CN104977336B - The method and instrument of a kind of quantitative determination oxide-film microdefect - Google Patents
The method and instrument of a kind of quantitative determination oxide-film microdefect Download PDFInfo
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Abstract
The invention discloses a kind of method of quantitative determination oxide-film microdefect, by determining, the pure electronics of oxide-film conducts electric current or resistance and ion migrates electric current or the impedance of formation into oxide-film, the difference and its numerical value of electric current or resistance, the microdefect come in quantization signifying oxide-film are conducted with pure electronics by Ion transfer electric current or impedance.The beneficial effects of the invention are as follows：The method energy objective quantification of the present invention characterizes the situation of oxide-film microdefect, such as defect yardstick, distribution density, and is more than qualitatively understanding, and can reflect distribution situation of the microdefect in macro-scale (10mm)；This method does not need sample preparation, can on sample direct measurement, it is convenient and swift, it is to avoid influence and the influence of human factor that sample making course is caused.
Description
Technical field
The present invention relates to material properties test technical field, in particular it relates to a kind of quantitative determination oxide-film microdefect
Method and instrument.
Background technology
Zircaloy, titanium alloy, uranium alloy, stainless steel etc. are critically important engineering materials, and decay resistance is to influence its work
One of Cheng Yingyong key factor.The oxide-film of densification, resistance can be formed during due to corroding in aqueous medium in material surface
Mass transfer during corrosion is hindered, these materials generally have preferable decay resistance.Corrode the microstructure of the oxide-film formed
Feature (such as internal tiny crack, space) has significant impact to the corrosion behavior of alloy, and alloying component, aqueous medium condition are to alloy
All it is the influence to oxide-film microstructure in the influence of corrosion behavior, its physical essence, therefore oxide-film microstructure characteristic
Analysis and characterization be important content in the research and development of the engineering materials such as zircaloy, titanium alloy, uranium alloy.
At present, the universal means of analysis oxide-film microstructure mainly have X-ray diffractometer, laser Raman spectrum, optical microphotograph
Mirror, scanning electron microscopy, transmission electron microscope etc..X-ray diffractometer and laser Raman spectrum can determine the crystal structure of oxide-film,
The defect in oxide-film can not be analyzed.Because multiplication factor is small, light microscope can observe the thickness of oxide-film roughly, it is impossible to point
Analyse the defect of oxide-film.SEM observable oxide thickness, grain morphology, space and micro-crack.Transmitted electron
The more fine structure of microscope observable oxide-film, such as crystal boundary, nanoscale hole hole, the crystal structure of microcell and crystal grain orientation.
There is following limitation with the microdefect of SEM and transmission electron microscopy microscope observation analysis oxide-film：
(1) microcell is observed, and observation area size is generally less than 10 μm, as a result can not reflect macroscopical situation of sample, in fact
The distribution of microdefect (especially micro-crack) is extremely uneven in oxide-film, it is impossible to represented with the situation of limited several visual fields grand
The situation of sight.
(2) destructive observation, observation oxide-film section, preparation method and analyst of the observed result by micro-analysis sample
The influence of subjective factor is larger.
(3) qualitative observation, cannot comparable, microdefect quantized data.
The content of the invention
The technical problems to be solved by the invention, which are to provide one kind, can reflect microdefect distribution situation, conveniently
The method and instrument of quantitative determination oxide-film microdefect.
Invention it is a kind of objectively, can quantitative determination oxide-film microdefect method to zircaloy, titanium alloy, uranium alloy,
The research and development of the engineering materials such as stainless steel is significant.There is alloying component to conduct electric current to the electronics of oxide-film in the world
Influence research report, but the microdefect influence of conducting electric current to electronics of oxide-film is smaller, therefore can not be used for quantitative determination
The microdefect of oxide-film.
It has been recognised by the inventors that because ion has certain size, if suitable with ion yardstick lack is not present in oxide-film
Fall into, ion will be unable to pass through.Therefore, can be with the yardstick of defect in quantitative analysis oxide-film with dividing by the migratory behaviour of ion
Cloth density.Following technical scheme is inventors herein proposed based on this principle.
The present invention the used technical scheme that solves the above problems is：
A kind of method of quantitative determination oxide-film microdefect, electric current or resistance are conducted by the pure electronics for determining oxide-film
Electric current or the impedance of formation are migrated into oxide-film with ion, electric current or electricity are conducted with pure electronics by Ion transfer electric current or impedance
The difference and its numerical value of resistance, the microdefect come in quantization signifying oxide-film.
The present invention principle be：In electrolyte solution (such as CuSO4Solution) in, there can be cation (such as Cu2+) and bear from
Son (such as SO4 2+), negative ions make directed movement under electric field action, and cation is molten to negative pole and anion to positive polar motion
The motion of negative ions forms electric current in liquid.Thus can be to aoxidize membrane sample as an electrode formation telegraph circuit measure oxidation
The pure electronics conduction electric current or resistance and ion of film migrate electric current or the impedance of formation into oxide-film, respectively by voltmeter and
Ammeter measures the voltage and current of the telegraph circuit.
Using U as impressed DC voltage, Rs is the internal resistance of external dc power supply, and Rv is the internal resistance of voltmeter, and Rc is ammeter
Internal resistance.Rm is the equivalent resistance of metallic matrix wire loop, and Ra is the equivalent resistance of electrolyte solution, and Re is the electricity of oxide-film
Sub- conduction resistance, Ri is the impedance that oxide-film intermediate ion is migrated.Due to big several order of magnitude of Re and Ri ratios Rc, Rm and Ra, because
Electric current I in this ammeter can be approximately：
For the measuring circuit of determination, U, Rv, Rs are known definite value, and the property with oxidation membrane sample to be measured is unrelated.Re and
Ri is relevant with the property of testing sample.The current-voltage correlation (Ie-V curves) for first measuring pure electronics conduction is obtained after resistance Re,
The current-voltage correlation (I-V curve) for determining Ion transfer again obtains Ion transfer impedance Ri.Because ion has certain size,
If oxide-film is very fine and close, ion is difficult to enter, and Ri value is very big, electric current I very littles, with the same order of magnitude at Ie.If oxidation
There are a large amount of defects in film, ion is easy to migrate in oxide-film, and electric current I can be very big.Such as under the voltage of several volts, electric current will
A milliampere magnitude is reached, more than 4 orders of magnitude about bigger than Ie.Therefore the I-V relations or Ri size of sample, directly reflect oxidation
The situation (defect size and quantity) of microdefect in film.
The pure electronics conduction electric current or resistance and ion of described oxide-film migrate electric current or the resistance of formation into oxide-film
Anti- assay method is：
A1 measuring circuit) is connected：The oxide-film for aoxidizing membrane sample is immersed into electrode solution, the metallic matrix of oxidation membrane sample connects
A pole of dc source is connect, another electrode contacted with electrode solution connects another pole of dc source, so that by electrode, electrode
Liquid, oxidation membrane sample formation electrode loop；
A2) the current value and magnitude of voltage in measuring electrode loop, obtains the current-voltage correlation of pure electronics conduction, and then obtains
Pure electronics conduction resistance Re；Obtain the current-voltage correlation of Ion transfer, and then obtain ion migrating impedance Ri into oxide-film.
Test uses DC circuit, and digital electronic ammeter is in series with current-limiting resistance, the resistance of current-limiting resistance 10K to 100K it
Between.
Also include one by the current-voltage correlation that the current-voltage correlation of Ion transfer and pure electronics conduct be converted to from
The step of current density that the current density of son migration is conducted to the relation of electric-field intensity and pure electronics is to the relation of electric-field intensity,
Described current density is the oxide-film area ratio that contact with electrode solution of electric current, electric-field intensity for voltage and oxide thickness it
Than the current density that the current density migrated by reference ion is conducted to the relation of electric-field intensity with pure electronics is to electric-field intensity
Relation reflection microdefect number, the current density of Ion transfer closer to pure electronics conduct when current density, show
Microdefect is fewer in the test spot region, and the current density of Ion transfer more deviates current density when electronics conducts, the survey
Try microdefect in spot region more much bigger.
Described measuring circuit also includes a verification loop in parallel with the electrode loop.Described verification loop one
The positive pole of end connection dc source, verification loop other end connection power cathode, verification is provided with switch on loop, verifies loop
Resistance value be divided into multi gear (such as 3~6 grades), every grade of resistance value is known definite value, and the resistance that one grade of resistance highest is in 100M
Ω magnitudes, minimum one grade of resistance is in 10K Ω magnitudes.
Described electrode solution is liquid metal or electrolyte aqueous solution, liquid when determining the pure electronics conduction electric current of oxide-film
State metal as electrode liquid, electrode solution is made during the Ion transfer electric current for determining oxide-film with electrolyte aqueous solution.
Described electrode is the hollow electrode that bottom is provided with shed cavity volume, and under shed cavity volume passes through portion disposed thereon
Through hole connection is outside, i.e. through hole connection exterior space and under shed cavity volume, the metallic matrix connection direct current of oxidation membrane sample
One pole in source, the hollow electrode connects another pole of dc source.During connection electrode loop, hollow electrode is overlaid on oxide-film sample
On the oxide-film of product, the lower surface of under shed cavity volume is closed by oxidation membrane sample, then passes through through hole iontophoresis electrode liquid, electrode solution
Leaching is overlying on positioned at the surface of under shed cavity volume internal oxidition film, and electrode solution contacts the side wall of under shed cavity volume simultaneously, so that in realizing
The electrical connection of empty electrode and electrode solution.
Described under shed cavity volume is circular cylindrical cavity, after hollow electrode is pressed on sample, can be passed through from its top logical
Hole adds electrode solution, the radius of under shed cavity volume 0.5 between 6mm, it is embedding on the end face that hollow electrode lower end is contacted with oxide-film
There is heat resistant rubber sealing ring.
Described oxidation membrane sample fixed placement is on sample stage, and sample stage is internally provided with to be added to oxidation membrane sample
The heater of heat.For example, sample stage can use stainless steel, it is internally provided with a sky for being used to accommodate heater
Chamber, heater is sealed in the cavity, so that sample stage turns into the rustless steel container of a receiving heater.Determine oxide-film
Pure electronics conduction electric current when, insert low-melting-point metal to the under shed cavity volume of the hollow electrode, the heater of sample stage can
To be heated to oxidation membrane sample, and then by aoxidizing low melting point gold of the heat transfer realization to oxidation membrane sample top of membrane sample
Category is heated, and by controlling the temperature of oxidation membrane sample, melts the low-melting-point metal in the under shed cavity volume of hollow electrode
Into liquid, it is filled in the under shed cavity volume of oxidation membrane closure, liquid metals leaching is overlying on positioned under shed cavity volume internal oxidition film
Surface, liquid metals contacts the side wall of under shed cavity volume to realize the electrical connection of hollow electrode and liquid metals simultaneously.
Described low-melting-point metal can be for gallium (Ga), indium (In) or gallium-indium alloy.
When determining the pure electronics conduction electric current of oxide-film, load gallium (Ga) in the inner chamber of hollow electrode, then by electricity
Pole is pressed on oxide-film.The positive pole of dc source is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Vacuum (-tight) housing is covered, starts vavuum pump.When the gas pressure intensity of sample room is less than 10kPa, begin to warm up.Make sample temperature
Stabilization is at 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, is covered in electrode on the oxide-film in alveolus, and with gold
Belong to hollow electrode interior contact, form positive electrode.
Dc source is opened, the current values under different voltages are recorded, the current-voltage correlation of pure electronics conduction is obtained
Ie-V curves.The resistance Re of oxide-film when can calculate pure electronics conduction by the curve.By the resistance and hollow electrode inner chamber
The thickness of radius and oxide-film, can calculate the resistivity of oxide-film.Usually, if gross imperfection is not present (such as in oxide-film
Be damaged) or oxide-film by before electric field breakdown, the resistivity of oxide-film is very big, 3 × 109More than Ω m, Ie very little.For
The Zircaloy Oxide Film that about 2 μm of thickness, the hollow electrode for being 6mm with inner chamber radius, under 40V voltages, Ie is less than 500nA,
Under 10V voltages, Ie is less than 50nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 107More than V/m.
After the completion of the current-voltage correlation Ie-V curves test of pure electronics conduction, stop heating, close dc source.Close
Vavuum pump, opening vacuum chamber, remove the gallium of hollow electrode inner chamber.
The electrolyte of described electrolyte aqueous solution can be lithium hydroxide, potassium hydroxide, sodium hydroxide, lithium chloride, chlorine
Change potassium, sodium chloride, calcium chloride, sodium sulphate, potassium sulfate, copper sulphate, the concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, transfer ability of the ion in oxide-film is variant, and I-V curve is variant.It is right
Than the microdefect situation for analyzing different samples, electrolyte aqueous solution of the same race need to be used.
When determining the Ion transfer electric current of oxide-film, electrode is moved on on oxide-film behind setting position, by hollow electrode pressure
Tightly on oxide-film.Electrolyte solution is instilled from the upper end of hollow electrode.Electrolyte is full of after hollow electrode, by vacuum electrode
Portion is connected with positive source.Dc source is opened, the current values under different voltages are recorded, the electric current electricity of Ion transfer is obtained
Press relations I-V curves.After having tested, dc source is closed.
By using the different hollow electrode of inner chamber radius, the uniform implementations of defect distribution in oxide-film can be determined.
The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radiuses is identical.By a plurality of
The difference of the current-voltage correlation I-V curve of Ion transfer and the current-voltage correlation Ie-V curves of pure electronics conduction can reflect
The uniform implementations of defect distribution in oxide-film.
The current-voltage correlation I-V curve of the Ion transfer measured and the current-voltage correlation Ie-V curves of pure electronics conduction
Contrast can not be used directly to, there are two aspect reasons：One is the thickness difference of oxide-film, under same voltage, oxide-film
Interior electric-field intensity is different, and the driving force that ion is subject to is different；Two be the inner chamber radius difference of hollow electrode, conduction
Area is different.The relation of current vs voltage is needed to be converted into relation (J-E curve) of the current density to electric-field intensity.Electricity
Current density is the oxide-film area ratio that electric current is contacted with electrode solution, and electric-field intensity is the ratio between voltage and oxide thickness.In order to
Intuitive and convenient, the unit of the two takes nA/mm respectively2With V/ μm.
The current density of Ion transfer is smaller, current density when being conducted closer to pure electronics, shows in test spot region,
Transference cell very little of the ion in oxide-film, that is, the microdefect in the area are seldom.The electric current of the electric current of Ion transfer is close
Degree is bigger, illustrates there is larger defect (such as crackle) in the area.
Implement a kind of instrument of the method for above-mentioned quantitative determination oxide-film microdefect, including sample stage, oxidation membrane sample,
Dc source and electrode, oxidation membrane sample are placed on sample stage, and one is provided with sample stage is used to carry out oxidation membrane sample
The electric heater of heating, electrode is overlaid on oxidation membrane sample, and by the under shed of oxidation membrane sample enclosed electrode, electrode base is set
Under shed cavity volume is equipped with, electrode upper is provided with through hole, and under shed cavity volume connects outside by the through hole in portion disposed thereon, electrode
Under shed cavity volume in be filled with electrode solution, electrode connects a pole of dc source, and the metallic matrix connection of oxidation membrane sample is straight
Flow and be provided with another pole of power supply, electrode, electrode solution, oxidation membrane sample formation electrode loop, electrode loop for measuring electricity
The current value in pole loop and the ammeter of magnitude of voltage and voltmeter, described sample stage, oxidation membrane sample and electrode are located at one
In vacuum chamber, vacuum chamber is made up of chassis and the vacuum (-tight) housing being covered on chassis.
Tester mainly includes vacuum specimen chamber and observing and controlling electronic circuit two large divisions.With oil-sealed rotary pump to sample room
Vacuumize.Sample stage is placed in sample room.Hollow electrode and test sample can be fixed by sample stage.Sample stage is also to test specimens
Product are heated.Different electrode solutions, such as liquid metal or electrolyte aqueous solution, topping up state gold are filled in the inner chamber of hollow electrode
The electronics conduction behavior of oxide-film, the migratory behaviour of measured ion when filling electrolyte aqueous solution are surveyed during category.
Also include a verification loop in parallel with the electrode loop, described verification loop one end connection dc source
Positive pole, verification loop other end connection power cathode, verification is provided with switch on loop, verify loop resistance value be divided into it is many
Shelves (such as 3~6 grades), every grade of resistance value is known definite value, and the resistance that one grade of resistance highest is in 100M Ω magnitudes, minimum one grade
Resistance in 10K Ω magnitudes.Due to atomic weak signal (10-10A measurement), easily disturbed by instrument thermal noise and environmental noise,
And influenceed by electronic component aging.In order to ensure test result accurately and reliably, school is parallel with the electrode loop of test
Test loop.Before sample test, with verification loop tester working condition whether normal reliable.Verify the resistance stepping in loop
Variable, each grade of resistance is known definite value.Minimum one grade of resistance value is most high-grade in 100M Ω magnitudes in 10K Ω magnitudes.School
Can be divided by testing the resistance value in loop by 3~6 grades, and stepping is more, and verification is more reliable, and the resistance difference between shelves is divided equally using logarithm.This instrument
Five grades, five grades of resistance value is divided to respectively may be about 10K Ω, 100K Ω, 1M Ω, 10M Ω and 100M Ω in device.Instrument is verified
When, instrument dc source is opened, closure verification loop simultaneously disconnects test loop.The voltage output of dc source is adjusted, in direct current
When voltage output is 1.0V, 2.0V, 3.0V, current value when verification loop takes different resistance values is measured respectively.Due to verifying back
Each shelves resistance on road is known fixed value, therefore when examining every time, the current value under identical voltage and resistance is to reproduce,
And energy and theoretical calculation.Otherwise the state of instrument is abnormal, needs to check.
When the state of instrument is normal, a ready Zircaloy Oxide Film sample is taken, is placed on sample stage.Make sample
The metal shell of the zirconium metal in close contact heater exposed on product, the resistance between measurement zirconium metal and sample stage, if resistance
Less than 2 Ω, illustrate that zirconium metal is good with sample stage and with the electrical contact of instrument common ground, follow-up test can be carried out.
Described under shed cavity volume is circular cylindrical cavity, after hollow electrode is pressed on sample, can be passed through from its top logical
Hole adds electrode solution, the radius of under shed cavity volume 0.5 between 6mm, it is embedding on the end face that hollow electrode lower end is contacted with oxide-film
There is heat resistant rubber sealing ring.The size of hollow electrode inner chamber has a significant impact to test result.Defect point in oxide-film
Cloth is extremely uneven.Chamber size is bigger in electrode, can more reflect macroscopical average effect of alumina diaphragm defect distribution.To analysis
The microcell difference of defect distribution, preferably with less interior chamber size.In the present invention, the inner chamber radius of hollow electrode has three kinds：
0.5mm, 3mm and 6mm, are measured for various purposes.
Digital instrument for atomic weak signal measurement is not only very expensive but also is easily damaged.Different sample oxidation films
Microdefect situation is widely different, the amplitude of variation of Ion transfer electric current will up to 6 orders of magnitude, from less than 1 na to several milliamperes.
Even if in same sample, due to the skewness of microdefect, different positions, Ion transfer current difference may also reach
To 5 number magnitudes.For the safety of digital electronic ammeter, digital electronic ammeter needs series limiting resistor, make whenever electric current
The electric current flowed through in table is no more than safety value.Current-limiting resistance can current-limiting resistance be about between 10K Ω to 100K Ω, in this instrument
10KΩ。
Mainly include using this instrument, the step of quantitative determination oxide-film microdefect：Preparation of samples, instrument state school
Test, electronics conduction Ie-V curve determinations, Ion transfer I-V curve measures, defect distribution uniformity, data processing six are walked
Suddenly.
Described electric heater passes through connection temperature controller.
Sample stage is fixed on the top on the chassis of vacuum chamber, and the side wall of electrode is in stepped ramp type, an adjustable for height level
Pressing plate is overlaid on the step surface of electrode, so as to be pressed in motor on oxidation membrane sample by pressing plate.
Multiple screwed holes are provided with described horizontal pressure foot, screw thread borehole jack is loaded on the screw rod being vertically arranged, and passes through rotation
The upright position of horizontal pressure foot can be adjusted by turning screw rod.It is preferred that, described sample stage passes through multiple strut supports, screw rod rotation
Pole is arranged above or on sample stage.
To sum up, the beneficial effects of the invention are as follows：
1st, method of the invention reflects distribution situation of the microdefect in macro-scale (10mm).
2nd, method energy objective quantification of the invention characterizes the situation of oxide-film microdefect, such as defect yardstick, distribution density
Deng, and be more than qualitatively understanding.
3rd, this method does not need sample preparation, can on sample direct measurement, it is convenient and swift, it is to avoid the shadow that sample making course is caused
The influence of sound and human factor.
Brief description of the drawings
Fig. 1 is the test philosophy figure of the present invention；
Fig. 2 is Fig. 1 equivalent circuit diagram；
Fig. 3 is the structural scheme of mechanism of instrument of the present invention；
Fig. 4 is different-thickness Zircaloy Oxide Film sample microdefect quantitative determination result；
Fig. 5 is the J-E curves of oxide-film when electrode radius is different.
Mark and corresponding parts title in accompanying drawing：
1- sample stages, 2- oxidation membrane samples, 3- dc sources, 4- electrodes, 5- electric heaters, 6- electrode solutions, 7- ammeters,
8- voltmeters, 9- verifications loop, 10- temperature controllers, 11- chassis, 12- vacuum (-tight) housings, 13- horizontal pressure foots, 14- screw rods, 15- poles.
Embodiment
The present invention will now be described in further detail with reference to the accompanying drawings and the accompanying drawings, but embodiments of the present invention
Not limited to this.
Embodiment：
A kind of method of quantitative determination oxide-film microdefect, electric current or resistance are conducted by the pure electronics for determining oxide-film
Electric current or the impedance of formation are migrated into oxide-film with ion, electric current or electricity are conducted with pure electronics by Ion transfer electric current or impedance
The difference and its numerical value of resistance, the microdefect come in quantization signifying oxide-film.
As shown in Figure 1, principle of the invention is：In electrolyte solution (such as CuSO4Solution) in, there can be cation
(such as Cu2+) and anion (such as SO4 2+), negative ions make directed movement under electric field action, and cation is to negative pole and anion
To positive polar motion, the motion of negative ions forms electric current in solution, its equivalent circuit such as accompanying drawing 2.Thus can be with oxide-film sample
Product are that the pure electronics that an electrode formation telegraph circuit determines oxide-film conducts electric current or impedance and ion is migrated into oxide-film
The electric current of formation or impedance, measure the voltage and current of the telegraph circuit by voltmeter and ammeter respectively.
In accompanying drawing 2, using U as impressed DC voltage, Rs is the internal resistance of external dc power supply, and Rv is the internal resistance of voltmeter, Rc
For the internal resistance of ammeter.Rm is the equivalent resistance of metallic matrix wire loop, and Ra is the equivalent resistance of electrolyte solution, and Re is oxygen
Change the electronics conduction resistance of film, Ri is the impedance that oxide-film intermediate ion is migrated.Due to the big several numbers of Re and Ri ratios Rc, Rm and Ra
Electric current I in magnitude, therefore ammeter can be approximately：
For the measuring circuit of determination, U, Rv, Rs are known definite value, and the property with oxidation membrane sample to be measured is unrelated.Re and
Ri is relevant with the property of testing sample.The current-voltage correlation (Ie-V curves) for first measuring pure electronics conduction is obtained after resistance Re,
The current-voltage correlation (I-V curve) for determining Ion transfer again obtains Ion transfer impedance Ri.Because ion has certain size,
If oxide-film is very fine and close, ion is difficult to enter, and Ri value is very big, electric current I very littles, with the same order of magnitude at Ie.If oxidation
There are a large amount of defects in film, ion is easy to migrate in oxide-film, and electric current I can be very big.Such as under the voltage of several volts, electric current will
A milliampere magnitude is reached, more than 4 orders of magnitude about bigger than Ie.Therefore the I-V relations or Ri size of sample, directly reflect oxidation
The situation (defect size and quantity) of microdefect in film.
The pure electronics conduction electric current or resistance and ion of described oxide-film migrate electric current or the resistance of formation into oxide-film
Anti- assay method is：
A1 measuring circuit) is connected：The oxide-film for aoxidizing membrane sample is immersed into electrode solution, the metallic matrix of oxidation membrane sample connects
A pole of dc source is connect, the metallic matrix of oxidation membrane sample can connect the negative pole or positive pole of dc source, it is preferable that oxidation
The metallic matrix of membrane sample connects the negative pole of dc source, and another electrode contacted with electrode solution connects the another of dc source
Pole, i.e., when the metallic matrix for aoxidizing membrane sample connects the negative pole of dc source, the connection of another electrode contacted with electrode solution
The positive pole of dc source, otherwise conversely, so as to form electrode loop by electrode, electrode solution, oxidation membrane sample；
A2) the current value and magnitude of voltage in measuring electrode loop, obtains the current-voltage correlation of pure electronics conduction, and then obtains
Pure electronics conduction resistance Re；Obtain the current-voltage correlation of Ion transfer, and then obtain ion migrating impedance Ri into oxide-film.
Test uses DC circuit, and digital electronic ammeter is in series with current-limiting resistance, and the resistance of current-limiting resistance is between 10K to 100K.
Also include one by the current-voltage correlation that the current-voltage correlation of Ion transfer and pure electronics conduct be converted to from
The step of current density that the current density of son migration is conducted to the relation of electric-field intensity and pure electronics is to the relation of electric-field intensity,
Described current density is the oxide-film area ratio that contact with electrode solution of electric current, electric-field intensity for voltage and oxide thickness it
Than the current density that the current density migrated by reference ion is conducted to the relation of electric-field intensity with pure electronics is to electric-field intensity
Relation reflection microdefect number, the current density of Ion transfer closer to pure electronics conduct when current density, show
Microdefect is fewer in the test spot region, and the electric current that the current density of the electric current of Ion transfer more deviates when electronics conducts is close
Microdefect is more much bigger in degree, the test spot region.
Described measuring circuit also includes a verification loop in parallel with the electrode loop.Described verification loop one
The positive pole of end connection dc source, verification loop other end connection power cathode, verification is provided with switch on loop, verifies loop
Resistance value be divided into multi gear (such as 3~6 grades), every grade of resistance value is known definite value, and the resistance that one grade of resistance highest is in 100M
Ω magnitudes, minimum one grade of resistance is in 10K Ω magnitudes.
Described electrode solution is liquid metal or electrolyte aqueous solution, liquid when determining the pure electronics conduction electric current of oxide-film
State metal as electrode liquid, electrode solution is made during the Ion transfer electric current for determining oxide-film with electrolyte aqueous solution.
Described electrode is the hollow electrode that bottom is provided with shed cavity volume, and under shed cavity volume passes through portion disposed thereon
Through hole connection is outside, i.e. through hole connection exterior space and under shed cavity volume, the metallic matrix connection direct current of oxidation membrane sample
One pole in source, the hollow electrode connects another pole of dc source.During connection electrode loop, hollow electrode is overlaid on oxide-film sample
On the oxide-film of product, the lower surface of under shed cavity volume is closed by oxidation membrane sample, then passes through through hole iontophoresis electrode liquid, electrode solution
Leaching is overlying on positioned at the surface of under shed cavity volume internal oxidition film, and electrode solution contacts the side wall of under shed cavity volume simultaneously, so that in realizing
The electrical connection of empty electrode and electrode solution.
The under shed cavity volume of described hollow electrode is circular cylindrical cavity, can be from it after hollow electrode is pressed on sample
Top adds electrode solution by through hole, and the radius of under shed cavity volume is 0.5 between 6mm, and hollow electrode lower end is contacted with oxide-film
End face on be embedded with heat resistant rubber sealing ring.
Described oxidation membrane sample fixed placement is on sample stage, and sample stage is internally provided with to be added to oxidation membrane sample
The heater of heat.For example, sample stage can use stainless steel, it is internally provided with a sky for being used to accommodate heater
Chamber, heater is sealed in the cavity, so that sample stage turns into the rustless steel container of a receiving heater.Determine oxide-film
Pure electronics conduction electric current when, insert low-melting-point metal to the under shed cavity volume of the hollow electrode, the heater of sample stage can
To be heated to oxidation membrane sample, and then by aoxidizing low melting point gold of the heat transfer realization to oxidation membrane sample top of membrane sample
Category is heated, and by controlling the temperature of oxidation membrane sample, melts the low-melting-point metal in the under shed cavity volume of hollow electrode
Into liquid, it is filled in the under shed cavity volume of oxidation membrane closure, liquid metals leaching is overlying on positioned under shed cavity volume internal oxidition film
Surface, liquid metals contacts the side wall of under shed cavity volume to realize the electrical connection of hollow electrode and liquid metals simultaneously.
Described low-melting-point metal can be for gallium (Ga), indium (In) or gallium-indium alloy.
When determining the pure electronics conduction electric current of oxide-film, load gallium (Ga) in the inner chamber of hollow electrode, then by electricity
Pole is pressed on oxide-film.The positive pole of dc source is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Vacuum (-tight) housing is covered, starts vavuum pump.When the gas pressure intensity of sample room is less than 10kPa, begin to warm up.Make sample temperature
Stabilization is at 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, is covered in electrode on the oxide-film in alveolus, and with gold
Belong to hollow electrode interior contact, form electrode.
Dc source is opened, the current values under different voltages are recorded, the current-voltage correlation of pure electronics conduction is obtained
Ie-V curves.The resistance Re of oxide-film when can calculate pure electronics conduction by the curve.By the resistance and hollow electrode inner chamber
The thickness of radius and oxide-film, can calculate the resistivity of oxide-film.Usually, if gross imperfection is not present (such as in oxide-film
Be damaged) or oxide-film by before electric field breakdown, the resistivity of oxide-film is very big, 3 × 109More than Ω m, Ie very little.For
The Zircaloy Oxide Film that about 2 μm of thickness, the hollow electrode for being 6mm with inner chamber radius, under 40V voltages, Ie is less than 500nA,
Under 10V voltages, Ie is less than 50nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 107More than V/m.
After the completion of the current-voltage correlation Ie-V curves test of pure electronics conduction, stop heating, close dc source.Close
Vavuum pump, opening vacuum chamber, remove the gallium of hollow electrode inner chamber.
The electrolyte of described electrolyte aqueous solution can be lithium hydroxide, potassium hydroxide, sodium hydroxide, lithium chloride, chlorine
Change potassium, sodium chloride, calcium chloride, sodium sulphate, potassium sulfate, copper sulphate, the concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, transfer ability of the ion in oxide-film is variant, and I-V curve is variant.It is right
Than the microdefect situation for analyzing different samples, electrolyte aqueous solution of the same race need to be used.
When determining the Ion transfer electric current of oxide-film, electrode is moved on on oxide-film behind setting position, by hollow electrode pressure
Tightly on oxide-film.Electrolyte solution is instilled from the upper end of hollow electrode.Electrolyte is full of after hollow electrode, by vacuum electrode
Portion is connected with positive source.Dc source is opened, the current values under different voltages are recorded, the electric current electricity of Ion transfer is obtained
Press relations I-V curves.After having tested, dc source is closed.
By using the different hollow electrode of inner chamber radius, the uniform implementations of defect distribution in oxide-film can be determined.
The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radiuses is identical.By a plurality of
The difference of the current-voltage correlation I-V curve of Ion transfer and the current-voltage correlation Ie-V curves of pure electronics conduction can reflect
The uniform implementations of defect distribution in oxide-film.
The current-voltage correlation I-V curve of the Ion transfer measured and the current-voltage correlation Ie-V curves of pure electronics conduction
Contrast can not be used directly to, there are two aspect reasons：One is the thickness difference of oxide-film, under same voltage, oxide-film
Interior electric-field intensity is different, and the driving force that ion is subject to is different；Two be the inner chamber radius difference of hollow electrode, conduction
Area is different.The relation of current vs voltage is needed to be converted into relation (J-E curve) of the current density to electric-field intensity.Electricity
Current density is the oxide-film area ratio that electric current is contacted with electrode solution, and electric-field intensity is the ratio between voltage and oxide thickness.In order to
Intuitive and convenient, the unit of the two takes nA/mm respectively2With V/ μm.
The current density of Ion transfer is smaller, current density when being conducted closer to pure electronics, shows in test spot region,
Transference cell very little of the ion in oxide-film, that is, the microdefect in the area are seldom.The current density of Ion transfer is bigger,
Illustrate there is larger defect (such as crackle) in the area.
As shown in figure 3, implement a kind of above-mentioned instrument of the method for quantitative determination oxide-film microdefect, including sample stage 1,
Membrane sample 2, dc source 3 and electrode 4 are aoxidized, oxidation membrane sample 2 is placed on sample stage 1, and one is provided with sample stage 1 is used for
The electric heater 5 heated to oxidation membrane sample 2, electrode 4 is overlaid on oxidation membrane sample 2, and electricity is sealed by oxidation membrane sample 2
The under shed of pole 4, the bottom of electrode 4 is provided with shed cavity volume, and the top of electrode 4 is provided with through hole, under shed cavity volume by positioned at
The through hole connection on its top is outside, and electrode solution 6, the one of the connection dc source 3 of electrode 4 are filled with the under shed cavity volume of electrode 4
Pole, the metallic matrix of oxidation membrane sample 2 connects another pole of dc source 3, and the metallic matrix of oxidation membrane sample 2 can be connected directly
Flow the negative pole or positive pole of power supply 3, it is preferable that the metallic matrix of oxidation membrane sample 2 connects the negative pole of dc source 3, and electrode 4 is connected
Another pole of dc source 3, i.e., when the metallic matrix for aoxidizing membrane sample 2 connects the negative pole of dc source 3, another and electrode
The electrode 4 that liquid 6 is contacted connects the positive pole of dc source 3, otherwise conversely, so as to which electrode 4, electrode solution, oxidation membrane sample 2 are formed
The ammeter 7 and voltmeter of the current value and magnitude of voltage for the loop of measuring electrode 4 are provided with the loop of electrode 4, the loop of electrode 4
8, described sample stage 1, oxidation membrane sample 2 and electrode 4 is located in a vacuum chamber, and vacuum chamber is by chassis 11 and is covered on chassis
Vacuum (-tight) housing 12 on 11 is constituted.
Tester mainly includes vacuum specimen chamber and observing and controlling electronic circuit two large divisions.With oil-sealed rotary pump to sample room
Vacuumize.Sample stage 1 is placed in sample room.Hollow electrode 4 and test sample can be fixed by sample stage 1.Sample stage 1 is also to surveying
Test agent is heated.Different electrode solutions 6 are filled in the inner chamber of hollow electrode 4, such as liquid metal or electrolyte aqueous solution fill
The electronics conduction behavior of oxide-film, the migratory behaviour of measured ion when filling electrolyte aqueous solution are surveyed during liquid metal.
Also include a verification loop 9 in parallel with the loop of electrode 4, the described one end of verification loop 9 connection direct current
The positive pole of power supply 3, the verification other end of loop 9 connection power cathode, verification is provided with switch on loop 9, verifies the resistance in loop 9
Value is divided into multi gear, and such as 3~6 grades, every grade of resistance value is known definite value, the resistance that one grade of resistance highest in 100M Ω magnitudes,
Minimum one grade of resistance is in 10K Ω magnitudes.Due to atomic weak signal (10-10A measurement), is easily made an uproar by instrument thermal noise and environment
The interference of sound and influenceed by electronic component aging.In order to ensure test result accurately and reliably, the electrode 4 times with test
Road is parallel with verification loop 9.Before sample test, with verification the tester of loop 9 working condition whether normal reliable.Verify back
The resistance stepping on road 9 is variable, and each grade of resistance is known definite value.Minimum one grade of resistance value in 10K Ω magnitudes, it is most high-grade
100M Ω magnitudes.The resistance value in verification loop 9 can divide 3~6 grades, and stepping is more, verify more reliable, the resistance difference use between shelves
Logarithm is divided equally.Five grades, five grades of resistance value is divided to respectively may be about 10K Ω, 100K Ω, 1M Ω, 10M Ω and 100M Ω in this instrument.
When instrument is verified, instrument dc source 3 is opened, closure verification loop 9 simultaneously disconnects test loop.Adjust dc source 3
Voltage output, when direct voltage output is 1.0V, 2.0V, 3.0V, measures electricity when verification loop 9 takes different resistance values respectively
Flow valuve.Because each shelves resistance for verifying loop 9 is known fixed value, therefore when examining every time, under identical voltage and resistance
Current value is to reproduce, and energy and theoretical calculation.Otherwise the state of instrument is abnormal, needs to check.
When the state of instrument is normal, a ready Zircaloy Oxide Film sample 2 is taken, is placed on sample stage 1.Make
The metal shell of the zirconium metal in close contact heater exposed on sample, the resistance between measurement zirconium metal and sample stage 1, if electric
Resistance is less than 2 Ω, illustrates that zirconium metal is good with sample stage 1 and with the electrical contact of instrument common ground, can carry out follow-up test.
Described under shed cavity volume is circular cylindrical cavity, after hollow electrode 4 is pressed on sample, can be passed through from its top logical
Hole adds electrode solution 6, the radius of under shed cavity volume 0.5 between 6mm, on the end face that the lower end of hollow electrode 4 is contacted with oxide-film
It is embedded with heat resistant rubber sealing ring.The size of the inner chamber of hollow electrode 4 has a significant impact to test result.Defect in oxide-film
Distribution is extremely uneven.Chamber size is bigger in electrode 4, can more reflect macroscopical average effect of alumina diaphragm defect distribution.To
The microcell difference of analyzing defect distribution, preferably with less interior chamber size.In the present invention, the inner chamber radius of hollow electrode 4 has three kinds：
0.5mm, 3mm and 6mm, are measured for various purposes.
Digital instrument for atomic weak signal measurement is not only very expensive but also is easily damaged.Different sample oxidation films
Microdefect situation is widely different, the amplitude of variation of Ion transfer electric current will up to 6 orders of magnitude, from less than 1 na to several milliamperes.
Even if in same sample, due to the skewness of microdefect, different positions, Ion transfer current difference may also reach
To 5 number magnitudes.For the safety of digital electronic ammeter 7, digital electronic ammeter 7 needs series limiting resistor, whenever electric makes
The electric current flowed through in flow table 7 is no more than safety value.Current-limiting resistance can be between 10K Ω to 100K Ω, current-limiting resistance in this instrument
About 10K Ω.
Mainly include using this instrument, the step of quantitative determination oxide-film microdefect：Preparation of samples, instrument state school
Test, electronics conduction Ie-V curve determinations, Ion transfer I-V curve measures, defect distribution uniformity, data processing six are walked
Suddenly.
Described electric heater 5 passes through connection temperature controller 10.
Described sample stage 1, oxidation membrane sample 2 and electrode 4 is located in a vacuum chamber.
Vacuum chamber is made up of chassis 11 and the vacuum (-tight) housing 12 being covered on chassis 11, and sample stage 1 is fixed on the bottom of vacuum chamber
The top of disk 11, the side wall of electrode 4 is in stepped ramp type, and an adjustable for height horizontal pressure foot 13 is overlaid on the step surface of electrode 4,
So as to motor is pressed on oxidation membrane sample 2 by pressing plate.There is an insulation spacer between pressing plate and 4, electrode.
Multiple screwed holes are provided with described horizontal pressure foot 13, screw thread borehole jack is loaded on the screw rod 14 being vertically arranged, and is led to
The upright position of horizontal pressure foot 13 can be adjusted by crossing rotary screw 14.Described sample stage 1 is supported by multiple poles 15.
Below by taking Zircaloy Oxide Film sample as an example, the quantization of microdefect in oxide-film of the present invention is described in detail
Method of testing and testing procedure.
1. test sample prepares
The sample of sheet is tested using the zircaloy corrosion of 10 different oxide thickness, sample size is about 20 × 30 ×
1.5mm, subordinate list 1 is the oxide thickness of sample.The sample of different oxide thickness, its preparation of samples and testing procedure are identical
's.
The oxide thickness (μm) of the Zircaloy Oxide Film sample of subordinate list 1
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | Re |
| Thickness | 0.9 | 1.7 | 4.4 | 5.3 | 11 | 21 | 31 | 43 | 59 | 1.5 |
In a termination of Zircaloy Oxide Film sample, oxide film dissolving is gone by mechanical means (as polished), to expose zirconium
Metal.The metal area field width about 2mm exposed, it is then that sample clean is clean, it is to be measured.
2. instrument state is verified
Instrument dc source is opened, closure verification loop simultaneously disconnects test loop.The voltage output of dc source is adjusted,
When direct voltage output is 1.0V, 2.0V, 3.0V, current value when verification loop takes different resistance values is measured respectively.Due to school
Each shelves resistance for testing loop is known fixed value, therefore when examining every time, the current value under identical voltage and resistance is can be again
Existing, and energy and theoretical calculation.Otherwise the state of instrument is abnormal, needs to check.
When the state of instrument is normal, a ready Zircaloy Oxide Film sample is taken, is placed on sample stage.Make sample
The metal shell of the zirconium metal in close contact heater exposed on product, the resistance between measurement zirconium metal and sample stage, if resistance
Less than 2 Ω, illustrate that zirconium metal is good with sample stage and with the electrical contact of instrument common ground, follow-up test can be carried out.
3. electronics conducts Ie-V curve determinations
Load gallium (Ga) in the inner chamber of hollow electrode, then electrode is pressed on oxide-film.By dc source
Positive pole is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Vacuum (-tight) housing is covered, starts vavuum pump.When the gas pressure intensity of sample room is less than 10kPa, begin to warm up.Make sample temperature
Stabilization is at 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, is covered in electrode on the oxide-film in alveolus, and with gold
Belong to hollow electrode interior contact, form positive electrode.
Dc source is opened, the current values under different voltages are recorded, the Ie-V curves of pure electronics conduction are obtained.By this
The resistance Re of oxide-film when curve can calculate pure electronics conduction.Radius and oxide-film by the resistance and hollow electrode inner chamber
Thickness, the resistivity of oxide-film can be calculated.Usually, if gross imperfection (being such as damaged) or oxidation is not present in oxide-film
Film is by before electric field breakdown, and the resistivity of oxide-film is very big, 3 × 109More than Ω m, Ie very little.For about 2 μm of zirconium of thickness
Alloy oxide film, the hollow electrode for being 6mm with inner chamber radius, under 40V voltages, Ie is less than 500nA, and under 10V voltages, Ie is small
In 50nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 107More than V/m.
After the completion of the Ie-V curves test of pure electronics conduction, stop heating, close dc source.Close vavuum pump, open
Vacuum chamber, removes the gallium of hollow electrode inner chamber.
4. Ion transfer I-V curve is determined
Prepare electrolyte aqueous solution.Available electrolyte has lithium hydroxide (LiOH), potassium hydroxide (KOH), sodium hydroxide
(NaOH), lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl2), sodium sulphate (Na2SO4), sulfuric acid
Potassium (K2SO4), copper sulphate (CuSO4).The concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, transfer ability of the ion in oxide-film is variant, and I-V curve is variant.It is right
Than the microdefect situation for analyzing different samples, electrolyte aqueous solution of the same race need to be used.
Electrode is moved on to after the other positions on oxide-film, hollow electrode is pressed on oxide-film.From hollow electrode
It (is LiOH and CuSO in the present embodiment that upper end, which instills electrolyte solution,4).Electrolyte is full of after hollow electrode, by vacuum electrode
Portion is connected with positive source.
Dc source is opened, the current values under different voltages is recorded, obtains I-V curve during ionic conduction.Survey
After having tried, dc source is closed.
5. defect distribution uniformity
By using the different hollow electrode of inner chamber radius, the uniform implementations of defect distribution in oxide-film can be determined.
The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radiuses is identical with step 4.
The hollow electrode for being first 0.5mm with inner chamber radius 10 points of random test on sample, obtain 10 I-V songs
Line.Because the defect at each measuring point can be different, such as some measuring points encounter micro-crack, and there were significant differences for the typically meeting of this 10 curves,
Represented using the minimum curve of current value as the group.The hollow electrode for being again 3mm with inner chamber radius surveys 4 points at random on sample,
4 I-V curves are obtained, are equally represented using the minimum curve of current value as the group.The hollow electrode for being finally 6mm with inner chamber radius
Survey 1 point at random on sample, obtain 1 I-V curve.
The difference of curve, an Ie-V curve and inner chamber radius as 6mm I-V curve, totally four curves is represented by two
The uniform implementations of defect distribution in oxide-film can be reflected.
6. data processing
There are two aspect reasons, the I-V curve measured can not be used directly to contrast.One is the thickness difference of oxide-film, even if
Under same voltage, the electric-field intensity in oxide-film is different, and the driving force that ion is subject to is different；Two be hollow electricity
The inner chamber radius of pole is different, and conduction surface is different.Need the relation (I-V curve) of current vs voltage to be converted into electric current close
Spend the relation (J-E curves) to electric-field intensity.Current density is the oxide-film area ratio that electric current is contacted with electrode solution, electric-field strength
Spend for the ratio between voltage and oxide thickness.For intuitive and convenient, the unit of the two takes nA/mm respectively2With V/ μm.
Accompanying drawing 4 is the test result of 10 Zircaloy Oxide Film samples in subordinate list 1, wherein numbering Re curve is pure electronics
J-E curves during conduction, its electrode solution of other curves is the LiOH aqueous solution, and solution concentration is 0.02M.It can be seen that J-E
Curve delicately reflects the situation of change of defect during oxide growth.With the increase of oxide thickness, curve is moved to left, and is said
The defect of bright inside is more and more.
Accompanying drawing 5 is the result tested with the electrode of three kinds of different inner chambers radiuses No. 3 samples.Electrode solution is CuSO4
The aqueous solution, solution concentration is 0.1M.When electrode inner chamber is small-sized, the oxidation membrane area very little being related to, in same electric field
Under intensity, current density very little, current density when almost being conducted close to pure electronics shows in test spot region, ion is in oxygen
Transference cell very little in change film, that is, the microdefect in the area are seldom.With measurement spot area increase, current density significantly increases
Greatly, this contribution for being mainly Ion transfer electric current, illustrates there is larger defect (such as crackle) in the area, that is, defect point
Cloth is not uniform, and there is crackle in the region of some in oxide-film, and other region may not have.Inner chamber radius is bigger, surveys in spot and exists
The probability of defect is bigger, therefore Ion transfer electric current is bigger.
When measurement spot radius (i.e. the radius of electrode inner chamber) increase to a certain extent, the J- on oxide-film at different measuring points
E curves are essentially identical, after illustrating measurement spot size greatly to a certain extent, inevitably there is larger defect such as crackle etc..
One field size of electron microscope observation is no more than 0.01mm2.In this method, survey spot area and reach 113mm2, more
It objective and accurate can reflect the distribution situation of oxide-film microdefect.
As described above, the present invention can be realized preferably.
Claims (2)
1. a kind of method of quantitative determination oxide-film microdefect, it is characterised in that conducted by the pure electronics for determining oxide-film
Electric current or resistance and ion migrate electric current or the impedance of formation into oxide-film, are passed by Ion transfer electric current or impedance with pure electronics
The difference and its numerical value of electrical conduction current or resistance, the microdefect come in quantization signifying oxide-film；
The pure electronics conduction electric current or resistance and ion of described oxide-film migrates electric current or the impedance of formation into oxide-film
Assay method is：
A1 measuring circuit) is connected：The oxide-film for aoxidizing membrane sample is immersed into electrode solution, the metallic matrix connection of oxidation membrane sample is straight
Flow power supply a pole, another electrode contact with electrode solution connection dc source another pole so that by electrode, electrode solution,
Aoxidize membrane sample formation electrode loop；
A2) the current value and magnitude of voltage in measuring electrode loop, obtains the current-voltage correlation of pure electronics conduction, and then obtains pure electricity
Sub- conduction resistance；Obtain the current-voltage correlation of Ion transfer, and then obtain ion migrating impedance into oxide-film；
The current-voltage correlation that the current-voltage correlation of Ion transfer and pure electronics conduct also is converted into ion including one to move
The step of current density that the current density of shifting is conducted to the relation of electric-field intensity and pure electronics is to the relation of electric-field intensity, it is described
Current density be the oxide-film area ratio that contact with electrode solution of electric current, electric-field intensity is the ratio between voltage and oxide thickness,
The current density that the current density migrated by reference ion is conducted to the relation of electric-field intensity with pure electronics is to electric-field intensity
Relation reflection microdefect number.
2. a kind of method of quantitative determination oxide-film microdefect according to claim 1, it is characterised in that described electricity
Pole liquid is liquid metal or electrolyte aqueous solution, and electrode solution is made with liquid metal during the pure electronics conduction electric current for determining oxide-film,
Make electrode solution with electrolyte aqueous solution during the Ion transfer electric current for determining oxide-film.
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| CN101581695A (en) * | 2009-06-19 | 2009-11-18 | 武汉钢铁(集团)公司 | Insoluble anode coating coat integrity detection method |
| CN103364472A (en) * | 2013-07-12 | 2013-10-23 | 北京工业大学 | Anticorrosion layer peeling testing device based on electrochemical impedance spectrum |
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| CN101581695A (en) * | 2009-06-19 | 2009-11-18 | 武汉钢铁(集团)公司 | Insoluble anode coating coat integrity detection method |
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