-5during the order of magnitude of A, controller controls fatigue tester to sample applying phase step type fatigue load from small to large, the time of often kind of load applying is 2 hours, and till sample fracture, in the process stretched, nitrogen pressure and Hydrogen Vapor Pressure all remain in 5 ± 0.1MPa; Electrochemical workstation obtains the infiltration of the hydrogen along with time variations current curve as shown in Figure 7
In the present embodiment, the upper fixture of fatigue tester can move up and down, and the sample near the first kettle cover lower surface is provided with spacing ring 36; Conducting solution is the KOH solution of 0.2mol/L; Sample is reduced gradually by two ends to middle part cross-sectional area; The thickness of nickel dam is 2 μm.
As shown in Figure 7, when nitrogen pressure and Hydrogen Vapor Pressure were positioned at 5 ± 0.1MPa scope after 3 hours, what electrochemical workstation detected flows through the hydrogen infiltration current stabilization of sample at I
∞=5 × 10
-5below A, now, fatigue tester applies phase step type fatigue load from small to large to sample, and the time of often kind of load applying is 2 hours, till sample fracture; Electrochemical workstation obtains the hydrogen infiltration current curve of Fig. 7.Hydrogen infiltration electric current is directly proportional to hydrogen infiltration capacity, and therefore the present invention obtains the change curve of hydrogen infiltration capacity by measuring hydrogen infiltration electric current.The horizontal ordinate of Fig. 7 is the time, and unit is hour; Ordinate is the hydrogen infiltration electric current detected, and unit is μ A/cm
2.
As seen from Figure 7, when fatigue load is 10kN and 12kN, the hydrogen permeation behavior of material does not change, and shows that, under this load, the directed movement of dislocation does not occur material internal; And when load reaches 14kN, hydrogen infiltration electric current is increased significantly, show under this load, material internal there occurs the directed movement of dislocation, and hydrogen is assembled in dislocation, and along with dislocation generation directed movement, thus cause the diffusion flux of hydrogen to increase, therefore, hydrogen infiltration electric current also increases thereupon.And along with the increase of load, hydrogen infiltration electric current increases gradually, show the increase of load, accelerate the directed movement of dislocation, the transmission quantity of hydrogen is caused to increase, dislocation motion and be mutually wound around the formation that can cause Micro porosity, and form micro-crack further, finally cause the fracture failure of material.
And show the classic fatigue life experiment of sample, when load is less than 12kN, can not there is fatigue break in material, and when load is greater than 14kN, material generation fatigue break, and the cycle time of increase generation fatigue break along with load, the experimental result that this and the present invention obtain is consistent.
As shown in Figure 8, traditional means of experiment measures fatigue limit needs to be performed for more than 1x10 to sample material
6individual circulation, sample (under a certain load) will be performed for more than the experiment of 270 hours, and utilize the present invention, the experimental result under only needing two hours just can judge this load, which reduce the test duration.And the hydrogen infiltration electric current that the present invention measures, reflect the hydrogen total amount through sample, the present invention is by analyzing its change procedure, indirect analysis go out material hydrogen diffusion coefficient in varied situations, acceleration amount, hydrogen acceleration amount all with dislocation motion, there is direct relation, thus be that the mensuration of dislocation desity improves authentic data foundation.Fig. 8 horizontal ordinate is maximum load, and unit is kN; Ordinate is times of fatigue, and unit is secondary.
Should be understood that the present embodiment is only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (10)
1. a High Pressure Hydrogen pervasion test device, described High Pressure Hydrogen pervasion test device is connected with fatigue tester (3) with electrochemical workstation (1), oil bath controller (2) respectively, and fatigue tester is provided with upper fixture (4) for connecting sample two ends and lower clamp (5); It is characterized in that, the reactor (9) comprising controller (37), hydrogen gas tank (6), nitrogen pot, ionic pump, hydrogen buffering still (8) and be located on fatigue tester; Described reactor comprise upper end open for the first kettle (10) of holding alkaline conducting liquid and the first kettle cover (11) be tightly connected with the first kettle, first kettle outer peripheral face is provided with the heating chamber (12) around the first kettle, and heating chamber is connected with oil bath controller; Described first kettle cover and the first kettle are respectively equipped with for carrying out the spacing upper hermetically-sealed construction (16) of sealing and lower seal structure (17) to the hollow rod-shape sample (15) vertically running through reactor; Described nitrogen pot is connected with the first kettle by nitrogen inlet duct (34), and the first kettle is provided with gas outlet (35); Reactor is provided with the first tensimeter (19) for detecting the nitrogen pressure in the first kettle; Sample two ends are connected with hydrogen buffering still respectively by snorkel (18), and ionic pump is connected with hydrogen buffering still;
First kettle cover is provided with the contrast electrode (20) and impressed current anode (21) that stretch into the first kettle inside; Electrochemical workstation is electrically connected with contrast electrode, impressed current anode and sample respectively;
The second kettle (22) that described hydrogen buffering still comprises upper end open and the second kettle cover (23) be tightly connected with the second kettle, described hydrogen gas tank is connected with the second kettle inside by two hydrogen conduction pipes (7); Hydrogen buffering still is provided with the second tensimeter (24) for detecting the Hydrogen Vapor Pressure in the second kettle;
Described controller is electrically connected with electrochemical workstation, oil bath controller, fatigue tester, the first solenoid valve (38) be located in hydrogen gas tank, the second solenoid valve (39) be located on nitrogen pot, the 3rd solenoid valve (44), ionic pump, the first tensimeter and the second tensimeter be located on gas outlet respectively.
2. High Pressure Hydrogen pervasion test device according to claim 1, it is characterized in that, described first kettle cover and the first autoclave body bottom are respectively equipped with upper through hole (25) for penetrating sample and lower through-hole, and described upper hermetically-sealed construction is between upper through hole and sample; Described lower seal structure is between lower through-hole and sample; The ladder that described upper through hole presents cross section area large is poroid, and described upper hermetically-sealed construction comprises two O RunddichtringOs (26) being located in through hole top and is positioned at through hole and compresses the gland nut (27) of two O RunddichtringOs downwards;
It is poroid that described lower through-hole is the large ladder of lower cross section area, and described lower seal structure comprises two O RunddichtringOs (26) being located in lower through-hole bottom and is positioned at lower through-hole and upwards compresses the gland nut (27) of two O RunddichtringOs.
3. High Pressure Hydrogen pervasion test device according to claim 1, it is characterized in that, described reactor is connected with fatigue tester by supporting construction (28), described supporting construction comprise around heating chamber support ring (29) and be located at two horizontal support arms (30) of support ring both sides, two horizontal support arms are connected with two montants (31) be located on fatigue tester respectively.
4. High Pressure Hydrogen pervasion test device according to claim 3, is characterized in that, described support ring is provided with the vertical hole (32) of several circle distribution along support ring, is equipped with internal thread in each vertical hole; Described support ring is also provided with the connecting hole (33) for inserting the screw be connected with reactor of several circle distribution along support ring.
5. the High Pressure Hydrogen pervasion test device according to claim 1 or 2 or 3 or 4, it is characterized in that, sample two ends are respectively equipped with the hollow ferrule fitting (40) be connected with the cavity in sample, two snorkels are connected with two ferrule fittings respectively; First autoclave body bottom is provided with liquid-leaking nozzle (41), and liquid-leaking nozzle is provided with sealing-plug (42).
6. be applicable to a method of testing for High Pressure Hydrogen pervasion test device according to claim 1, it is characterized in that, comprise the steps:
(6-1) utilize electrochemical operation to stand in sample outside surface and plate nickel dam; The bar samples of hollow to be inserted in the first kettle and to make sample lower end pass the first autoclave body bottom, between sample lower end and reactor, loading lower seal structure;
(6-2) contrast electrode and impressed current anode are arranged on the first kettle cover, alkaline conducting liquid is poured in the first kettle, first kettle cover is covered on the first kettle, sample upper end is passed from the first kettle cover, between sample upper end and the first kettle cover, installs hermetically-sealed construction; Contrast electrode and impressed current anode bottom are all stretched in alkaline conducting liquid;
(6-3) 2 soft stainless steel snorkels are utilized to be connected with hydrogen buffering still respectively in sample upper end, lower end;
(6-4) be installed on fatigue tester by reactor, and sample upper end is connected with upper fixture, sample lower end is connected with lower clamp;
(6-5) nitrogen inlet duct lower end is stretched in alkaline conduction liquid, and gas outlet lower end is near the first kettle cover lower surface; Controller controls the second solenoid valve and the 3rd solenoid valve is opened, and enters in the first kettle under making the effect of the pressure differential of nitrogen between nitrogen cylinder and the first kettle, and make nitrogen be alkaline conduction liquid deoxygenation after 10 to 20 minutes, controller controls the second closed electromagnetic valve;
(6-6) controller controls oil bath controller and pass into heating oil in heating chamber, makes the temperature stabilization of heating chamber at 45 DEG C in 55 DEG C;
(6-7) start electrochemical workstation, electrochemical workstation is arranged on potentiostatic mode, potential setting is on the current potential of relative saturation mercurous chloride electrode OV; Treat that the current density that electrochemical workstation catches is less than 5 × 10
-7Atime, proceed to step (6-8);
(6-8) controller control ionic pump vacuumizes the hydrogen buffering still be communicated with and sample, after vacuum tightness reaches 0.5 Pascal, controls ionic pump and quits work;
Controller controls the first solenoid valve and opens, and under the effect of the pressure differential between hydrogen gas tank and hydrogen buffering still, hydrogen enters in hydrogen buffering still and sample;
While filling hydrogen to hydrogen buffering still and sample, controller controls the second solenoid valve and opens, and makes nitrogen enter the first kettle inner;
(6-9) Hydrogen Vapor Pressure detected when nitrogen pressure and second voltage table of the first voltage table detection is all positioned at the pressure limit preset in the controller, and when the specimen current of electrochemical workstation detection is stabilized in 10
-5during the order of magnitude of A, controller controls the phase step type fatigue load that fatigue tester applies from small to large to sample, and the time of often kind of load applying is M hour, till sample fracture; Electrochemical workstation obtains the hydrogen infiltration current curve along with time variations.
7. the method for testing of High Pressure Hydrogen pervasion test device according to claim 6, is characterized in that, the upper fixture of described fatigue tester can move up and down, and sample top is provided with annular groove, and annular groove is provided with spacing ring (36).
8. the method for testing of High Pressure Hydrogen pervasion test device according to claim 6, is characterized in that, described conducting solution is the KOH solution of 0.19mol/L to 0.23mol/L.
9. the method for testing of the High Pressure Hydrogen pervasion test device according to claim 6 or 7 or 8, is characterized in that, the pressure limit preset is 4.5 to 5.4MPa.
10. the method for testing of the High Pressure Hydrogen pervasion test device according to claim 6 or 7 or 8, is characterized in that, sample is reduced gradually by two ends to middle part cross-sectional area; The thickness of nickel dam is 1 μm to 4 μm.
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| CN114778649B (en) * | 2022-05-09 | 2024-01-09 | 西安交通大学 | Electrochemical testing device suitable for subcritical/supercritical water system |
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