CN106872349B - A kind of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance and its experimental method - Google Patents
A kind of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance and its experimental method Download PDFInfo
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- CN106872349B CN106872349B CN201710040935.6A CN201710040935A CN106872349B CN 106872349 B CN106872349 B CN 106872349B CN 201710040935 A CN201710040935 A CN 201710040935A CN 106872349 B CN106872349 B CN 106872349B
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Abstract
The invention discloses a kind of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance and its experimental methods, wherein imitative experimental appliance includes electrolytic bath, test device, terminal and electrochemical workstation.Wherein, test device is placed in electrolytic bath；Electrolyte in electrolytic bath is wriggled by high precision peristaltic pump forced circulation.Imitative experimental appliance overall structure is simple, static pressure continuously adjustable.The screw rod that its experimental method passes through adjusting test device, to apply different static pressure stress to magnesium alloy sample, and the flow velocity of electrolyte is adjusted by peristaltic pump, simulation quality simulates organism microenvironment in vitro, to carry out a series of electro-chemical test operations such as open circuit potential, polarization curve, ac impedance spectroscopy and electrochemistry noise, test result is really stablized, and reproducibility is good with reproducibility.The present invention can sufficiently meet magnesium alloy and use in the correlative study that people's bone microenvironment bears static pressure stress.
Description
Technical field
The present invention relates to a kind of Corrosion Behaviors of Magnesium Alloys electrochemical behavior imitative experimental appliance and its experimental methods more particularly to one
Kind magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance and its experimental method, belong to electrochemical field.
Technical background
Bio-medical material includes the material that can be medically implanted into organism or can combine with bio-tissue, main
It is used to treat or replace original tissue and organ damaged in living organism, with amendment, compensation or improves its function.
In pharmaceutical sanitary field, degradable medical metal material has obtained Devoting Major Efforts To Developing, has been widely used in organism
Tissue engineering material, internal suture, surgery bonesetting material etc., there is good application prospect.Biomedical metallic material
Require following performance: nontoxic, teratogenesis is not carcinogenic, and no allergic reaction is immune with interference body, does not destroy adjacent tissue；Object
Physicochemical property is stablized, and intensity, hardness and elasticity meet actual demand, corrosion resistance and wearability and stablizes；Processing forming is excellent,
It is easily formed the various shape of needs；Meanwhile degradable medical metal material is gone back in above performance for meeting implantation material
It should be well compatible with organism on degradation property: while degradation, meeting mechanical property requirements of implantation material itself, again
Adverse reaction will not be generated to organism, catabolite is nontoxic and can exclude organism in time.
In the orthopaedics inner implantation material of clinical application at present, stainless steel and titanium alloy are with good biocompatibility, anti-corrosion
Performance and mechanical property become widely used material.
But there are a common problems in the existing metal implant material such as stainless steel and titanium alloy is and organism bone group
The mechanical compatibility knitted is poor, and material can generate very big " stress shielding " effect after being implanted into human body to local bone tissue.Bone tissue
There is negative balance, bone resorption are caused to increase in suffered stress stimulation decline, bone remodeling, and bon e formation is reduced, and induce blocking property sclerotin and lack
It loses.
In general, implantation material and biological tissue's mechanical compatibility difference medically will lead to three kinds of serious consequences:
(1) it is implanted into original biological bone fragility of surrounding materials；
(2) it is implanted into the area of new bone undergrowth of surrounding materials；
(3) there is stress concentration in the interface being implanted between material and biological bone, so as to cause inflammation.
Stainless steel, titanium alloy bone plate, bone nail etc., which implant, to be needed to increase by taking-up of performing the operation again after bone tissue recovery from illness
The pain and medical expense burden of patient are added.In addition, the intravascular stent of clinical application at present is mainly closed with stainless steel and titanium nickel
Based on gold, these intravascular stents in addition to there are nickel ion dissolution may cause toxic side effect other than, there is also revascularization it is narrow and
Thrombus, vascellum endometrial hyperplasia occur that the drawbacks such as vascular reconstructive surgery can not be carried out when accident.
It can be seen that difference existing for the elasticity modulus and organism bone tissue of medical metal material will be controlled in certain model
Within enclosing, research and development mechanical compatibility and biocompatibility more preferably medical material become (the orthopaedics interplantation of above-mentioned field
Object, endovascular stent) important development direction.Magnesium and magnesium alloy are one because of its good biocompatibility and bone tissue inductivity
The promising biomaterial of kind, mechanical property and human body nature bone are closest, can be effectively reduced " stress-shielding effect ", promote
The healing of bone tissue.Magnesium alloy yield strength with higher simultaneously, can bear biggish load, be applied to organism bone group
It knits carrying position, also can be applied to endovascular stent, play the role of support blood vessels.Magnesium be the important nutrient of human body it
One, the 4th metallic element is only second to K into the cell+Cation；Magnesium elements participate in catalysis or activation 325 kinds of enzyme systems of organism,
All energetic supersessions in vivo are participated in, to contraction of muscle, nervimotion function, physiological function and prevention circulation system disease and ischemic
Property heart disease plays an important role；Magnesium alloy will be slow degradation and not will lead to the apparent increase of serum magnesium content after implanting,
It is drained mainly by urinary system, and can take out implant bring pain and high Operation Fee to avoid second operation
With, greatly reduction operation risk.Therefore, using biology, the good magnesium alloy of mechanical compatibility as medical degradable biology material
Material has medical safety basis, is particularly suitable for orthopedic implant material and blood vessel inner bracket material.
However, the corrosion resisting property difference of magnesium alloy strongly limits the application of magnesium alloy, when medium pH value less than 11.5 or
Corrosive environment existing for person's chloride ion corrodes especially serious.It is implanted into structural material as biology, magnesium alloy must be in the usage phase
Between strictly meet necessary mechanical property and morphology requirement, therefore it is required that Corrosion Behaviors of Magnesium Alloys degradation rate is unsuitable too fast.Human body
There are a large amount of chloride ions 7.4 or so, and in body fluid for the normal ph of interior environment, are a complicated corruption in human body in addition
Environment is lost, these can all cause magnesium alloy in the intracorporal corrosion rate of people full of uncertainty.Organism degradable medical at present
The research of implantation field of magnesium alloy is concentrated mainly on that develop corrosion resistance good and mechanical property especially plastic deformation ability is excellent
Alloy, and this two o'clock is difficult to meet simultaneously.Into the magnesium alloy orthopaedics inner implantation material of clinical application, that there are intensity is low, drop at present
Solve too fast problem；And the magnesium alloy as angiocarpy bracket has that plastic deformation ability is inadequate, degradation is too fast.This
Outside, the medical magnesium alloy studied at present all contains Al element mostly, and aluminium is not the essential trace element of human body, is considered to have mind
It is the factor for leading to alzheimer's disease, the tenability limit in human body of the magnesium alloy containing Al is only 1g/year through toxicity.
Currently, there are no the unified standards of Corrosion Behaviors of Magnesium Alloys rate determination both at home and abroad；Immersion test in simulated body fluid
And there are very big deviations between experimental result in vivo；It is high to be faced with experimental cost for experiment in vivo, test week
Phase is long, is as a result not easy to the problem of quantization.
Therefore, external analogue simulation experiments in vivo becomes one important research direction of Corrosion Behaviors of Magnesium Alloys research field.
Under the practical service condition of bone implant, magnesium alloy be not be immersed in body fluid, but with human connective tissue,
Capillary and bone tissue etc. form many microenvironments, one of microenvironment can approximation be considered as a static pressure stress electrochemistry
Erosion model.
Summary of the invention
It is an object of the invention to provide one kind can simulation quality analog bone tissue microenvironment, magnesium alloy bear static pressure
The experimental apparatus for testing of Corrosion Behaviors of Magnesium Alloys electrochemical behavior when stress, structure is simple, static pressure continuously adjustable.
Present invention technical solution used for the above purpose is a kind of magnesium alloy static pressure stress corrosion electrification scholarship and moral conduct
For imitative experimental appliance, which is characterized in that including electrolytic bath, test device, terminal and electrochemical workstation four
Point, wherein electrolytic bath is in the body structure without upper cover, and test device is placed in electrolytic bath；
A feed liquor nozzle and an outlet tube mouth, feed liquor nozzle are respectively arranged on the arranged on left and right sides wall of the electrolytic bath
A circulation loop is connected into the reservoir and high precision peristaltic pump on outlet tube mouth respectively by pipeline and outside；
The test device is sub-assembly, including rack, digital intelligent pressure transmitter and screw rod regulating part, the machine
Frame is a rectangle frame, and the top margin frame center position of rectangle frame offers a first penetrating screw hole；
The screw rod regulating part is sub-assembly, including screw rod and end plate two parts, the upper surface center position of end plate are set
It is equipped with the second screw hole, the lower part of screw rod is detachably connected by the second screw hole and end plate formation；
The screw rod passes through the top margin frame of rectangle frame through the first screw hole, and the top margin frame of rectangle frame is protruded into the lower part of screw rod
Lower section, screw rod top stretch out rectangle frame top margin frame top；
Radial direction at the upper end position of screw rod along screw rod offers a through-hole, and socket joint is connected with a tune in through-hole
Pole；
The upper surface of the bottom edge frame of rectangle frame is provided with an objective table, and the central point of objective table is located in the screw rod
On the extended line of mandrel line；
The digital intelligent pressure transmitter is bonded in the lower surface of the end plate；
Magnesium alloy sample to be tested is lain in a horizontal plane on objective table；
Digital intelligent pressure transmitter passes through data line and terminal communication connection；
Above-mentioned magnesium alloy sample is square plate, and in four side elevations of plate, a side elevation is completely exposed, and two
Side elevation is closed with epoxy coating, another side elevation is welded with conducting wire, after conducting wire is drawn, the side elevation epoxy resin
Encapsulation, integral sealing；
Surfaces externally and internally, the screw rod of above-mentioned rectangle frame protrude into that section of the lower section of the top margin frame of rectangle frame outer surface,
On the outer surface of end plate and the outer surface of pressure sensor, it is coated with insulating coating respectively；
Above-mentioned conducting wire is connect with electrochemical workstation, at this point, magnesium alloy sample becomes a work of electrochemical workstation
Make electrode, together with another working electrode of electrochemical workstation itself institute band, collectively constitutes as in Electrochemical Test Procedure
To electrode.
The technical effect brought directely by the technical proposal is that whole device structure is simple, can easily be accommodated, it is easy to use；
Working electrode is soaked in electrolyte, not only controllable with liquid contact surface product, moreover it is possible to which with to electrode, reference is electric for control
The distance between pole is effectively reduced diffusion control bring solution ohmmic drop, hydrogen is effectively reduced to magnesium alloy electrochemical corrosion
It is electrochemical to can be realized open circuit potential, polarization curve, AC impedance and electrochemistry noise etc. under static pressure stress condition for the influence of process
Learn test；
Magnesium alloy working electrode is totally submerged in the solution, on the one hand avoids the interference of surface tension of liquid, on the other hand
Also it is able to maintain that electric double layer is stablized, obtains well stable corrosion electrochemical action test data.
Under the driving of peristaltic pump, Hank ' the s solution in electrolytic bath is slowly wriggled, can analogue simulation vivo environment；It is logical
The flow of peristaltic pump is overregulated, the adjusting of electrolytic bath electrolyte inside exchange rate can be carried out, carries out human body with can be convenient
The state simulation constantly exchanged under interior true fluid environment；Also, more truly pass through load static pressure stress condition simulation life
Object inner bone tissues environment and body fluid flow the influence to magnesium alloy electrochemical corrosion, are further ensured that the true of experimental result
Property, stability and accuracy.
Further preferably, the material of the electrolytic cell is organic glass.
The direct bring of the optimal technical scheme has the technical effect that the material of electrolytic bath wooden partition is transparent material, is convenient for
Comprehensive timely observation is carried out in experimentation.
Further preferably, the screw thread on above-mentioned first screw hole and screw rod is fine thread.
The direct bring of the optimal technical scheme has the technical effect that, using the shorter fine thread of lead, advantageously reduces
The appearance of maloperation when adjusting, and the adjusting of the static pressure stress value of " serialization variation " is realized as much as possible.
The second purpose of the invention is to provide a kind of above-mentioned magnesium alloy static pressure stress corrosion electrochemical behavior simulated experiments
The experimental method of device, easy to operate, (static pressure numerical value) flexible adjustment, suitable for once carrying out different magnesium alloy samples
(batch) analog detection.
Present invention technical solution used for the above purpose is, a kind of such as above-mentioned magnesium alloy static pressure stress corrosion
The experimental method of electrochemical behavior imitative experimental appliance, which comprises the following steps:
The first step, starting terminal, adjusting screw rod, until the numerical pressure sensor that terminal is shown
Pressure value is zero；
Second step is slowly injected into Hank ' s solution into electrolytic cell, until magnesium alloy sample is integrally immersed under liquid level
Side；
The working electrode of electrochemical workstation and reference electrode are inserted into Hank ' s solution by third step respectively；
4th step, imitative experimental appliance is moved entirely into carbon dioxide incubator, and set temperature is 37.5 DEG C；To electricity
Hank ' s solution temperature in solution slot rises to 37.5 DEG C, starts peristaltic pump, to drive Hank ' the s solution in electrolytic cell slow
Circulation is wriggled；
5th step starts electrochemical workstation, detects open circuit potential, polarization curve and AC electrochemical impedance spectrum；
6th step is examined again by adjusting screw rod so that the pressure registration of digital pressure sensor is increased to setting value
Survey detection open circuit potential, polarization curve and electrochemical impedance spectroscopy under the setting pressure；
7th step repeats the 6th step, until terminating.
In conclusion the present invention compared with the existing technology, has the advantages that
1, whole device structure is simple, easy to adjust；
The experimental provision adjusts the flow velocity of electrolyte by application static pressure stress and by peristaltic pump, in vitro simulation quality mould
Quasi- organism microenvironment, especially influence of the analog bone tissue microenvironment to Corrosion Behaviors of Magnesium Alloys behavior further ensure external
The electrochemical corrosion situation of experimental result and true organism endoskeleton tissue microenvironment mutually approaches；
2, electrolytic cell slot avoids prolonged reaction process, electrolyte component ratio using the method for constantly exchange electrolyte
Example imbalance；
3, in the solution, tested surface is vertical with liquid level for working electrode (magnesium alloy sample) submergence, it is possible to prevente effectively from test
Hydrogen is gathered in test surfaces to the stability for influencing corrosion electrochemical action test in the process；
4, the experimental provision is suitable for a series of electricity such as open circuit potential, polarization curve, ac impedance spectroscopy and electrochemistry noise
Test chemical project can meet the experiment needs of corrosion electrochemical action of the research magnesium alloy under static pressure stress.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance of the invention；
Fig. 2 is that Mg-4Li-1Ca alloy sample does not load under static pressure stress condition, the corrosion electrification in Hank ' s solution
Scholarship and moral conduct is the polarization curve of test result；
Fig. 3 is that Mg-4Li-1Ca alloy sample does not load under static pressure stress condition, the corrosion electrification in Hank ' s solution
Scholarship and moral conduct is that the Nyquist of test result schemes；
Fig. 4 is that Mg-4Li-1Ca alloy sample does not load under static pressure stress condition, the corrosion electrification in Hank ' s solution
Scholarship and moral conduct is that the Bode of test result schemes；
Fig. 5 is that Mg-4Li-1Ca alloy sample loads under 1.5MPa static pressure stress condition, the corrosion in Hank ' s solution
The polarization curve of electrochemical behavior test result；
Fig. 6 is that Mg-4Li-1Ca alloy sample loads under 1.5MPa static pressure stress condition, the corrosion in Hank ' s solution
The Nyquist of electrochemical behavior test result schemes；
Fig. 7 is that Mg-4Li-1Ca alloy sample loads under 1.5MPa static pressure stress condition, the corrosion in Hank ' s solution
The Bode of electrochemical behavior test result schemes；
Fig. 8 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The polarization curve of chemical behavior test result；
Fig. 9 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The Nyquist of chemical behavior test result schemes；
Figure 10 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The Bode of chemical behavior test result schemes.
Specific embodiment
With reference to the accompanying drawings and examples, to further explanation of the invention.
As shown in Figure 1, magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance of the invention comprising electrolysis
Liquid bath 7,9 four part of test device, terminal 8 and electrochemical workstation, wherein electrolytic bath is in the cabinet knot without upper cover
Structure, test device are placed in electrolytic bath；
A feed liquor nozzle 4 and an outlet tube mouth 5, inlet tube are respectively arranged on the arranged on left and right sides wall of above-mentioned electrolytic bath
It is connected into respectively by pipeline and external reservoir and high precision peristaltic pump (omit and be not drawn into figure) on mouth and outlet tube mouth
One circulation loop；
Above-mentioned test device is sub-assembly, including rack 1, digital intelligent pressure transmitter 13 and screw rod regulating part, on
Stating rack is a rectangle frame, and the top margin frame center position of rectangle frame offers a first penetrating screw hole；
Above-mentioned screw rod regulating part is sub-assembly, including 3 two parts of screw rod 2 and end plate, the upper surface center position of end plate
It is provided with the second screw hole, the lower part of screw rod is detachably connected by the second screw hole and end plate formation；
Above-mentioned screw rod passes through the top margin frame of rectangle frame through the first screw hole, and the top margin frame of rectangle frame is protruded into the lower part of screw rod
Lower section, screw rod top stretch out rectangle frame top margin frame top；
Radial direction at the upper end position of screw rod along screw rod offers a through-hole, and socket joint is connected with a tune in through-hole
Pole 15；
The upper surface of the bottom edge frame of rectangle frame is provided with an objective table, and the central point of objective table is located in above-mentioned screw rod
On the extended line of mandrel line；
Above-mentioned digital intelligent pressure transmitter is bonded in the lower surface of above-mentioned end plate；
Magnesium alloy sample to be tested is lain in a horizontal plane on objective table；
Digital intelligent pressure transmitter passes through data line 6 and terminal communication connection；
Above-mentioned magnesium alloy sample is square plate, and in four side elevations of plate, a side elevation is completely exposed, and two
Side elevation is closed with epoxy coating, another side elevation is welded with conducting wire, after conducting wire is drawn, the side elevation epoxy resin
Encapsulation, integral sealing；
Surfaces externally and internally, the screw rod of above-mentioned rectangle frame protrude into that section of the lower section of the top margin frame of rectangle frame outer surface,
On the outer surface of end plate and the outer surface of pressure sensor, it is coated with insulating coating respectively；
Above-mentioned conducting wire is connect with electrochemical workstation, at this point, magnesium alloy sample becomes a work of electrochemical workstation
Make electrode, together with another working electrode 12 of electrochemical workstation itself institute band, collectively constitutes as Electrochemical Test Procedure
In to electrode.
The material of above-mentioned electrolytic cell is organic glass.
Screw thread on above-mentioned first screw hole and screw rod is fine thread.
For a better understanding of the invention, with reference to the accompanying drawing, magnesium alloy static pressure stress corrosion electricity of the invention is discussed in detail
The experimental method of chemical behavior imitative experimental appliance.
As shown in Figure 1, the experimental method of above-mentioned magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance,
It is characterized in that, comprising the following steps:
The first step, starting terminal, adjusting screw rod, until the numerical pressure sensor that terminal is shown
Pressure value is zero；
Second step is slowly injected into Hank ' s solution into electrolytic cell, until magnesium alloy sample is integrally immersed under liquid level
Side；
The working electrode 12 of electrochemical workstation and reference electrode 13 are inserted into Hank ' s solution by third step respectively；
4th step, imitative experimental appliance is moved entirely into carbon dioxide incubator, and set temperature is 37.5 DEG C；To electricity
Hank ' s solution temperature in solution slot rises to 37.5 DEG C, starts peristaltic pump, to drive Hank ' the s solution in electrolytic cell slow
Circulation is wriggled；
5th step starts electrochemical workstation, detects open circuit potential, AC electrochemical impedance spectrum and polarization curve；
6th step is examined again by adjusting screw rod so that the pressure registration of digital pressure sensor is increased to setting value
Survey detection open circuit potential, polarization curve and electrochemical impedance spectroscopy under the setting pressure；
7th step repeats the 6th step, until terminating.
To be further understood that the present invention, now in conjunction with embodiment, the present invention is described in detail.
Illustrate: in following embodiment, the material of magnesium alloy sample to be measured is Mg-4Li-1Ca alloy (As-extruded)；Magnesium
The preprocess method of alloy sample is all the same: magnesium alloy being sliced using wire cutting, having a size of 20mm × 20mm × 5mm, successively
With 150#、400#、800#、1200#、1500#With 2500#Silicon carbide silicon carbide paper polish each surface of magnesium alloy, touch detection with hand,
Until each surface is smooth, after impulse- free robustness, rinsed well with dehydrated alcohol, hot-air quickly dries up.
Embodiment 1
The static pressure stress of application is 0.0MPa.
Test result see the table below 1.
As shown in Fig. 2, three curves are the polarization curve of three groups of Duplicate Samples under same experimental conditions respectively in Fig. 2.
The corrosion current density I of the corresponding Mg-4Li-1Ca alloy sample of polarization curve 1,2,3corrAnd corrosion potential
Ecorr
As shown in table 1.Electrochemical parameter in table 1 shows in conjunction with the test result of the parallel sample of multiple groups: in static pressure stress
For the corrosion current density I measured when 0MPacorrWith corrosion potential EcorrClose, the reproducibility between Duplicate Samples is good, energy
The reliable test result of enough influences for excluding accidentalia in experiment, the device is stablized.
Fig. 3 and Fig. 4 is to load the AC impedance spectroscopy (Nyquist figure) that static pressure stress is 0.0MPa.
As shown in figure 3, the trend of Nyquist figure curve 1,2,3 is also close in figure, and the capacitive reactance arc radius of three curves
It is also close.
Fig. 4 is to load the AC impedance spectroscopy (Bode figure) that static pressure stress is 0.0MPa.
As shown in figure 4, three curves are bent in the Bode figure of three groups of Duplicate Samples under same experimental conditions respectively in figure
The high frequency region of line 1,2,3 and area's line trend of low frequency range are all almost consistent.
According to the analysis to Bode figure and Nyquist figure, show in conjunction with the test result of the parallel sample of multiple groups:
When static pressure stress is 0.0MPa the Bode figure curve that measures be bordering on coincidence, curve capacitive reactance arc half in Nyquist figure
Diameter is close, this experimental provision test result is stablized really, and the reproducibility between parallel sample is good, can exclude in experiment accidentally
The influence of factor.
Table 1:Mg-4Li-1Ca alloy sample loads chemical property ginseng of the 0.0MPa static pressure stress in Hank ' s solution
Number
Embodiment 2
The static pressure stress of application is 1.5MPa.
Test result see the table below 2.
Fig. 5 is that Mg-4Li-1Ca alloy sample loads under 1.5MPa static pressure stress condition, the corrosion in Hank ' s solution
The polarization curve of electrochemical behavior test result
As shown in figure 5, three curves are the polarization curve of three groups of Duplicate Samples under same test conditions respectively in figure.Pole
Change the corrosion current density I of the corresponding sample of curve 1,2,3corrWith corrosion potential EcorrAs shown in table 2.
Electrochemical parameter in table 2 shows in conjunction with the test result of the parallel sample of multiple groups: when static pressure stress is 1.5MPa
The corrosion current density I measuredcorrWith corrosion potential EcorrClose, the reproducibility between Duplicate Samples is good, the experimental provision
Test result stablize, can exclude experiment in accidentalia influence.
Table 2:Mg-4Li-1Ca alloy sample loads chemical property ginseng of the 1.5MPa static pressure stress in Hank ' s solution
Number
| Polarization curve | Corrosion current density (A/cm2) | Corrosion potential (V/SCE) |
| 1 | 2.886×10-5 | -1.597 |
| 2 | 5.165×10-5 | -1.608 |
| 3 | 2.139×10-5 | -1.601 |
Fig. 6 is to load the AC impedance spectroscopy (Nyquist figure) that static pressure stress is 1.5MPa.
As shown in fig. 6, the trend of Nyquist figure curve 1,2,3 is also close in figure, and the capacitive reactance arc radius of three curves
It is also close.
Fig. 7 is to load the AC impedance spectroscopy (Bode figure) that static pressure stress is 1.5MPa..
As shown in fig. 7, three curves are the Bode figure curves of three groups of Duplicate Samples under same experimental conditions in Fig. 7, it is bent
The high frequency region of line 1,2,3 and area's line trend of low frequency range are all very close.
According to the analysis to Bode figure and Nyquist figure, show in conjunction with the test result of the parallel sample of multiple groups: in static pressure
The Bode figure curve that measures is bordering on that coincidence, curve capacitive reactance arc radius is close in Nyquist figure when stress is 1.5MPa, this experiment fills
It sets test result to stablize really, the reproducibility between parallel sample is good, can exclude the influence of accidentalia in experiment.
Embodiment 3
The static pressure stress of application is respectively 0.0MPa, 1.5MPa, 3.0MPa.
Test result see the table below 3.
Fig. 8 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The polarization curve of chemical behavior test result.
As shown in figure 8, Mg-4Li-1Ca alloy sample is molten in Hank ' s in figure under 0MPa, 1.5MPa, 3MPa compression
Electrochemical tests in liquid, and polarization curve in figure is fitted calculates its corrosion potential E respectivelycorrWith corruption certainly
Lose current density Icorr.Corrosion potential EcorrIt is corrosion electrochemistry thermodynamic quantity, negative value is higher, illustrates that material exists in system
Corrosion tendency in solution is stronger, and material is easy to happen electrochemical corrosion；And corrosion current density IcorrIt is corrosion electrochemistry
Dynamics amount, numerical value is bigger, then illustrates that the Electrochemical corrosion rate of material in the solution is faster in system.
Table 3:Mg-4Li-1Ca alloy sample loads chemical property parameter of the different static pressure stress in Hank ' s solution
| Static pressure stress (MPa) | Corrosion current density (A/cm2) | Corrosion potential (V) |
| 0.0 | 4.845×10-6 | -1.557 |
| 1.5 | 2.100×10-5 | -1.597 |
| 3.0 | 3.217×10-5 | -1.602 |
Electrochemical data in above-mentioned table 3 in Hank ' s solution, does not apply alloy sample in conjunction with multiple groups test result
Static pressure stress and application static pressure stress, there is biggish difference: under the action of static pressure stress, Mg-4Li-1Ca alloy sample
Corrosion potential EcorrBecome more negative, illustrates Mg-4Li-1Ca alloy sample electrochemical corrosion tendency aggravation, and its self-corrosion is electric
Current density IcorrThen have the variation of an order of magnitude, illustrate Mg-4Li-1Ca alloy sample Electrochemical corrosion rate increase compared with
Greatly.We can say that, under the action of static pressure stress, the electrochemical corrosion reaction of Mg-4Li-1Ca alloy sample is lived herein
Change and promote, meets expected experimental result.With the increase of load static pressure stress, the self-corrosion of Mg-4Li-1Ca alloy sample
Current potential EcorrValue is more negative, while corrosion current density IcorrIt has increased slightly, meets above-mentioned analysis.But since the static pressure of load is answered
Power is to change (yield strength is about 100MPa) in the smaller range of Mg-4Li-1Ca alloy elastic deformation, so Mg-4Li-
The corrosion potential E of 1Ca alloy samplecorrWith corrosion current density IcorrVariation it is smaller.
Fig. 9 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The Nyquist of chemical behavior test result schemes；
Figure 10 is that Mg-4Li-1Ca alloy sample loads under different static pressure stress conditions, the corrosion electricity in Hank ' s solution
The Bode of chemical behavior test result schemes.
As shown in figure 9, Mg-4Li-1Ca alloy sample is in Hank ' s solution under 0MPa, 1.5MPa, 3MPa compression
The Nyquist of electrochemical alternate impedance spectrum schemes, as can be seen that static pressure stress produces Mg-4Li-1Ca alloy sample capacitive reactance arc in figure
It is raw apparent to change, material corrosion resistance correlation in the solution in the radius and system of capacitive reactance arc, and radius is bigger, it is resistance to
Corrosion is better.
Therefore, load static pressure stress reduces the corrosion resistance of Mg-4Li-1Ca alloy sample, this conclusion and polarization curve
Measurement results match.
And in the Bode figure of Figure 10, it can be seen that its result and Nyquist map analysis result are essentially identical, static pressure stress
Impedance to Mg-4Li-1Ca alloy sample in low frequency range generates large effect, and the Mg-4Li-1Ca for not loading static pressure stress is closed
Its impedance of golden sample is significantly greater than two other curve, i.e. the corrosion resistance of Mg-4Li-1Ca alloy sample drops in load static pressure stress
It is low.
It is combined in the present embodiment to polarization curve, Nyquist figure and Bode map analysis, it will thus be seen that static pressure answers masterpiece
With the corrosion electrochemistry of Mg-4Li-1Ca alloy sample can be promoted to react, and result is obvious.
To sum up whole embodiments, actual corrosion electrochemistry test result meet the expection before experiment, and the weight tested
Existing property and reproducibility are good, illustrate having good stability for the experimental rig, can sufficiently meet magnesium alloy and bear in people's bone microenvironment
The correlative study of static pressure stress uses.
Claims (4)
1. a kind of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance, which is characterized in that including electrolytic bath, survey
Trial assembly sets, four part of terminal and electrochemical workstation, wherein electrolytic bath is in the body structure without upper cover, test dress
Placement location is in electrolytic bath；
It is respectively arranged with a feed liquor nozzle and an outlet tube mouth on the arranged on left and right sides wall of the electrolytic bath, feed liquor nozzle and goes out
A circulation loop is connected by pipeline and external reservoir and high precision peristaltic pump respectively on liquid pipe mouth；
The test device is sub-assembly, including rack, digital intelligent pressure transmitter and screw rod regulating part, the rack are
One rectangle frame, the top margin frame center position of rectangle frame offer a first penetrating screw hole；
The screw rod regulating part is sub-assembly, including screw rod and end plate two parts, the upper surface center position of end plate are provided with
The lower part of second screw hole, screw rod is detachably connected by the second screw hole and end plate formation；
The screw rod passes through the top margin frame of rectangle frame through the first screw hole, and the lower part of screw rod is protruded under the top margin frame of rectangle frame
The top of the top margin frame of rectangle frame is stretched out on square, screw rod top；
Radial direction at the upper end position of screw rod along screw rod offers a through-hole, and socket joint is connected with an adjusting in through-hole
Bar；
The upper surface of the bottom edge frame of rectangle frame is provided with an objective table, and the central point of objective table is located at the central axis of the screw rod
On the extended line of line；
The digital intelligent pressure transmitter is bonded in the lower surface of the end plate；
Magnesium alloy sample to be tested is lain in a horizontal plane on objective table；
Digital intelligent pressure transmitter passes through data line and terminal communication connection；
Above-mentioned magnesium alloy sample is square plate, and in four side elevations of plate, a side elevation is completely exposed, and two edge-on
Face is closed with epoxy coating, another side elevation is welded with conducting wire, and after conducting wire is drawn, which is sealed with epoxy resin
Dress, integral sealing；
Surfaces externally and internally, the screw rod of above-mentioned rectangle frame protrude into the outer surface of that section of the lower section of the top margin frame of rectangle frame, end plate
Outer surface and pressure sensor outer surface on, respectively be coated with insulating coating；
Above-mentioned conducting wire is connect with electrochemical workstation, at this point, magnesium alloy sample becomes the job electricity of electrochemical workstation
Pole collectively constitutes together with another working electrode of electrochemical workstation itself institute band as pair in Electrochemical Test Procedure
Electrode.
2. magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance according to claim 1, which is characterized in that
The material of the electrolytic bath is organic glass.
3. magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance according to claim 1, which is characterized in that
Screw thread on first screw hole and screw rod is fine thread.
4. the experimental method of magnesium alloy static pressure stress corrosion electrochemical behavior imitative experimental appliance as described in claim 1,
It is characterized in that, comprising the following steps:
The first step starts terminal, adjusting screw rod, until the pressure for the numerical pressure sensor that terminal is shown
Value is zero；
Second step is slowly injected into Hank ' s solution into electrolytic bath, until magnesium alloy sample is integrally immersed in below liquid level；
The working electrode of electrochemical workstation and reference electrode are inserted into Hank ' s solution by third step respectively；
4th step, imitative experimental appliance is moved entirely into carbon dioxide incubator, and set temperature is 37.5 DEG C；Liquid to be electrolysed
Hank ' s solution temperature in slot rises to 37.5 DEG C, starts peristaltic pump, to drive Hank ' the s solution in electrolytic bath slow
Circulation is wriggled；
5th step starts electrochemical workstation, detects open circuit potential, AC electrochemical impedance spectrum and polarization curve；
6th step detects again by adjusting screw rod so that the pressure registration of digital pressure sensor is increased to setting value
Detection open circuit potential, electrochemical impedance spectroscopy and polarization curve under the setting pressure；
7th step repeats the 6th step, until terminating.
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