CN104321636B - For the analysis method for the cleannes level for quantifying parts surface - Google Patents
For the analysis method for the cleannes level for quantifying parts surface Download PDFInfo
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- CN104321636B CN104321636B CN201380025490.4A CN201380025490A CN104321636B CN 104321636 B CN104321636 B CN 104321636B CN 201380025490 A CN201380025490 A CN 201380025490A CN 104321636 B CN104321636 B CN 104321636B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
- G01N27/423—Coulometry
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Abstract
For quantifying conduction sample (P) cleannes on surface (S) and/or the analysis method of activity level.This method includes：The surface of counterelectrode (2) and sample (P) is put into the electrolyte (1) comprising ion；Apply voltage (V) between counterelectrode (2) and the surface (S) for the sample (P) that quantify its cleannes and/or activity level using current generator (G)；The electric current (I) flowed between counterelectrode (2) and the surface (S) of conduction sample (P) is measured to change with time；And the cleannes and/or activity level of measurement assessment surface (S) according to the change to the electric current (I).
Description
The present invention relates to the horizontal side of the cleannes for allowing to analyze conduction sample surface and/or liveness (activation)
Method and apparatus field.
Background of invention
It is expected to apply to sample surface if the surface it is unclean if quality may affected surface treatment or coating
When, the assessment to the cleannes on the surface of the sample is particularly useful.The measurement of cleannes for example allows right before surface treatment
The preparation (pr é paration) of sample carries out qualitative.Pay attention to, if surface is unclean, the coating formed on sample is (at certain
Even sample is in itself in the case of a little) may be brittle.
The known method of cleannes for analyzing sample includes being taken by the moisture film being poured on sample by observation
Form assess the wetability of sample (mouillabilit é).Distribution of the moisture film on sample allows to position to be included on sample
Prepare the region of defect.One shortcoming of this measurement is：Because only allowing to observe macroscopical and hydrophobic Polluted area, this
Kind measurement is inaccurate.Another shortcoming of this test is：It is qualitatively non-quantitation.
Subject matter
Subject of the present invention is a kind of method and/or equipment of the cleannes and/or liveness for allowing to quantify sample surface.
The content of the invention
Therefore, the present invention relates to a kind of analysis for being used to quantify the cleannes and/or activity level on conduction sample surface
Method.The method is characterized mainly in that the method includes：
- counterelectrode is put into the electrolyte comprising ion and it is expected to quantify the institute of its cleannes and/or activity level
State the surface of sample；
- current generator is used in the counterelectrode and the sample that quantify its cleannes and/or activity level
The surface between apply voltage；
The electric current that-measurement is flowed between the counterelectrode and the surface of the conduction sample changes with time；
And
The cleannes and/or activity level on the surface are assessed in the measurement of change of-the foundation to electric current.
In order to allow to understand the present invention, it is noted that liveness is the ability that conductive surface interacts with electrolyte environment.This is active
Degree is bigger, and the electrochemical reaction on surface is better.Therefore, the good surface of liveness will improve faraday's yield rate and (reduce electric work
Consume and save the time) and more preferable electrolyte deposition will be caused to bond.
At least it is expected the table that quantify its cleannes and/or liveness of the sample of its cleannes of quantization and/or liveness
Face region must be conductive.
Flowing, electrolyte through the sample surface and the counterelectrode between the sample surface and the counterelectrode
Electric current is influenceed by the cleannes and/or liveness degree on this surface.Because test sample surface area and counterelectrode away from
The distance of this sample surface is constant (this area and this distance is preferably known and are default before measuring),
So it was observed that the change of the electric current flowed between counterelectrode and sample surface be substantially dependent on this surface cleannes and/or
Liveness, the cleannes and/or liveness especially determine the electric conductivity of its per unit area in two aspects of both macro and micro.
Therefore, polytype sample that method of the invention allows to detect the per unit area electric conductivity that may influence this sample lacks
Fall into.Such defect can be it is macroscopical, microcosmic, hydrophilic, hydrophobic, even under the surface of the sample simultaneously
It is and therefore sightless for simple Visual Observations Observations.As seen below, the method according to the invention is by means of COTTRELL
The physical property of (Cotterell) theorem, COTTRELL theorems are a kind of electrochemistry theorems.
This theorem proving：Mole expansion for the ion elements for depending in electrolyte being reduced with the curent change curve of time
Dissipate dynamics.However, this mole of diffusion depends on the state on the surface of the sample in itself, and particularly depend on its cleannes
And/or its liveness.Therefore, observation electric current, which changes with time, causes, has been said to be the reference sample of cleaning in use in advance
In the case of obtaining the model curve that electric current changes with time, the cleannes relative to cleaning reference sample and/or work are assessed
The cleannes and/or liveness state of sample measured by jerk state are possibly realized.
Pay attention to, the non-destructive method using the present invention especially has novelty come the activity level for quantifying conductive surface.
Therefore, method of the invention allows objective quantification cleannes and/or liveness state, such as to make objective decision
It must make it possible the type of processing that sample is subjected to.The present invention allows depending on being adjusted using field for sample is desired
Cleannes and/or activity level.Therefore, for being intended to the sample for requiring relatively not high environment, with being intended to be used to want
The sample of very high environment is asked to compare, lower cleannes and/or activity level may be received.
The invention further relates to for any reality in each embodiment using the analysis method described in the present patent application
Example is applied to manufacture the process of element (mechanical organ such as aircraft).
According to being characterized mainly in that for the first embodiment for being used to manufacture the process of element of the present invention：
- the element and sample are subjected to identical surface and prepare operation；Then
- by realizing such standard quantified according to the analysis method of any embodiment of each embodiment described in this application
The cleannes and/or activity level on the surface of the standby sample；Then
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to default
Standard satisfaction, then the element is subjected to additional operations to handle its surface；And
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to described
Preset standard is unsatisfied, then the element is again subjected to the surface preparation operation.
Statement " additional surface processing operation " is understood to mean that the operation for being intended to that adeditive attribute is provided to element, such as
Corrosion-resistant treatments, or improve the hardness of the element or provide protection to the surface.For example, additional operations may include to apply to the element
Application layer is such as probably the layer of painting layer, is mixed via the metal coating of electrolyte bath deposition or by spraying powder
Thing is come the coating that deposits.
This embodiment allows to assess the cleannes of manufactured element using multiple cleanliness testing sample/test samples
And/or liveness.Therefore cleannes/liveness of the element can be assessed without directly performing test to the element.Therefore, limit
The risk of the pollution/element that degrades during analyzing is made.
Because the realization to the additional operations of the element is to reach given cleannes/activity level in advance as condition
, so it was observed that this element is subjected to identical additional behaviour when showing than being not reaching to the given cleannes/activity level
The defects of element of work is statistically less.
It is not (such as foregoing using single sample/test sample according to the second embodiment of the process for manufacturing element
In first embodiment), but cleannes/liveness of the element is statistically assessed using multiple sample/test samples.
This second embodiment of the element manufacturing process is characterized mainly in that：
- the element and multiple samples are subjected to the preparation operation of identical surface, and (generally, surface, which prepares operation, is cleaning or deoils
Fat operates, such as performed in the bath comprising detergent)；And
The analysis method of any embodiment of-realization in each embodiment described in this application is with for so preparing
Each sample quantization surface cleanness and/or activity level；Then
If these cleannes and/or activity level of-the sample surface so quantified are considered as relative to default
Standard satisfaction, then the element is subjected to additional operations to handle its surface；And
If these cleannes and/or activity level of-the sample surface so quantified are considered as relative to described
Preset standard is unsatisfied, then the element is again subjected to the surface preparation operation.
Here, equally, the realization of surface treatment operations is to reach in advance via the survey performed to the sample/test sample
It is condition to try as the cleannes and/or activity level of element estimation.
Using the present invention, the surface treatment that the element performs is not measured than the cleannes and/or liveness in advance/
Situation during assessment has higher quality.
Specifically, if surface treatment operations include overlay, this layer will once reach the estimation of the element
Applied after cleannes and/or activity level.If not yet reaching the estimated level, the table of the element is then performed
The additional preparation operation in face, additional surface processing operation required cleannes and/or activity level are performed until reaching
Untill.Therefore, using the present invention, the coupling for statistically improving the layer formed on that element is possible.
Finally, the present invention relates to a kind of equipment for being used to quantify the cleannes and/or activity level on conduction sample surface.
This equipment is characterized mainly in that this equipment includes：
- it is used for the container that introducing includes the electrolyte of ion；
The sealing device of the periphery extension in-hole in the container, these sealing devices are arranged in the container
The institute towards the container for being intended to the interior zone comprising the electrolyte and the conduction sample comprising the surface
Establishment seals between stating a part for interior zone；
- towards the counterelectrode being put into the container of the container hole；
- it is connected to the current generator of the counterelectrode；
- preferably, the reference electrode of the electric current delivered for adjusting the maker；And
- at least one region for being arranged to allow the sample and the arrangements of electric connection of maker electrical connection,
- the maker, which is arranged between the counterelectrode and the arrangements of electric connection, delivers voltage, and
- the equipment also includes being used to measure the electric current flowed between the counterelectrode and the arrangements of electric connection at any time
Between change device.
The equipment of the present invention is particularly suitable for realizing the either method in the analysis method according to the present invention.
Using this equipment, the hole of the container is located against the current-carrying part placement of the sample.It is expected to assess its cleannes and/or
The sample surface of liveness is then placed against the container hole and the counterelectrode.Next, electrolyte and ion are introduced in
In the container, on the one hand this electrolyte contacts with the counterelectrode, on the other hand contacted with the surface of the sample, the surface is away from this
Counterelectrode certain distance.The subsequent maker delivers D/C voltage electric current and the measurement apparatus assesses the counterelectrode and the sample surface
Between the change of electric current that passes through.
As explained above, this measurement allows cleannes and/or the liveness for characterizing the sample surface.
It is desirable that this equipment includes the surface for automating the sample measured by the analysis and automatically delivering representative
(term " reading " is understood to mean that may take e-command and/or paper to the device of the reading of cleannes and/or liveness
The information of the form of matter printing).Depending on this information, operator can be directed to his/her sample for having manufactured or element is necessary
The additional treatments being subjected to are maked decision.
As will be seen, can utilize relative to the potential selected by known reference to measure electric current.
This kind equipment implement it is not expensive, and can easily by be not surface state assayer operator
Using and directly can use in a manufacturing environment, to measure the cleannes of sample or element and/or liveness.
Brief description
Explained and in the description that is given with reference to the accompanying drawings from below by non-limiting, it is of the invention (method, process and to set
It is standby) other feature and advantage will become apparent, in the accompanying drawings：
- Fig. 1 shows to allow for the first embodiment of the equipment of the method according to the invention；
- Fig. 1 a show the front view with the sample for it is expected surface for assessing its cleannes and/or liveness；
- Fig. 1 b show the rearview of the sample in Fig. 1 a；
- Fig. 2 shown for reference to for conductive surface, as the curve of the change of the measured electric current of the function of time,
According to formula √ (1/T) by herein time T expression on the horizontal scale (in order that this figure be easier to understand, give with
The corresponding time T of second meter)；
- Fig. 3 is shown as the example of three curves of the change of the electric current of the function of time, and these curves are using the present invention
Method and apparatus to each sample measurement (be used herein as scale √ (1/T) and using in seconds nonlinear scale T by when
Between shown on transverse axis)；
- Fig. 4 is the cleannes of conductive surface and/or the analytical equipment of the invention of activity level for allowing quantized samples
One embodiment viewgraph of cross-section.
Embodiment
As described above, the present invention relates to a kind of cleannes and/or liveness of the conductive surface for being suitable for quantized samples
Horizontal analysis method.
If for example, to the cleaning or processing step on sample surface or the surface of the element associated with sample
Realization be to be considered as using the surface analyzed clean enough as condition, then the cleannes and/or liveness on surface are entered
The ability that row quantifies is critically important.
Generally, conduction sample is made of metal alloy (such as steel alloy, aluminium alloy or nickel alloy).
As being seen below, sample P can be：
- sample, the aircraft landing gear axle such as obtained from production line；Or
- being used on indirect assessment production line the test sample of the cleannes of the element and liveness manufactured, (element is for example
Can be undercarriage axle and the sample is then the test sample that same treatment is experienced with the axle, this test sample sample is preferably
By being made with manufacture element identical material).
In order to analyze conductive surface S cleannes/liveness, the sample P surface S to be analyzed is defined, thus allowed
Tested surface area is fixed.Defining surface S allows to influence between sample P and counterelectrode (contre- é lectrode) 2
An electric current I parameter of change fixed.
Surface S is defined as so that its area keeps constant between different sample P, and thereby increase measuring condition can
Repeatability simultaneously to compare measured result.
If surface S area is identical, using identical measurement parameter (between identical electrolyte, counterelectrode and surface S
Identical distance D, identical ion dose) measured by the curent changes of two different samples can be compared to each other.As
It is seen below, if one of these samples are considered as reference sample Pref, another sample P cleannes/liveness
Can be by the way that the property for the curent change of these samples Pref and P measurements be compared to quantify.
Fig. 1 a and 1b show defining surface S first way, including are intended to be connect with electrolyte in addition to the S of surface
Tactile electrode/sample P all parts apply electric insulation layer 9 (being in this example plastifying film for self-adhesive).In Figure 1b, can be with
See another in test sample sample P two surfaces.Electrical connection area except being intended to keep certain distance with electrolyte
Outside domain 12, this surface is covered by insulating barrier 9 completely.In fig 1 a, insulation strip 9 separates electric coupling area 12 and surface S.Electricity
Solution matter liquid level is located above the S of surface and flushed with insulation strip, but does not touch region 12.Therefore, even if electrolyte levels change,
In the case that it is still flushed with insulation strip 9, the immersed surface S made electrical contact with electrolyte will ensure always there is identical
Area.
Shown in Fig. 4 and limit this surface S area to make it keep constant and consistent another between different samples
Kind mode.In this figure, the equipment 0 for quantifying surface S cleannes/activity level includes being used to introduce electrolyte 1
Container 4, and the sealing device 5 of the periphery extension in hole 6 in container 4.Herein, these sealing devices 5 are by the flexibility in hole 6
What ring packing was formed.This sealing is arranged such that when this is sealed against on flat surfaces the sealing produces sealing,
And Ring like suction disc is preferably formed, the Ring like suction disc maintains to be pressed against sample P sealing.For this reason, this sealed bundle contains
(on the one hand, generation seals the annular groove of formation sucker between the interior zone 12 and a part for sample of container 4, another
Aspect maintains container 4 on sample P).Thus inner periphery that surface S is sealed defines that (container is rigid and maintained
The shape of sealing so that the area defined between two samples keeps constant).Subsequent only sample P surface S in face of hole 6 so as to
Touch the electrolyte 1 accommodated in container 4.
Using these characteristics of sealing device 5, for any sample of the sample portion with given geometry, create
Be close to sample portion P sealing ensure that surface S be defined part will always be to maintain it is identical.
The method according to the invention, and as shown in figs. 1 and 4, in order to analyze ,/measurement surface S cleannes/are enlivened
Degree：
The surface S of-counterelectrode 2 and sample is placed in container 4 so that their fixations relative to each other and apart it is pre-
If distance D；
- reference electrode 3 is placed in container 4 so that the reference electrode is also away from the fixed ranges of surface S mono-；And
- arrangements of electric connection 7 is used to electrically connect sample P at least one region and current generator G.
Perform aforesaid operations and make it that counterelectrode 2 and reference electrode 3 are fastened via fastener, so as to surface S and these
Electrode 2, the distance between 3 keeps constant and sample P by another sample P of the part with equivalent geometry during measurement
It is reproduced during substitution.
In the case, reference electrode 3 be potassium chloride saturation calomel electrode or Ag/AgCl electrodes (for example, having
KCl 3mol/L electrolyte and the salt bridge of salt bridge) and counterelectrode 2 is platinum or gold electrode.
Once these electrodes 2,3 and surface S have been placed into container, then electric electrolyte is introduced in container.Via electricity
Attachment means 7 are electrically connected to counterelectrode 2, the maker G of electric current I to reference electrode 3 and to surface S be then powered up so as to
The default D/C voltage of generation.In Fig. 1, arrangements of electric connection 7 includes being anchored on leading for the part for the sample P not being immersed in electrolyte
Electricity folder.In Fig. 4, arrangements of electric connection 7 includes the conductive component fixed to metal sample P and positioned at away from the container and surface S
At a certain distance from least one electrical contact, it is towards the inside of the container.It should be noted that under a particular case, the sealing can
Current-carrying part including being placed on the external container, away from electrolyte, to allow surface S to be electrically connected to maker G and these
Attachment means 7 do not contact with electrolyte 1 again.
Maker G delivers constant voltage V between counterelectrode 2 and arrangements of electric connection 7, thus allows in surface S and anti-electricity
Constant voltage V ' is obtained between pole 2.Measured by using reference electrode 3 to assess/adjust in counterelectrode 2 and be connected to surface S
Arrangements of electric connection 7 between this voltage V for applying.Electric current I between counterelectrode 2 and surface S, should using amperometric measurement
Galvanometer belongs to device M, is changed with time for measuring electric current I.
Electric current I change is stored in memory to be then analyzed.
It is connected to electrode 2,3 it should be noted that maker G and measurement apparatus M can belong to and is connected to the voltage-stablizer of device 7, this
Voltage-stablizer records I measurement result.It is furthermore noted that for the correct operation of the equipment, can be used can have preset resistance
Negative electrode obtains cathode resistor.
When regulation current generator G keeps constant so as to voltage V, voltage V ' (that is, the electricity between surface S and counterelectrode 2
Pressure) also keep constant during measurement electric current I changes with time.This voltage-regulation make it that these constant voltages V's or V ' is exhausted
Value is kept below or equal to predetermined threshold value voltage.In the case, threshold voltage is less than 0.5 volt, is preferably lower than 0.2 volt,
And preferably lower than or equal to 0.15 volt and more than 0.05 volt.Preferably, the threshold value for selecting constant voltage V to be equal to 0.15 volt, by
This to prevent surface S from during analysis degrading, because voltage V ' (it is less than or equal to V) will not be over 0.15
Volt.
The equipment of the present invention performs the measurement of three electrode voltammetries, and it allows to characterize entering for the electrochemical reaction in electrolyte 1
Journey.In order to adjust the constant voltage V ' being applied between counterelectrode 2 and surface S, measurement is represented between reference electrode 3 and surface S
Voltage voltage.The electric charge stream that electric current I measurement allows to flow through surface S is quantized, and voltage V and voltage V ' keeps constant.
According to the COTTRELL equations of the simplification relevant with electrochemical properties：
I=n.F.S ' .C0 ° .D01/2√ (1/t)=K. √ (1/t)
Wherein：I:Electric current (in terms of A or C/s)
n:The electron number that the system is exchanged
F:Faraday constant=96500C/mol
S’:Active area of S ': negative electrode (m2)
C0°:It is reduced the initial concentration (mol/m of element3)
D0:It is reduced the mole diffusion coefficient (m of element2/s)
By write down electric current I with time T value and draw curve I=f (√ (1/t) (as shown in Figure 2), it is likely that
Parameter K is derived, parameter K is the value of the slope K of the straight line obtained on measuring section X.Sample P for indexing n, is obtained
The straight line Dn that slope is Kn is obtained, it especially characterizes this sample Pn cathode surface.
Parameter K, Kn represents the electric current I measured on measuring section X rate of change.By by this parameter and to reference sample
The predetermined threshold value value Kref that Pref (in terms of its surface S is prepared, this sample is considered as optimal) is measured compares, surface S
(attribue) value can be then assigned, the value quantifying surface S cleannes and activity level.
Kn and Kref are compared by ratio calculated Kn/KRef (in terms of %).
Kn is the slope of the linear regression line of the electric current I measured on period X change, and wherein sample Pn will be tested
And under constant potential V '.
Kref is the slope of the linear regression line of the electric current I measured on period X change, wherein reference sample Pref
It is tested and is under constant potential V '.
As shown in Figure 2, period X starts to be supplied to counterelectrode after electric current preset time, and the preset time is preferred
Ground is longer than 5 seconds and is preferably incorporated between 10 seconds and 20 seconds.The curve of electric current I change more represents period X rather than period Y
Middle surface S cleannes/liveness is (whole when period Y is when since being supplied the electric current of counterelectrode and period X
Only).
Fig. 3 is shown, for period X, respectively for each sample P1, P2, PRefFor electric current I change curve C1, C2,
Cref。
Curve C2Corresponding to the electric current I measured with the sample P2 of grease change, sample P2 once stayed in degreasing bath
In some seconds.
Curve C1Corresponding to the electric current I measured with sample P1 change, sample P1 experienced it is more more preferable than sample P2 cleaning/
Degreasing is handled.
Curve Cref with corresponding with the electric current I measured by the reference sample Pref of ideally degreasing change (Pref is
Prepare in the following manner：In degreasing bath Immersion time of the submergence than sample P1 to the time of 6 times of the youthful and the elderly, then with logical
Cross and wipe the acetone that applies to rebuild Pref surface, then carry out secondary degreasing processing and newly rebuild, connect with acetone
Is sandblasting and minute surface finishing polishing).
In described Fig. 3, because period Y is considered as that estimation with the preparation to surface S is unrelated, it is not shown
Period Y and merely illustrate period X.The timeorigin of measurement has been shifted to be overlapped with the starting point with relevant time period X.
Use wherein R2Linear regression method (the hint linear regression Correct effect) of the coefficient higher than 0.9, for
These curves C1,C2,CRefEach of calculate the corresponding linear tropic respective slope K1,K2,KRef.In this example,
In order to define these linear regression lines, the I measured in period Y the first value is excluded, because the effect as time goes by
Surface S cleannes/liveness should be become more to represent.Herein, the R greater than or equal to 0.95 is obtained2, and K1=-7.21 ×
10-5、K2=-1.0026 × 10-4And KRef=-1.34 × 10-4.For curve C1, K1/Kref=53.8%.For curve C2:K2/
KRef=74.8%.Finally, and logically, for curve CRef：KRef/KRef=100%.
Pay attention to, sample is dirtier, ratio Kn/KRefIt is lower.In turn, sample more cleans, ratio Kn/KRefIt is higher, until reaching
Untill 100% preferable cleannes/enliven angle value.This ratio R=Kn/KRefIt is a particularly accurate value, it allows to quantify sample
This Pn preparation/liveness state and its surface cleanness.For example, if threshold value is provided with (for example, R=for ratio R
70%), then it may be said that the sample with the ratio R less than 70% is uncleanly and is subjected to additional surface and prepares,
And the sample Pn with the ratio R higher than 70% be considered as cleaning and may therefore undergo additional surface treatment step
Suddenly, painting layer is such as applied.
When realizing of the invention, for each in these measurements, electrolyte 1 is identical.Electrolyte 1 includes：
- the salt selected from halogen, ammonium salt, such as carbonate, carboxylate, cyanide salt and the organic salt of organic magnesium salts；
The polar solvent of-possibility relative tack, such as ketone, alcohols, aldehydes, aqueous medium or gel；And
In-the solvent naturally occurring or not at least one sour and/or at least one alkali (base).
The acid is from the selection in the sour group including the following：Such as mineral acid of phosphoric acid, sulfuric acid, and such as
The organic acid of carboxylic acid.
Alkali is selected from the group by the alkali of the following：Caustic soda, caustic potash and ammonia.
Electrolyte 1 can take the form of liquid or gel, wherein gel because flowing less than liquid with more
The advantages of being easy to apply to sample surface.Gel can be the gel based on silica and/or agar.
It is desirable that in order to ensure electrolyte is with the useful work model of the sample to being analyzed made of steel and stainless steel
Enclose, electrolyte includes：
-0.1g/l<[ferrocyanide, such as potassium ferrocyanide]<0.5g/l；
-0.1g/l<[iron cyanide, such as potassium ferricyanide]<0.5g/l；
-0ml/l<[strong acid]<1ml/l；
-0ml/l<[weak acid]<10ml/l；
- there is no halogen (they make steel degrade)；
-0g/l<[ammonium salt]<0.1g/l；And
- without carbonate (they are passivated the steel layer of activation)
Other salt that can be used:
-0g/l<Caustic soda<10g/l；And
-0g/l<Caustic potash<10g/l.
Pay attention to, Fe2+ the and Fe3+ ions of ferrocyanide and the iron cyanide form electrochemistry coupling, and the electrochemistry coupling helps
In observation Cotterell theorems without to carrying out undesirable deposition on the surface S analyzed.In addition, the Fe2+/Fe3+ couplings
To work under low-down potential V, oxygen will not be reduced under potential V.Therefore pressure nitrogen is not had to
The container is purified to avoid the risk of blast.Another advantage of ferrocyanide and the iron cyanide is：Cyanide makes this be
System is stable (Fe2+ ions generally become unstable over time).
It is for performing the ideal conditions currently measured：
The temperature of-electrolyte is between 15 DEG C and 30 DEG C；
- constant potential the V applied：Between 0.2V and 0.05V；And
- for acceptable result, linear regression coeffficient R2>0.98；
The type that the air of electrolyte is surrounded in-operating pressure (electrolyte pressure) and container may depend on needed for measurement
Accuracy selects.Therefore, the pressure can be the pressure of atmospheric pressure, vacuum or superatmospheric.
The type of-used air can be air or its derivative (air rich in oxygen, pure O2、N2、CO2)
Or (pollution causes the ripple of electrochemical impedance to one or more organic gas in medium used in being even dissolved in
It is dynamic, thus destroy measurement or cause result to be difficult to understand)；And
- in order that must measure more reliable, the ferrari case of ground connection can be placed in the complete of container 4, sample P and/or maker G
Portion or portion.
As shown in Figure 4, equipment 0 of the invention further comprises being connected hydraulically to electrolyte accumulator tank 11 and container 4
Interior zone Z pump 10.The pump 10 controlled device Cde is controlled optionally to fill or empty the appearance with electrolyte
Device.Therefore, after the container has been applied in/be fastened to sample P, after on surface, S has been defined and in arrangements of electric connection 7
After being connected, the filling container 4 of electrolyte 1 is used in control device Cde requests, to submerge electrode 2,3 and surface S therein.Connect
Get off, device Cde requests：
- maker G delivering upon mediation voltages V electric current；And
- measurement apparatus M assesses changes of the electric current I with time T.
Once the measurement has been performed and recorded, then container 4 is emptied into accumulator tank 11 by device Cde requests pump 10.
The temperature of catalyst 1 is preferably adjusted by the heat regulating device of the equipment, so as to the temperature be included in it is pre-
If in temperature values (15 DEG C -30 DEG C).
In order to help this measurement, the convection current in container 4 is limited as far as possible.For this reason, electrode 2,3 is at least
Fixed during whole current measurement.
It is desirable that the element for assessing its cleannes/liveness is undercarriage axle and this assessment is by preparing on its surface
Multiple sample/test samples are placed in the axial default key position to perform by the stage.Next, use this
The method of invention analyzes these sample/test samples (it is respectively provided with conductive surface), and therefore derives each shaft position
The state that the surface of the axle at place prepares.The method of the present invention can be used for the figure for the cleannes and/or liveness for producing the axle.
The use of multiple samples (being test sample in the case) is favourable, because this permission divides via indirect method
Analyse cleannes/liveness of the axle and make the risk of its degradation without risking.If each value obtained is satisfactory, perform
Additional surface treatment operations (for example, to the axle coat coating).
Finally, it is noted that because the present invention allows the cleannes/liveness for measuring sample, the present invention can be used for table
The quality for levying set-up procedure (for example, handling defect area so as to prominent, or then bathes aging in degreasing or is possible to qualitative
(qualifier) detergent).
Claims (19)
1. the cleannes on surface (S) and/or the analysis method of activity level for quantifying conduction sample (P), its feature exist
In methods described includes：
- surface (S) of counterelectrode (2) and the sample (P) is put into the electrolyte (1) comprising ion；
- use current generator (G) in the counterelectrode (2) and to quantify the sample of its cleannes and/or activity level
Apply voltage (V) between the surface (S) of this (P)；
The electric current (I) that-measurement is flowed between the counterelectrode (2) and the surface (S) of the conduction sample (P) is with the time
Change；And
The cleannes and/or activity level of the surface (S) are assessed in the measurement of change of-the foundation to electric current (I),
Wherein in order to assess cleannes and/or activity level according to the measurement of the change to the electric current, it is determined that when representing
Between electric current measured in section (X) rate of change parameter (Kn) and this parameter (Kn) and predetermined threshold value value (Kref) are carried out
Compare, then depending on this compares, to the surface (S) assignment (R) of the sample (P), described value quantifies the surface
Cleannes and/or activity level.
2. according to the method for claim 1, it is characterised in that in the counterelectrode (2) and the table of the sample (P)
The voltage (V) applied between face (S) is come what is measured using the reference electrode (3) being also disposed in the electrolyte (1).
3. according to the method described in any one of foregoing claim, it is characterised in that the current generator (G) be conditioned so that
It is constant that the voltage (V), which is obtained, during measuring the electric current (I) and changing with time, and causes this constant voltage (V)
Absolute value be less than or equal to predetermined voltage threshold.
4. according to the method for claim 3, it is characterised in that the predetermined voltage threshold is less than 0.5 volt.
5. according to the method for claim 4, it is characterised in that the predetermined voltage threshold is less than or equal to 0.15 volt.
6. according to the method for claim 4, it is characterised in that the predetermined voltage threshold is higher than 0.05 volt.
7. according to the method for claim 2, it is characterised in that the reference electrode (3) is the protochloride of potassium chloride saturation
Mercury electrode or Ag/AgCl electrodes, and the counterelectrode is platinum or gold electrode.
8. according to the method for claim 1, it is characterised in that the parameter for representing the rate of change of the electric current is to be based on
The slope K n of the straight line (Dn) defined within the period to the measurement that the electric current changes with time by linear regression, institute
It is default slope value Kref to state predetermined threshold value value, and the comparison includes ratio calculated R=Kn/Kref, and the value of this ratio R allows
Quantify the cleannes and/or activity level on the surface (S) of the sample (P).
9. according to the method for claim 1, it is characterised in that the period (X) has been applied in institute in the electric current
State and start between counterelectrode (2) and the surface (S) of the conduction sample (P) after a time span (Y).
10. according to the method for claim 9, it is characterised in that the time span (Y) is at least 5 seconds.
11. according to the method for claim 9, it is characterised in that the time span (Y) is at least 20 seconds.
12. method according to claim 1 or 2, wherein the electrolyte (1) includes：
- the salt selected from halogen, ammonium salt, carbonate, organic salt；
- polar solvent；And
- at least one sour and/or at least one alkali,
- at least one acid is selected from including following various sour groups：Mineral acid, and organic acid, and
- at least one alkali is selected from the group including following various alkali：Caustic soda, caustic potash and ammonia.
13. according to the method for claim 12, it is characterised in that the organic salt includes carboxylate, cyanide salt and had
Machine magnesium salts, the polar solvent include ketone, alcohols, aldehydes, aqueous medium and gel, and the mineral acid includes phosphoric acid and sulfuric acid,
And the organic acid includes carboxylic acid.
14. method according to claim 1 or 2, it is characterised in that what its cleannes and/or activity level were quantized
Defined by the electric insulation layer (9) carried by the sample (P) on the surface (S) of the sample (P).
15. the process for manufacturing element, it is characterised in that：
- the element and sample are subjected to identical surface and prepare operation；Then
- by realizing according to the analysis method of any one of preceding claims quantify the surface of the sample so prepared
Cleannes and/or activity level；Then
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to preset standard
Satisfied, then the element is subjected to additional operations to handle its surface；And
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to described default
Standard is unsatisfied, then the element is again subjected to the surface preparation operation.
16. the process according to claim 15 for being used to manufacture element, it is characterised in that the element is aircraft landing gear
Axle.
17. the process for manufacturing element, it is characterised in that：
- the element is subjected to the operation on the surface for preparing the element；Then
- by realizing according to any one of claim 1-14 analysis method quantify the surface of the element so prepared
Cleannes and/or activity level；Then
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to preset standard
Satisfied, then the element is subjected to additional operations to handle its surface；And
If the cleannes and/or activity level of-the sample surface so quantified are considered as relative to described default
Standard is unsatisfied, then the element is again subjected to the surface preparation operation.
18. the cleannes on surface and/or the equipment of activity level for quantifying conduction sample, it is characterised in that described to set
It is standby to include：
- it is used for the container (4) that introducing includes the electrolyte (1) of ion；
The sealing device (5) of the periphery extension in-hole (6) in the container (4), these sealing devices (5) are arranged in
The container (4) is intended to the interior zone (Z) comprising the electrolyte (1) and the conductive sample comprising the surface (S)
Sealing is created between the part towards the interior zone (Z) of the container (4) of this (P)；
- towards the counterelectrode (2) being put into the container (4) in the container (4) hole (6)；
- it is connected to electric current (I) makers (G) of the counterelectrode (2)；And
- at least one region for being arranged to allow the sample (P) and the arrangements of electric connection of the maker (G) electrical connection
(7),
- the maker (G), which is arranged between the counterelectrode (2) and the arrangements of electric connection (7), delivers voltage (V),
And
- the equipment also includes the electric current flowed for measurement between the counterelectrode (2) and the arrangements of electric connection (7)
(I) device (M) to change with time,
Wherein in order to assess cleannes and/or activity level according to the measurement of the change to the electric current, it is determined that when representing
Between electric current measured in section (X) rate of change parameter (Kn) and this parameter (Kn) and predetermined threshold value value (Kref) are carried out
Compare, then depending on this compares, to the surface (S) assignment (R) of the sample (P), described value quantifies the surface
Cleannes and/or activity level.
19. equipment according to claim 18, it is characterised in that the sealing device (5) is arranged such that when in institute
It is only described when stating establishment sealing between the interior zone (Z) of container (4) and the part of the conduction sample (P)
The expectation of sample quantifies the surface (S) of its cleannes and/or activity level towards the hole in the container (4)
(6) and can be contacted with the electrolyte (1) included in the container (4).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1254380A FR2990513B1 (en) | 2012-05-14 | 2012-05-14 | ANALYSIS METHOD FOR QUANTIFYING A LEVEL OF CLEANLINESS OF A WORKPIECE |
| FR1254380 | 2012-05-14 | ||
| PCT/EP2013/059823 WO2013171163A1 (en) | 2012-05-14 | 2013-05-13 | Analysis method for quantifying a level of cleanliness of a surface of a part |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104321636A CN104321636A (en) | 2015-01-28 |
| CN104321636B true CN104321636B (en) | 2018-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380025490.4A Active CN104321636B (en) | 2012-05-14 | 2013-05-13 | For the analysis method for the cleannes level for quantifying parts surface |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN104321636B (en) |
| CA (1) | CA2872590C (en) |
| FR (1) | FR2990513B1 (en) |
| GB (1) | GB2516393B (en) |
| MX (1) | MX339609B (en) |
| WO (1) | WO2013171163A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104007147B (en) * | 2014-06-06 | 2016-07-13 | 华进半导体封装先导技术研发中心有限公司 | The detecting device of bottom electrode surface and detection method in high aspect ratio microstructures |
| CN105351720B (en) * | 2015-11-20 | 2017-08-25 | 莱芜钢铁集团有限公司 | A kind of thin oil oil return pond and its detection method of filter core pollution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283267A (en) * | 2005-10-06 | 2008-10-08 | 空中客车德国有限公司 | Method for detecting residues on a component |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515643A (en) * | 1982-10-22 | 1985-05-07 | Henkel Kommanditgesellschaft Auf Aktien | Method for determining and adjusting the potency and effectiveness of a metal phosphate conversion coating process |
| WO1998050788A1 (en) * | 1997-05-07 | 1998-11-12 | Spellane Peter J | Electrochemical test for measuring corrosion resistance |
| US6365034B1 (en) * | 1997-05-07 | 2002-04-02 | Polymer Alloys Llc | High throughput electrochemical test for measuring corrosion resistance |
| DE19749111C2 (en) * | 1997-11-06 | 2001-10-18 | Siemens Ag | Measuring cell for examining a metallic object |
| JP2008292408A (en) * | 2007-05-28 | 2008-12-04 | Nippon Steel & Sumikin Stainless Steel Corp | Temporal evaluation method for crevice corrosion initiation |
| US8221603B2 (en) * | 2008-06-27 | 2012-07-17 | Reactive Innovations, Llc | Membrane transducer surface contact sensor |
-
2012
- 2012-05-14 FR FR1254380A patent/FR2990513B1/en active Active
-
2013
- 2013-05-13 CA CA2872590A patent/CA2872590C/en active Active
- 2013-05-13 CN CN201380025490.4A patent/CN104321636B/en active Active
- 2013-05-13 MX MX2014013804A patent/MX339609B/en active IP Right Grant
- 2013-05-13 GB GB1419735.4A patent/GB2516393B/en active Active
- 2013-05-13 WO PCT/EP2013/059823 patent/WO2013171163A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283267A (en) * | 2005-10-06 | 2008-10-08 | 空中客车德国有限公司 | Method for detecting residues on a component |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201419735D0 (en) | 2014-12-17 |
| FR2990513B1 (en) | 2020-03-20 |
| WO2013171163A1 (en) | 2013-11-21 |
| CA2872590C (en) | 2017-07-18 |
| GB2516393B (en) | 2017-08-02 |
| CA2872590A1 (en) | 2013-11-21 |
| FR2990513A1 (en) | 2013-11-15 |
| MX339609B (en) | 2016-05-31 |
| CN104321636A (en) | 2015-01-28 |
| MX2014013804A (en) | 2015-04-10 |
| GB2516393A (en) | 2015-01-21 |
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