CN104977336A - Method and device used for quantitative determination of oxidation film microdefects - Google Patents
Method and device used for quantitative determination of oxidation film microdefects Download PDFInfo
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Abstract
The invention discloses a method used for quantitative determination of oxidation film microdefects. According to the method, quantitative characterization of microdefects in oxidation film is realized via measuring on pure electronic conduction current of the oxidation film, or electric current or impedance formed by migration of electrical resistance or ions into the oxidation film, and calculation of the difference and the value of ion migration current or impedance with electronic conduction current or electrical resistance. Beneficial effects are that: not only qualitative characterization but objective quantitative characterization of oxidation film microdefects, such as defect scale and distribution density, can be realized, distribution situation of microdetects on macroscale (10mm) can be reflected; sample preparation is not needed, direct measurement on samples can be realized; the method is convenient and fast; and influences caused by sample preparation and human factors are avoided.
Description
Technical field
The present invention relates to material properties test technical field, particularly, relate to a kind of method and instrument of quantitative determination oxide film microdefect.
Background technology
Zircaloy, titanium alloy, uranium alloy, stainless steel etc. are very important construction materials, and decay resistance is one of key factor affecting its engineer applied.Owing to can form fine and close oxide film at material surface when there is corrosion in aqueous medium, hinder mass transfer during corrosion, these materials have good decay resistance usually.The corrosion behavior of microstructure characteristic (as internal tiny crack, the space etc.) alloy of the oxide film that corrosion is formed has significant impact, the impact of alloying component, aqueous medium condition alloy corrosion behavior, its physical essence is all the impact on oxide film micromechanism, therefore the analysis and characterization of oxide film microstructure characteristic is the important content in the research and development of the construction materials such as zircaloy, titanium alloy, uranium alloy.
At present, the universal means analyzing oxide film micromechanism mainly contains X-ray diffractometer, laser Raman spectrum, optical microscope, scanning electron microscopy, transmission electron microscope etc.X-ray diffractometer and laser Raman spectrum can measure the crystal structure of oxide film, can not analyze the defect in oxide film.Because enlargement factor is little, light microscope can observe roughly the thickness of oxide film, can not analyze the defect of oxide film.Scanning electron microscope observable oxide thickness, grain morphology, space and micro-crack.The more fine structure of transmission electron microscope observable oxide film, as the crystal structure and grain orientation etc. of crystal boundary, nanoscale hole, microcell.There is following limitation in the microdefect analyzing oxide film with scanning electron microscope and transmission electron microscopy microscopic examination:
(1) microcell is observed, observation area size is generally less than 10 μm, result can not reflect macroscopical situation of sample, and in fact in oxide film, the distribution of microdefect (especially micro-crack) is extremely uneven, can not represent the situation of macroscopic view by the situation of limited several visual field.
(2) destructive observation, observes oxide film cross section, and observed result is subject to the impact of the preparation method of micro-analysis sample and analyst's subjective factor larger.
(3) qualitative observation, can not get quantized data that is comparable, microdefect.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of method and the instrument that can reflect microdefect distribution situation, conveniently quantitative determination oxide film microdefect.
Invent a kind of objectively, can the research and development of method to construction materials such as zircaloy, titanium alloy, uranium alloy, stainless steels of quantitative determination oxide film microdefect significant.Have alloying component to report the influence research of the electronic conduction electric current of oxide film in the world, but the impact of the microdefect of oxide film on electronic conduction electric current is less, therefore can not be used for the microdefect of quantitative determination oxide film.
Inventor thinks, because ion has certain size, if there is not the defect suitable with ion yardstick in oxide film, ion cannot pass through.Therefore, by the migratory behaviour of ion, can the yardstick of defect and distribution density in quantitative analysis oxide film.Following technical scheme is inventors herein proposed based on this principle.
The present invention's adopted technical scheme that solves the problem is:
A kind of method of quantitative determination oxide film microdefect, in oxide film, electric current or the impedance of formation is moved by measuring the pure electronic conduction electric current of oxide film or resistance and ion, by difference and the numerical value thereof of Ion transfer electric current or impedance and electronic conduction electric current or resistance, carry out the microdefect in quantization signifying oxide film.
Principle of the present invention is: at electrolyte solution (as CuSO
4solution) in, positive ion can be there is (as Cu
2+) and negative ion (as SO
4 2+), negative ions, under electric field action, does directed movement, and negative ion is to positive polar motion to negative pole for positive ion, and in solution, the motion of negative ions forms electric current.Thus can be that electrode forms telegraph circuit and measures electric current or the impedance that the pure electronic conduction electric current of oxide film or resistance and ion move formation in oxide film with oxide film sample, measure the voltage and current of this telegraph circuit respectively by voltage table and reometer.
Take U as impressed DC voltage, Rs is the internal resistance of external dc power supply, and Rv is the internal resistance of voltage table, and Rc is the internal resistance of reometer.Rm is the equivalent resistance of metallic matrix wire loop, and Ra is the equivalent resistance of electrolyte solution, and Re is the electronic conduction resistance of oxide film, and Ri is the impedance of oxide film intermediate ion migration.Due to Re and Ri several orders of magnitude larger than Rc, Rm and Ra, the electric current I therefore in reometer can be approximately:
（1）
For the metering circuit determined, U, Rv, Rs are known definite value, have nothing to do with the character of oxide film sample to be measured.Re with Ri is relevant with the character of testing sample.After the current-voltage correlation (Ie-V curve) first measuring pure electronic conduction obtains resistance Re, then the current-voltage correlation (I-V curve) measuring Ion transfer obtains Ion transfer impedance Ri.Because ion has certain size, if oxide film is very fine and close, ion is difficult to enter, and the value of Ri is very large, and electric current I is very little, the order of magnitude same as Ie place.If there is a large amount of defect in oxide film, ion is easy to move in oxide film, and electric current I can be very large.As under the voltage of a few volt, electric current will reach a milliampere magnitude, more than 4 orders of magnitude about larger than Ie.Therefore the I-V relation of sample or the size of Ri, directly reflects the situation (defect size and quantity) of microdefect in oxide film.
The assay method of electric current or impedance that the pure electronic conduction electric current of described oxide film or resistance and ion move formation in oxide film is:
A1) metering circuit is connected: the oxide film of oxide film sample is immersed electrode solution, the metallic matrix of oxide film sample connects a pole of direct supply, another pole of the Electrode connection direct supply that another contacts with electrode solution, thus form electrode loop by electrode, electrolytic solution, oxide film sample;
A2) current value in potential electrode loop and magnitude of voltage, obtain the current-voltage correlation of pure electronic conduction, and then obtain pure electronic conduction resistance Re; Obtain the current-voltage correlation of Ion transfer, and then obtain ion move impedance Ri in oxide film.
Test adopts 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 comprise the current density of the current density current-voltage correlation of the current-voltage correlation of Ion transfer and pure electronic conduction being converted to Ion transfer to the relation of electric field intensity and pure electronic conduction to the step of the relation of electric field intensity, described current density is the oxide film area ratio that electric current contacts with electrode solution, electric field intensity is voltage and the ratio of oxide thickness, the current density of being moved by reference ion reflects the number of microdefect to the relation of electric field intensity to the current density of the relation of electric field intensity and pure electronic conduction, the current density of Ion transfer is more close to current density during pure electronic conduction, show that in this test spot region, microdefect is fewer, the current density of Ion transfer gets over current density when deflects electrons is conducted, in this test spot region, microdefect is more much larger.
Described metering circuit also comprises a verification loop in parallel with described electrode loop.Described one end, verification loop connects the positive pole of direct supply, the verification loop other end connects power cathode, loop is provided with switch in verification, the resistance value in verification loop is divided into many grades (such as 3 ~ 6 grades), the resistance value of every grade is known definite value, the resistance that resistance is the highest one grade is in 100M Ω magnitude, and the resistance of minimum a grade is in 10K Ω magnitude.
Described electrode solution is liquid metal or electrolyte aqueous solution, makes electrode solution when measuring the pure electronic conduction electric current of oxide film with liquid metal, makes electrode solution when measuring the Ion transfer electric current of oxide film with electrolyte aqueous solution.
Described electrode is the hollow electrode that bottom is provided with under shed cavity volume, under shed cavity volume is communicated with outside by the through hole being located thereon portion, namely this through hole is communicated with space outerpace and under shed cavity volume, the metallic matrix of oxide film sample connects a pole of direct supply, and this hollow electrode connects another pole of direct supply.During connecting electrode loop, hollow electrode is overlaid on the oxide film of oxide film sample, the lower surface of under shed cavity volume is closed by oxide film sample, then by through hole iontophoresis electrode liquid, electrode immersion is overlying on the surface being positioned under shed cavity volume internal oxidition film, electrode solution contacts the sidewall of under shed cavity volume simultaneously, thus realizes the electrical connection of hollow electrode and electrode solution.
Described under shed cavity volume is circular cylindrical cavity, hollow electrode is pressed on after on sample, can add electrode solution from its top by through hole, the radius of under shed cavity volume, between 0.5 to 6mm, the end face that hollow electrode lower end contacts with oxide film is embedded with heat resistant rubber sealing ring.
Described oxide film sample fixed placement is on sample stage, and sample stage inside is provided with the well heater heated oxide film sample.Such as, sample stage can adopt stainless steel, and its inside is provided with one, and for holding the cavity of well heater, well heater is sealed in this cavity, thus sample stage becomes the rustless steel container of an accommodation well heater.When measuring the pure electronic conduction electric current of oxide film, under shed cavity volume to described hollow electrode inserts low-melting-point metal, the well heater of sample stage can heat oxide film sample, and then realize heating the low-melting-point metal on oxide film sample top by the heat transfer of oxide film sample, by the temperature of controlled oxidization membrane sample, the low-melting-point metal in the under shed cavity volume of hollow electrode is made to be fused into liquid, be filled in the under shed cavity volume closed by oxide film, liquid metals leaching is overlying on the surface being positioned under shed cavity volume internal oxidition film, liquid metals contacts the sidewall of under shed cavity volume simultaneously thus realizes the electrical connection of hollow electrode and liquid metals.
Described low-melting-point metal can be gallium (Ga), indium (In) or gallium-indium alloy.
When measuring the pure electronic conduction electric current of oxide film, load gallium (Ga) at the inner chamber of hollow electrode, then electrode is pressed on oxide film.The positive pole of direct supply is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Cover vacuum (-tight) housing, start vacuum pump.When the gas pressure intensity of sample chamber is lower than 10kPa, start heating.Sample temperature is made to be stabilized in 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, covers on the oxide film in alveolus in electrode, and with metal hollow electrode internal contact, formed positive electrode.
Open direct supply, be recorded in the current values under different voltage, obtain the current-voltage correlation Ie-V curve of pure electronic conduction.The resistance Re of oxide film when can calculate pure electronic conduction by this curve.By this resistance and the radius of hollow electrode inner chamber and the thickness of oxide film, the resistivity of oxide film can be calculated.Usually, if oxide film does not exist gross imperfection (as being damaged) or oxide film by before electric field breakdown, the resistivity of oxide film is very large, 3 × 10
9more than Ω m, Ie are very little.For the Zircaloy Oxide Film of thickness about 2 μm, be the hollow electrode of 6mm with inner chamber radius, under 40V voltage, Ie is less than 500 nA, and under 10V voltage, Ie is less than 50 nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 10
7more than V/m.
After the current-voltage correlation Ie-V curve of pure electronic conduction has been tested, stop heating, close direct supply.Close vacuum pump, open vacuum chamber, remove the gallium of hollow electrode inner chamber.
The electrolyte of described electrolyte aqueous solution can be lithium hydroxide, potassium hydroxide, NaOH, lithium chloride, potassium chloride, sodium chloride, lime chloride, sodium sulphate, potassium sulfate, copper sulphate, and the concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, the transfer ability of ion in oxide film is variant, and I-V curve is variant.Want the microdefect situation of the different sample of comparative analysis, electrolyte aqueous solution of the same race need be adopted.
When measuring the Ion transfer electric current of oxide film, electrode is moved on on oxide film after desired location, hollow electrode is pressed on oxide film.From the upper end instillation electrolyte solution of hollow electrode.After electrolyte is full of hollow electrode, vacuum electrode top is connected with positive source.Open direct supply, be recorded in the current values under different voltage, obtain the current-voltage correlation I-V curve of Ion transfer.After testing, close direct supply.
By the hollow electrode adopting inner chamber radius different, the homogeneity situation of defect distribution in oxide film can be measured.The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radius is identical.The homogeneity situation of defect distribution in oxide film can be reflected by the difference of the current-voltage correlation I-V curve of many Ion transfer and the current-voltage correlation Ie-V curve of pure electronic conduction.
The current-voltage correlation I-V curve of the Ion transfer recorded and the current-voltage correlation Ie-V curve of pure electronic conduction can not directly be used for contrasting, there are two reasons: one is that the thickness of oxide film is different, even if under same voltage, electric field intensity in oxide film is different, and the driving force that ion is subject to is different; Two is that the inner chamber radius of hollow electrode is different, and conduction surface is different.The relation of current vs voltage is needed to convert the relation (J-E curve) of current density to electric field intensity to.Current density is the oxide film area ratio that electric current contacts with electrode solution, and electric field intensity is voltage and the ratio of oxide thickness.In order to intuitive and convenient, nA/mm gets respectively in the unit of the two
2with V/ μm.
The current density of Ion transfer is less, more close to current density during pure electronic conduction, shows that in test spot region, the transference cell of ion in oxide film is very little, and namely the microdefect in this district is little.The current density of the electric current of Ion transfer is larger, illustrates in the larger defect (as crackle) of this district existence.
Implement the instrument of the method for above-mentioned a kind of quantitative determination oxide film microdefect, comprise sample stage, oxide film sample, direct supply and electrode, oxide film sample is placed on sample stage, an electric heater for heating oxide film sample is provided with in sample stage, electrode is overlaid on oxide film sample, by the under shed of oxide film sample enclosed electrode, electrode base is provided with under shed cavity volume, electrode upper is provided with through hole, under shed cavity volume is communicated with outside by the through hole being located thereon portion, electrode solution is filled with in the under shed cavity volume of electrode, one pole of Electrode connection direct supply, the metallic matrix of oxide film sample connects another pole of direct supply, electrode, electrolytic solution, oxide film sample forms electrode loop, electrode loop is provided with for the current value in potential electrode loop and the reometer of magnitude of voltage and voltage table, described sample stage, oxide film sample and electrode are positioned at a vacuum chamber, vacuum chamber is made up of chassis and the vacuum (-tight) housing be covered on chassis.
Testing tool mainly comprises vacuum specimen chamber and observing and controlling electronic circuit two large divisions.With oil-sealed rotary pump, sample chamber is vacuumized.Sample stage is placed in sample chamber.Hollow electrode and test sample are fixed by sample stage.Sample stage also heats test sample.In the electrode solution that the inner chamber filling of hollow electrode is different, as liquid metal or electrolyte aqueous solution, survey the electronic conduction behavior of oxide film when filling liquid metal, fill the migratory behaviour of measured ion during electrolyte aqueous solution.
Also comprise a verification loop in parallel with described electrode loop, described one end, verification loop connects the positive pole of direct supply, the verification loop other end connects power cathode, loop is provided with switch in verification, the resistance value in verification loop is divided into many grades (such as 3 ~ 6 grades), the resistance value of every grade is known definite value, and the resistance that resistance is the highest a grade is in 100M Ω magnitude, and the resistance of minimum a grade is in 10K Ω magnitude.Due to atomic weak signal (10
-10a) measurement, is subject to the interference of instrument thermal noise and environmental noise and is subject to the impact that electronic component is aging.In order to ensure that test result accurately and reliably, being parallel with the electrode loop of test and verifying loop.Before sample test, by the duty of verification loop tester whether normal reliable.The resistance stepping in verification loop is variable, and the resistance of each grade is known definite value.Resistance value minimum one grade in 10K Ω magnitude, the most high-grade in 100M Ω magnitude.The resistance value in verification loop can divide 3 ~ 6 grades, and stepping is more, verifies more reliable, and the resistance difference between shelves adopts logarithm to divide equally.Divide five grades in this instrument, the resistance value of five grades is about 10 K Ω, 100 K Ω, 1 M Ω, 10M Ω and 100M Ω respectively.When instrument verifies, open instrument direct supply, closed verification loop also disconnects test loop.Regulate the voltage of direct supply to export, when direct voltage output is 1.0V, 2.0V, 3.0V, measure current value when different resistance values is got in verification loop respectively.Be known fixed value owing to verifying each shelves resistance in loop, when therefore checking, the current value under identical voltage and resistance can reproduce at every turn, and energy and theoretical calculation.Otherwise the state of instrument is abnormal, need to check.
When the state of instrument is normal, gets a ready Zircaloy Oxide Film sample, be placed on sample stage.Make the metal shell of the zirconium metal in close contact heater that sample exposes, measure the resistance between zirconium metal and sample stage, if resistance is less than 2 Ω, illustrates zirconium metal and sample stage and with the electrical contact of instrument common ground well, can follow-up test be carried out.
Described under shed cavity volume is circular cylindrical cavity, hollow electrode is pressed on after on sample, can add electrode solution from its top by through hole, the radius of under shed cavity volume, between 0.5 to 6mm, the end face that hollow electrode lower end contacts with oxide film is embedded with heat resistant rubber sealing ring.The size of hollow electrode inner chamber has a significant impact test result.Defect distribution in oxide film is extremely uneven.Electrode inner cavity size is larger, more can reflect macroscopical average effect that alumina diaphragm defect distributes.To the microcell difference of analyzing defect distribution, less inner cavity size should be used.In the present invention, the inner chamber radius of hollow electrode has three kinds: 0.5mm, 3mm and 6mm, measures for different object.
Digital instrument for atomic weak signal measurement is not only very expensive but also easily impaired.Different sample oxidation film microdefect situation is widely different, and the amplitude of variation of Ion transfer electric current will reach 6 orders of magnitude, receives peace to several milliamperes from being less than 1.Even if in same sample, due to the skewness of microdefect, different positions, Ion transfer current difference also may reach 5 number magnitude.In order to the safety of digital electronic ammeter, digital electronic ammeter needs series limiting resistor, makes the electric current flow through in whenever reometer be no more than safety value.Current-limiting resistance can between 10K Ω to 100K Ω, current-limiting resistance about 10 K Ω in this instrument.
Utilize this instrument, the step of quantitative determination oxide film microdefect mainly comprises: the verification of preparation of samples, instrument state, electronic conduction Ie-V curve determination, Ion transfer I-V curve determination, defect distribution uniformity, data processing six steps.
Described electric heater is by connection temperature controller.
Sample stage is fixed on the top on the chassis of vacuum chamber, and the sidewall of electrode is stepped ramp type, and an adjustable for height horizontal pressure foot is overlaid on the step surface of electrode, thus is pressed on oxide film sample by motor by pressing plate.
Described horizontal pressure foot is provided with multiple threaded hole, and threaded hole is set on the screw rod of vertically setting, can be regulated the upright position of horizontal pressure foot by rotary screw.Preferably, described sample stage is by multiple strut support, and screw rod rotary setting is on pole or on sample stage.
To sum up, the invention has the beneficial effects as follows:
1, method of the present invention reflects the distribution situation of microdefect in macro-scale (10mm).
2, method energy objective quantification of the present invention characterizes the situation of oxide film microdefect, as defect yardstick, distribution density etc., and does not just understand qualitatively.
3, this method does not need sample preparation, directly can measure on sample, convenient and swift, avoids the impact of impact that sample making course causes and human factor.
Accompanying drawing explanation
Fig. 1 is test philosophy figure of the present invention;
Fig. 2 is the equivalent circuit diagram of Fig. 1;
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;
The J-E curve of oxide film when Fig. 5 is electrode radius difference.
Mark and corresponding parts title in accompanying drawing:
1-sample stage, 2-oxide film sample, 3-direct supply, 4-electrode, 5-electric heater, 6-electrode solution, 7-reometer, 8-voltage table, 9-verifies loop, 10-temperature controller, 11-chassis, 12-vacuum (-tight) housing, 13-horizontal pressure foot, 14-screw rod, 15-pole.
Embodiment
Below in conjunction with embodiment and accompanying drawing, to the detailed description further of the present invention's do, but embodiments of the present invention are not limited thereto.
Embodiment:
A kind of method of quantitative determination oxide film microdefect, in oxide film, electric current or the impedance of formation is moved by measuring the pure electronic conduction electric current of oxide film or resistance and ion, by difference and the numerical value thereof of Ion transfer electric current or impedance and electronic conduction electric current or resistance, carry out the microdefect in quantization signifying oxide film.
As shown in Figure 1, principle of the present invention is: at electrolyte solution (as CuSO
4solution) in, positive ion can be there is (as Cu
2+) and negative ion (as SO
4 2+), negative ions, under electric field action, does directed movement, and negative ion is to positive polar motion to negative pole for positive ion, and in solution, the motion of negative ions forms electric current, and its equivalent electrical circuit is as accompanying drawing 2.Thus can be that electrode forms telegraph circuit and measures electric current or the impedance that the pure electronic conduction electric current of oxide film or impedance and ion move formation in oxide film with oxide film sample, measure the voltage and current of this telegraph circuit respectively by voltage table and reometer.
In accompanying drawing 2, take U as impressed DC voltage, Rs is the internal resistance of external dc power supply, and Rv is the internal resistance of voltage table, and Rc is the internal resistance of reometer.Rm is the equivalent resistance of metallic matrix wire loop, and Ra is the equivalent resistance of electrolyte solution, and Re is the electronic conduction resistance of oxide film, and Ri is the impedance of oxide film intermediate ion migration.Due to Re and Ri several orders of magnitude larger than Rc, Rm and Ra, the electric current I therefore in reometer can be approximately:
（1）
For the metering circuit determined, U, Rv, Rs are known definite value, have nothing to do with the character of oxide film sample to be measured.Re with Ri is relevant with the character of testing sample.After the current-voltage correlation (Ie-V curve) first measuring pure electronic conduction obtains resistance Re, then the current-voltage correlation (I-V curve) measuring Ion transfer obtains Ion transfer impedance Ri.Because ion has certain size, if oxide film is very fine and close, ion is difficult to enter, and the value of Ri is very large, and electric current I is very little, the order of magnitude same as Ie place.If there is a large amount of defect in oxide film, ion is easy to move in oxide film, and electric current I can be very large.As under the voltage of a few volt, electric current will reach a milliampere magnitude, more than 4 orders of magnitude about larger than Ie.Therefore the I-V relation of sample or the size of Ri, directly reflects the situation (defect size and quantity) of microdefect in oxide film.
The assay method of electric current or impedance that the pure electronic conduction electric current of described oxide film or resistance and ion move formation in oxide film is:
A1) metering circuit is connected: the oxide film of oxide film sample is immersed electrode solution, the metallic matrix of oxide film sample connects a pole of direct supply, the metallic matrix of oxide film sample can connect negative pole or the positive pole of direct supply, preferably, the metallic matrix of oxide film sample connects the negative pole of direct supply, another pole of the Electrode connection direct supply that another contacts with electrode solution, namely when the metallic matrix of oxide film sample connects the negative pole of direct supply, the positive pole of the Electrode connection direct supply that another contacts with electrode solution, otherwise otherwise, thus by electrode, electrolytic solution, oxide film sample forms electrode loop,
A2) current value in potential electrode loop and magnitude of voltage, obtain the current-voltage correlation of pure electronic conduction, and then obtain pure electronic conduction resistance Re; Obtain the current-voltage correlation of Ion transfer, and then obtain ion move impedance Ri in oxide film.Test adopts 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 comprise the current density of the current density current-voltage correlation of the current-voltage correlation of Ion transfer and pure electronic conduction being converted to Ion transfer to the relation of electric field intensity and pure electronic conduction to the step of the relation of electric field intensity, described current density is the oxide film area ratio that electric current contacts with electrode solution, electric field intensity is voltage and the ratio of oxide thickness, the current density of being moved by reference ion reflects the number of microdefect to the relation of electric field intensity to the current density of the relation of electric field intensity and pure electronic conduction, the current density of Ion transfer is more close to current density during pure electronic conduction, show that in this test spot region, microdefect is fewer, the current density of the electric current of Ion transfer gets over current density when deflects electrons is conducted, in this test spot region, microdefect is more much larger.
Described metering circuit also comprises a verification loop in parallel with described electrode loop.Described one end, verification loop connects the positive pole of direct supply, the verification loop other end connects power cathode, loop is provided with switch in verification, the resistance value in verification loop is divided into many grades (such as 3 ~ 6 grades), the resistance value of every grade is known definite value, the resistance that resistance is the highest one grade is in 100M Ω magnitude, and the resistance of minimum a grade is in 10K Ω magnitude.
Described electrode solution is liquid metal or electrolyte aqueous solution, makes electrode solution when measuring the pure electronic conduction electric current of oxide film with liquid metal, makes electrode solution when measuring the Ion transfer electric current of oxide film with electrolyte aqueous solution.
Described electrode is the hollow electrode that bottom is provided with under shed cavity volume, under shed cavity volume is communicated with outside by the through hole being located thereon portion, namely this through hole is communicated with space outerpace and under shed cavity volume, the metallic matrix of oxide film sample connects a pole of direct supply, and this hollow electrode connects another pole of direct supply.During connecting electrode loop, hollow electrode is overlaid on the oxide film of oxide film sample, the lower surface of under shed cavity volume is closed by oxide film sample, then by through hole iontophoresis electrode liquid, electrode immersion is overlying on the surface being positioned under shed cavity volume internal oxidition film, electrode solution contacts the sidewall of under shed cavity volume simultaneously, thus realizes the electrical connection of hollow electrode and electrode solution.
The under shed cavity volume of described hollow electrode is circular cylindrical cavity, hollow electrode is pressed on after on sample, can add electrode solution from its top by through hole, the radius of under shed cavity volume, between 0.5 to 6mm, the end face that hollow electrode lower end contacts with oxide film is embedded with heat resistant rubber sealing ring.
Described oxide film sample fixed placement is on sample stage, and sample stage inside is provided with the well heater heated oxide film sample.Such as, sample stage can adopt stainless steel, and its inside is provided with one, and for holding the cavity of well heater, well heater is sealed in this cavity, thus sample stage becomes the rustless steel container of an accommodation well heater.When measuring the pure electronic conduction electric current of oxide film, under shed cavity volume to described hollow electrode inserts low-melting-point metal, the well heater of sample stage can heat oxide film sample, and then realize heating the low-melting-point metal on oxide film sample top by the heat transfer of oxide film sample, by the temperature of controlled oxidization membrane sample, the low-melting-point metal in the under shed cavity volume of hollow electrode is made to be fused into liquid, be filled in the under shed cavity volume closed by oxide film, liquid metals leaching is overlying on the surface being positioned under shed cavity volume internal oxidition film, liquid metals contacts the sidewall of under shed cavity volume simultaneously thus realizes the electrical connection of hollow electrode and liquid metals.
Described low-melting-point metal can be gallium (Ga), indium (In) or gallium-indium alloy.
When measuring the pure electronic conduction electric current of oxide film, load gallium (Ga) at the inner chamber of hollow electrode, then electrode is pressed on oxide film.The positive pole of direct supply is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Cover vacuum (-tight) housing, start vacuum pump.When the gas pressure intensity of sample chamber is lower than 10kPa, start heating.Sample temperature is made to be stabilized in 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, covers on the oxide film in alveolus in electrode, and with metal hollow electrode internal contact, formed electrode.
Open direct supply, be recorded in the current values under different voltage, obtain the current-voltage correlation Ie-V curve of pure electronic conduction.The resistance Re of oxide film when can calculate pure electronic conduction by this curve.By this resistance and the radius of hollow electrode inner chamber and the thickness of oxide film, the resistivity of oxide film can be calculated.Usually, if oxide film does not exist gross imperfection (as being damaged) or oxide film by before electric field breakdown, the resistivity of oxide film is very large, 3 × 10
9more than Ω m, Ie are very little.For the Zircaloy Oxide Film of thickness about 2 μm, be the hollow electrode of 6mm with inner chamber radius, under 40V voltage, Ie is less than 500 nA, and under 10V voltage, Ie is less than 50 nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 10
7more than V/m.
After the current-voltage correlation Ie-V curve of pure electronic conduction has been tested, stop heating, close direct supply.Close vacuum pump, open vacuum chamber, remove the gallium of hollow electrode inner chamber.
The electrolyte of described electrolyte aqueous solution can be lithium hydroxide, potassium hydroxide, NaOH, lithium chloride, potassium chloride, sodium chloride, lime chloride, sodium sulphate, potassium sulfate, copper sulphate, and the concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, the transfer ability of ion in oxide film is variant, and I-V curve is variant.Want the microdefect situation of the different sample of comparative analysis, electrolyte aqueous solution of the same race need be adopted.
When measuring the Ion transfer electric current of oxide film, electrode is moved on on oxide film after desired location, hollow electrode is pressed on oxide film.From the upper end instillation electrolyte solution of hollow electrode.After electrolyte is full of hollow electrode, vacuum electrode top is connected with positive source.Open direct supply, be recorded in the current values under different voltage, obtain the current-voltage correlation I-V curve of Ion transfer.After testing, close direct supply.
By the hollow electrode adopting inner chamber radius different, the homogeneity situation of defect distribution in oxide film can be measured.The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radius is identical.The homogeneity situation of defect distribution in oxide film can be reflected by the difference of the current-voltage correlation I-V curve of many Ion transfer and the current-voltage correlation Ie-V curve of pure electronic conduction.
The current-voltage correlation I-V curve of the Ion transfer recorded and the current-voltage correlation Ie-V curve of pure electronic conduction can not directly be used for contrasting, there are two reasons: one is that the thickness of oxide film is different, even if under same voltage, electric field intensity in oxide film is different, and the driving force that ion is subject to is different; Two is that the inner chamber radius of hollow electrode is different, and conduction surface is different.The relation of current vs voltage is needed to convert the relation (J-E curve) of current density to electric field intensity to.Current density is the oxide film area ratio that electric current contacts with electrode solution, and electric field intensity is voltage and the ratio of oxide thickness.In order to intuitive and convenient, nA/mm gets respectively in the unit of the two
2with V/ μm.
The current density of Ion transfer is less, more close to current density during pure electronic conduction, shows that in test spot region, the transference cell of ion in oxide film is very little, and namely the microdefect in this district is little.The current density of Ion transfer is larger, illustrates in the larger defect (as crackle) of this district existence.
As shown in Figure 3, implement the instrument of the method for above-mentioned a kind of quantitative determination oxide film microdefect, comprise sample stage 1, oxide film sample 2, direct supply 3 and electrode 4, oxide film sample 2 is placed on sample stage 1, an electric heater 5 for heating oxide film sample 2 is provided with in sample stage 1, electrode 4 is overlaid on oxide film sample 2, by the under shed of oxide film sample 2 enclosed electrode 4, under shed cavity volume is provided with bottom electrode 4, electrode 4 top is provided with through hole, under shed cavity volume is communicated with outside by the through hole being located thereon portion, electrode solution 6 is filled with in the under shed cavity volume of electrode 4, electrode 4 connects a pole of direct supply 3, the metallic matrix of oxide film sample 2 connects another pole of direct supply 3, the metallic matrix of oxide film sample 2 can connect negative pole or the positive pole of direct supply 3, preferably, the metallic matrix of oxide film sample 2 connects the negative pole of direct supply 3, electrode 4 connects another pole of direct supply 3, namely when the metallic matrix of oxide film sample 2 connects the negative pole of direct supply 3, another electrode 4 contacted with electrode solution 6 connects the positive pole of direct supply 3, otherwise otherwise, thus, electrode 4, electrolytic solution, oxide film sample 2 forms electrode 4 loop, electrode 4 loop is provided with for the current value in potential electrode 4 loop and the reometer 7 of magnitude of voltage and voltage table 8, described sample stage 1, oxide film sample 2 and electrode 4 are positioned at a vacuum chamber, vacuum chamber is made up of chassis 11 and the vacuum (-tight) housing 12 be covered on chassis 11.
Testing tool mainly comprises vacuum specimen chamber and observing and controlling electronic circuit two large divisions.With oil-sealed rotary pump, sample chamber is vacuumized.Sample stage 1 is placed in sample chamber.Hollow electrode 4 and test sample are fixed by sample stage 1.Sample stage 1 also heats test sample.In the electrode solution 6 that the inner chamber filling of hollow electrode 4 is different, as liquid metal or electrolyte aqueous solution, survey the electronic conduction behavior of oxide film when filling liquid metal, fill the migratory behaviour of measured ion during electrolyte aqueous solution.
Also comprise a verification loop 9 in parallel with described electrode 4 loop, described one end, verification loop 9 connects the positive pole of direct supply 3, verification loop 9 other end connects power cathode, loop 9 is provided with switch in verification, the resistance value in verification loop 9 is divided into many grades, such as 3 ~ 6 grades, and the resistance value of every grade is known definite value, the resistance that resistance is the highest one grade is in 100M Ω magnitude, and the resistance of minimum a grade is in 10K Ω magnitude.Due to atomic weak signal (10
-10a) measurement, is subject to the interference of instrument thermal noise and environmental noise and is subject to the impact that electronic component is aging.In order to ensure that test result accurately and reliably, being parallel with electrode 4 loop of test and verifying loop 9.Before sample test, by the duty of verification loop 9 tester whether normal reliable.The resistance stepping in verification loop 9 is variable, and the resistance of each grade is known definite value.Resistance value minimum one grade in 10K Ω magnitude, the most high-grade in 100M Ω magnitude.The resistance value in verification loop 9 can divide 3 ~ 6 grades, and stepping is more, verifies more reliable, and the resistance difference between shelves adopts logarithm to divide equally.Divide five grades in this instrument, the resistance value of five grades is about 10 K Ω, 100 K Ω, 1 M Ω, 10M Ω and 100M Ω respectively.When instrument verifies, open instrument direct supply 3, closed verification loop 9 also disconnects test loop.Regulate the voltage of direct supply 3 to export, when direct voltage output is 1.0V, 2.0V, 3.0V, measure current value when different resistance values is got in verification loop 9 respectively.Are known fixed values owing to verifying each shelves resistance in loop 9, when therefore checking, the current value under identical voltage and resistance can reproduce at every turn, and energy and theoretical calculation.Otherwise the state of instrument is abnormal, need to check.
When the state of instrument is normal, gets a ready Zircaloy Oxide Film sample 2, be placed on sample stage 1.Make the metal shell of the zirconium metal in close contact heater that sample exposes, measure the resistance between zirconium metal and sample stage 1, if resistance is less than 2 Ω, illustrates zirconium metal and sample stage 1 and with the electrical contact of instrument common ground well, can follow-up test be carried out.
Described under shed cavity volume is circular cylindrical cavity, hollow electrode 4 is pressed on after on sample, can add electrode solution 6 from its top by through hole, the radius of under shed cavity volume, between 0.5 to 6mm, the end face that hollow electrode 4 lower end contacts with oxide film is embedded with heat resistant rubber sealing ring.The size of hollow electrode 4 inner chamber has a significant impact test result.Defect distribution in oxide film is extremely uneven.Electrode 4 inner cavity size is larger, more can reflect macroscopical average effect that alumina diaphragm defect distributes.To the microcell difference of analyzing defect distribution, less inner cavity size should be used.In the present invention, the inner chamber radius of hollow electrode 4 has three kinds: 0.5mm, 3mm and 6mm, measures for different object.
Digital instrument for atomic weak signal measurement is not only very expensive but also easily impaired.Different sample oxidation film microdefect situation is widely different, and the amplitude of variation of Ion transfer electric current will reach 6 orders of magnitude, receives peace to several milliamperes from being less than 1.Even if in same sample, due to the skewness of microdefect, different positions, Ion transfer current difference also may reach 5 number magnitude.In order to the safety of digital electronic ammeter 7, digital electronic ammeter 7 needs series limiting resistor, makes the electric current flow through in whenever reometer 7 be no more than safety value.Current-limiting resistance can between 10K Ω to 100K Ω, current-limiting resistance about 10 K Ω in this instrument.
Utilize this instrument, the step of quantitative determination oxide film microdefect mainly comprises: the verification of preparation of samples, instrument state, electronic conduction Ie-V curve determination, Ion transfer I-V curve determination, defect distribution uniformity, data processing six steps.
Described electric heater 5 is by connection temperature controller 10.
Described sample stage 1, oxide film sample 2 and electrode 4 are positioned at a vacuum chamber.
Vacuum chamber is made up of chassis 11 and the vacuum (-tight) housing 12 be covered on chassis 11, sample stage 1 is fixed on the top on the chassis 11 of vacuum chamber, the sidewall of electrode 4 is stepped ramp type, an adjustable for height horizontal pressure foot 13 is overlaid on the step surface of electrode 4, thus is pressed on oxide film sample 2 by motor by pressing plate.An insulation spacer is had between pressing plate and 4, electrode.
Described horizontal pressure foot 13 is provided with multiple threaded hole, and threaded hole is set on the screw rod 14 of vertically setting, can be regulated the upright position of horizontal pressure foot 13 by rotary screw 14.Described sample stage 1 is supported by multiple pole 15.
Below for Zircaloy Oxide Film sample, describe quantification method of testing and the testing procedure of microdefect in oxide film of the present invention in detail.
1. test preparation of samples
Adopt the sample of the zircaloy corrosion test sheet of 10 different oxide thickness, sample size is about 20 × 30 × 1.5mm, and subordinate list 1 is the oxide thickness of sample.The sample of different oxide thickness, its preparation of samples and testing procedure are identical.
the oxide thickness of subordinate list 1 Zircaloy Oxide Film sample (μ
m)
In a termination of Zircaloy Oxide Film sample, remove oxide film, to expose zirconium metal by mechanical means (as polishing).The metal area field width exposed is about 2mm, then sample clean is clean, to be measured.
2. instrument state verification
Open instrument direct supply, closed verification loop also disconnects test loop.Regulate the voltage of direct supply to export, when direct voltage output is 1.0V, 2.0V, 3.0V, measure current value when different resistance values is got in verification loop respectively.Be known fixed value owing to verifying each shelves resistance in loop, when therefore checking, the current value under identical voltage and resistance can reproduce at every turn, and energy and theoretical calculation.Otherwise the state of instrument is abnormal, need to check.
When the state of instrument is normal, gets a ready Zircaloy Oxide Film sample, be placed on sample stage.Make the metal shell of the zirconium metal in close contact heater that sample exposes, measure the resistance between zirconium metal and sample stage, if resistance is less than 2 Ω, illustrates zirconium metal and sample stage and with the electrical contact of instrument common ground well, can follow-up test be carried out.
3. electronic conduction Ie-V curve determination
Load gallium (Ga) at the inner chamber of hollow electrode, then electrode is pressed on oxide film.The positive pole of direct supply is connected with the upper end of hollow electrode, and ensures that electrical contact is good.
Cover vacuum (-tight) housing, start vacuum pump.When the gas pressure intensity of sample chamber is lower than 10kPa, start heating.Sample temperature is made to be stabilized in 45 DEG C.Now, the gallium of hollow electrode inner chamber is fused into liquid, covers on the oxide film in alveolus in electrode, and with metal hollow electrode internal contact, formed positive electrode.
Open direct supply, be recorded in the current values under different voltage, obtain the Ie-V curve of pure electronic conduction.The resistance Re of oxide film when can calculate pure electronic conduction by this curve.By this resistance and the radius of hollow electrode inner chamber and the thickness of oxide film, the resistivity of oxide film can be calculated.Usually, if oxide film does not exist gross imperfection (as being damaged) or oxide film by before electric field breakdown, the resistivity of oxide film is very large, 3 × 10
9more than Ω m, Ie are very little.For the Zircaloy Oxide Film of thickness about 2 μm, be the hollow electrode of 6mm with inner chamber radius, under 40V voltage, Ie is less than 500 nA, and under 10V voltage, Ie is less than 50 nA.The resistance to electric field breakdown of Zircaloy Oxide Film is very capable, reaches 3 × 10
7more than V/m.
After the Ie-V curve of pure electronic conduction has been tested, stop heating, close direct supply.Close vacuum pump, open vacuum chamber, remove the gallium of hollow electrode inner chamber.
4. Ion transfer I-V curve determination
Prepare electrolyte aqueous solution.Available electrolyte has lithium hydroxide (LiOH), potassium hydroxide (KOH), NaOH (NaOH), lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), lime chloride (CaCl
2), sodium sulphate (Na
2sO
4), potassium sulfate (K
2sO
4), copper sulphate (CuSO
4).The concentration of electrolyte aqueous solution is between 0.01M to 0.1M.
Different electrolyte aqueous solutions, the transfer ability of ion in oxide film is variant, and I-V curve is variant.Want the microdefect situation of the different sample of comparative analysis, electrolyte aqueous solution of the same race need be adopted.
After electrode being moved on to other position on oxide film, hollow electrode is pressed on oxide film.Instilling electrolyte solution from the upper end of hollow electrode (is LiOH and CuSO the present embodiment
4).After electrolyte is full of hollow electrode, vacuum electrode top is connected with positive source.
Open direct supply, be recorded in the current values under different voltage, obtain I-V curve during ionic conduction.After testing, close direct supply.
5. defect distribution uniformity
By the hollow electrode adopting inner chamber radius different, the homogeneity situation of defect distribution in oxide film can be measured.The radius of hollow electrode inner chamber is from 0.5mm to 6mm.The test process of the hollow electrode of different inner chamber radius is identical with step 4.
First be hollow electrode random test 10 points on sample of 0.5mm with inner chamber radius, obtain 10 I-V curves.Because the defect at each measuring point place can be different, as some measuring point encounters micro-crack, these 10 curves generally can there were significant differences, with the minimum curve of current value for this group represents.Being that the hollow electrode of 3mm is random on sample with inner chamber radius again surveys 4 points, obtains 4 I-V curves, equally with the minimum curve of current value for this group represents.Be finally hollow electrode random survey 1 point on sample of 6mm with inner chamber radius, obtain 1 I-V curve.
Represent by two the I-V curve that curve, an Ie-V curve and inner chamber radius are 6mm, the difference of totally four curves can reflect the homogeneity situation of defect distribution in oxide film.
6. data processing
Have two reasons, the I-V curve recorded can not directly be used for contrasting.One is that the thickness of oxide film is different, 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 is that the inner chamber radius of hollow electrode is different, and conduction surface is different.The relation of current vs voltage (I-V curve) is needed to convert the relation (J-E curve) of current density to electric field intensity to.Current density is the oxide film area ratio that electric current contacts with electrode solution, and electric field intensity is voltage and the ratio of oxide thickness.In order to intuitive and convenient, nA/mm gets respectively in the unit of the two
2with V/ μm.
Accompanying drawing 4 is test results of 10 Zircaloy Oxide Film samples in subordinate list 1, J-E curve when wherein the curve of numbering Re is pure electronic conduction, and other its electrode solution of curve is LiOH aqueous solution, and solution concentration is 0.02M.As known in the figure, J-E curve reflects the situation of change of defect in oxide growth process delicately.With the increase of oxide thickness, curve moves to left, and illustrates that inner defect gets more and more.
Accompanying drawing 5 is the results of testing with the electrode of three kinds of different inner chamber radiuses No. 3 samples.Electrode solution is CuSO
4aqueous solution, solution concentration is 0.1M.When electrode inner cavity size is very little, the oxide film area related to is very little, under same electric field intensity, current density is very little, almost close to current density during pure electronic conduction, shows in test spot region, the transference cell of ion in oxide film is very little, and namely the microdefect in this district is little.Increase with measurement spot area, current density enlarges markedly, the contribution of this mainly Ion transfer electric current, illustrate in the larger defect (as crackle) of this district existence, the namely distribution of defect is not uniform, and in oxide film, there is crackle in some regions, and other region may not have.Inner chamber radius is larger, and the probability surveying existing defects in spot is larger, and therefore Ion transfer electric current is larger.
When the radius (i.e. the radius of electrode inner chamber) measuring spot increases to a certain degree, on oxide film, the J-E curve at different measuring points place is substantially identical, after illustrating that measurement spot size greatly to a certain extent, inevitably there is larger defect as crackle etc.
A field size of electron microscope observation is no more than 0.01mm
2.In this method, survey spot area and reach 113mm
2, more objective and accurately can reflect the distribution situation of oxide film microdefect.
As mentioned above, the present invention can be realized preferably.
Claims (9)
1. the method for a quantitative determination oxide film microdefect, it is characterized in that, in oxide film, electric current or the impedance of formation is moved by measuring the pure electronic conduction electric current of oxide film or resistance and ion, by difference and the numerical value thereof of Ion transfer electric current or impedance and electronic conduction electric current or resistance, carry out the microdefect in quantization signifying oxide film.
2. the method for a kind of quantitative determination oxide film microdefect according to claim 1, is characterized in that, the assay method of electric current or impedance that the pure electronic conduction electric current of described oxide film or resistance and ion move formation in oxide film is:
A1) metering circuit is connected: the oxide film of oxide film sample is immersed electrode solution, the metallic matrix of oxide film sample connects a pole of direct supply, another pole of the Electrode connection direct supply that another contacts with electrode solution, thus form electrode loop by electrode, electrolytic solution, oxide film sample;
A2) current value in potential electrode loop and magnitude of voltage, obtain the current-voltage correlation of pure electronic conduction, and then obtain pure electronic conduction resistance; Obtain the current-voltage correlation of Ion transfer, and then obtain ion move impedance in oxide film.
3. the method for a kind of quantitative determination oxide film microdefect according to claim 2, it is characterized in that, also comprise the current density of the current density current-voltage correlation of the current-voltage correlation of Ion transfer and pure electronic conduction being converted to Ion transfer to the relation of electric field intensity and pure electronic conduction to the step of the relation of electric field intensity, described current density is the oxide film area ratio that electric current contacts with electrode solution, electric field intensity is voltage and the ratio of oxide thickness, the current density of being moved by reference ion reflects the number of microdefect to the relation of electric field intensity to the current density of the relation of electric field intensity and pure electronic conduction.
4. the method for a kind of quantitative determination oxide film microdefect according to claim 2, it is characterized in that, described electrode solution is liquid metal or electrolyte aqueous solution, make electrode solution with liquid metal when measuring the pure electronic conduction electric current of oxide film, when measuring the Ion transfer electric current of oxide film, make electrode solution with electrolyte aqueous solution.
5. implement the instrument as the method for a kind of quantitative determination oxide film microdefect in Claims 1 to 4 as described in any one, it is characterized in that, comprise sample stage (1), oxide film sample (2), direct supply (3) and electrode (4), oxide film sample (2) is placed on sample stage (1), an electric heater (5) for heating oxide film sample (2) is provided with in sample stage (1), electrode (4) is overlaid on oxide film sample (2), by the under shed of oxide film sample (2) enclosed electrode (4), electrode (4) bottom is provided with under shed cavity volume, under shed cavity volume is communicated with outside by the through hole being located thereon portion, electrode solution (6) is filled with in the under shed cavity volume of electrode (4), electrode (4) connects a pole of direct supply (3), the metallic matrix of oxide film sample (2) connects another pole of direct supply (3), electrode (4), electrolytic solution, oxide film sample (2) forms electrode (4) loop, electrode (4) loop is provided with for the current value in potential electrode (4) loop and the reometer (7) of magnitude of voltage and voltage table (8), described sample stage (1), oxide film sample (2) and electrode (4) are positioned at a vacuum chamber, vacuum chamber is made up of chassis (11) and the vacuum (-tight) housing (12) be covered on chassis (11).
6. the instrument of a kind of quantitative determination oxide film microdefect according to claim 5, is characterized in that, also comprises a verification loop (9) in parallel with described electrode (4) loop.
7. the instrument of a kind of quantitative determination oxide film microdefect according to claim 1, it is characterized in that, described under shed cavity volume is circular cylindrical cavity, and the end face that hollow electrode (4) lower end contacts with oxide film is embedded with heat resistant rubber sealing ring.
8. the instrument of a kind of quantitative determination oxide film microdefect according to claim 1, is characterized in that, described electric heater (5) is by connection temperature controller (10).
9. the instrument of a kind of quantitative determination oxide film microdefect according to claim 1, it is characterized in that, sample stage (1) is fixed on the top on the chassis (11) of vacuum chamber, the sidewall of electrode (4) is stepped ramp type, an adjustable for height horizontal pressure foot (13) is overlaid on the step surface of electrode (4), thus is pressed on oxide film sample (2) by motor by pressing plate.
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| CN111487267A (en) * | 2020-04-09 | 2020-08-04 | 哈尔滨工业大学 | Method for stripping double-layer oxide film defect in aluminum bronze alloy |
| CN112129825A (en) * | 2019-06-25 | 2020-12-25 | 深圳市裕展精密科技有限公司 | Oxide film detection method and oxide film detection device |
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