CN1723298A - Method for protecting metal-containing structures deposited on substrates against corrosion - Google Patents

Method for protecting metal-containing structures deposited on substrates against corrosion Download PDF

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Publication number
CN1723298A
CN1723298A CNA2004800019553A CN200480001955A CN1723298A CN 1723298 A CN1723298 A CN 1723298A CN A2004800019553 A CNA2004800019553 A CN A2004800019553A CN 200480001955 A CN200480001955 A CN 200480001955A CN 1723298 A CN1723298 A CN 1723298A
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China
Prior art keywords
voltage
passivation
deposited
corrosion
metal
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CNA2004800019553A
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Chinese (zh)
Inventor
H·莫伊泽尔
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Saint Gobain Glass France SAS
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Publication of CN1723298A publication Critical patent/CN1723298A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/005—Anodic protection
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/04—Controlling or regulating desired parameters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G01N27/223—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance for determining moisture content, e.g. humidity

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Ecology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Environmental Sciences (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)

Abstract

The invention concerns a method for protecting metal-containing structures, in particular electrically conductive structures, deposited on a substrate, against corrosive attacks, in particular electrocorrosion attacks. Said method is characterized in that it consists in applying at least temporarily to the structure a passivation electric voltage in the passivation range of the conductive material concerned.

Description

The structure that contains metal that protection is deposited on the base material is avoided corroding method
The present invention relates to protect the structure that contains metal that is deposited on the base material to avoid corroding method, prevent the conductor rail corroding method especially.
Usually people know, have all placed conductor rail or bottom surface structure that various application are arranged on vehicle glazing, and they are made with glass often, but also use synthetic materials (for example polycarbonate) manufacturing more and more.These structures are used as antenna, heating field, transmitter etc.In addition, in buildings, particularly in the roof glass window, rain sensor has constituted the part of this technology status.Some structure example, are used as and damage transmitter (current circuit of interruption) for example for internal application as being used on the toughened glass plate like this.
Usually, by the slurry to be solidified of a kind of high silver content of silk screen printing on glass basis, make described structure in large quantities.If relate to the monolithic glass plate, then often when making it crooked, carry out roasting with heating glass plate, then quench.
Place under the situation of more such conductive structures in this sheet glass outside,, after using under the long-term severe weather, some corrosion phenomenons may occur as humidity or especially this situation of rain sensor.Some different sfgd.s have been proposed for this reason.
So publication DE-A 2 231 095 has described deposition a kind of dielectric materials (varnish) on some conductive structures, this structure is used as thermal conductor on glass pane surface.Publication DE-C1-100 15 430 has described the transmitter that plays a role with capacitive way, and it can detect the condensation product of glass pane surface, has deposited one deck dielectric passivation layer on its electrode.In this production method, on the structure of roasting, on purpose deposit one deck extra play and but be very affined, tediously long and an irksome intermediate steps, because it should process very accurately.If a kind of like this transmitter for example is that then As time goes on this protective layer can wear and tear within this windscreen wiper steam circle, therefore necessary words should be upgraded.
Just say that people know in essence, it may prevent electrocorrosion when applying voltage effectively some metal pairs.The file of relevant this theme can obtain from following internet address:
http:∥docserver.bis.uni-oldenburg.de/publikationen/dissertation/2000/ducperOO/pdf/kapO2.pdf。Relate to German paper and extract (the 2nd chapter) " Periodische und chaotischeOszillationserscheinungen anMetallelektroden und elektrochemische Modellexperimente zurErregungsleitung am Nerven "/Matthias Ducci.-2000.-IX, 268S.+s é quences vid é o sur CD-ROM.-Univ.Oldenburg, 2000.For preventing iron rot, this file conclusion confirms, applies sufficiently high external voltage and can regulate the passivation potential to be determined that mesh voltage in this metal is higher than this material.In case reach this passivation potential, just can keep this state by low-down current density.This passivation current density and this corrosion electric current density should be comparable, and the corrosion electric current density of iron is about 10 μ A/cm 2, and this passivation current density is about 0.2A/cm 2
Publication WO-A1-01/07 683 has described the application that prevents concrete reinforcement erosion of this respect.By applying a controlled low dc voltage to reinforcing bar by means of an anode system, eliminating these surface electrical potential differences, and produce a uniform electromotive force, prevent its corrosion like this.
In known other used, proposed to use alternating voltage to come passive metal, prevent corrosion.But, to observe, when using alternation passivation voltage, the gradual change corrodibility of steel is fast during than the situation of using volts DS.This available alternating voltage degenerates the passive surface layer and makes an explanation.
But also observe, the frequency that improves alternating voltage can make the corrodibility trend of the structure that has applied alternating voltage reduce, and has correspondingly improved the protection effect to it.The change in polarity of this available current direction than the diffusion of corresponding current carrier by passivation layer faster make an explanation.
Should determine this passivation magnitude of voltage for the treatment of anticorrosive individually.Usually possible is reduces to minimumly according to corrosion current (to degrade speed proportional with metal), even external voltage or passivation magnitude of voltage when going to zero are determined significant passivation scope, this means any etching problem no longer takes place.Under the situation of low-down external voltage; do not reach abundant inhibition corrosive effect (" activity " scope); and under the situation of very high external voltage, (be higher than " triggering electromotive force "); the state of " transpassivation " has appearred being called as; at this moment no longer shield, and corrosion current obviously increases again.
In the metal construction field of buildings, people have known the application of this electric passivation in fact.
The objective of the invention is to propose a kind of base material that prevents to be deposited on, the structure that contains metal on the sheet glass particularly, be exposed to the corroding method that causes because of severe weather under the severe weather, and this method allows not need to replenish passivating coating on these conductive structures.
These features by claim 1 can realize purpose of the present invention.The mark sheet of these independent claim is understood the favourable improvement and the application thereof of this method.
The present invention is based on such consideration: these conductive surface structures contain above-mentioned metal, and particularly silver-colored, such surface tissue can also constitute by applying suitable voltage can prevent the corrosive passivation system.
When carrying out battery of tests, observed, for at the industrial employed material of structure that is printed on sheet glass or the synthetic materials plate, can prevent quick corrosion effectively by applying volts DS and alternating voltage, described structure example is humidity sensor, damage detector, antenna and heater in this way, promptly a kind of silk screen printing slurry of being made up of the frit of high silver content.But do not press for to electrode and apply passivation voltage enduringly.
The layout of conductive structure is conclusive.For this electric passivation, therefore actively prevent this corrosion, on substrate surface in same or another kind of mode each other very near placing, rather than between two electrical conductor that are electrically connected to each other, the potential difference that is up to passivation voltage is necessary.Under the situation of the transmitter that moves with capacitive way, can realize this point in simple especially mode.But other applicable cases for example may can adopt method described herein to carry out passivation also with capacitive way link coupled antenna structure, and its condition is to be arranged in the suitable space with respect to an antipole.So for example might be by selecting the amplitude of signal, if necessary, by the frequency of the signal selecting to use, make by be parallel to ground bar (or+system's passivation that the conductor of 12V) current signal constitutes.
Up to today, for carrying out salt spray test according to DIN 50021, normally and (according to some structural trial standard) allow the conductor structure of existing printing is covered on the vehicle glazing panels of testing, they are not exposed under the artificial rodent severe weather, because should allow these strict more test conditionss, owing to simulated the infection that is subjected to this component in its whole usage period, therefore be certain to destroy these structures.
Carrying out duration of test, allow applying of some amount the test sample of passivation voltage carry out described test, carry out visual valuation thereafter, even after 240 hours residence time, carried out visual valuation, the corrosion of just observing appearance reduces relatively.But this corrosion does not cause dependency structure to stop the performance of its function fully.
The possibility that applies the electric passivation of low relatively voltage (alternation) generation provides the possibility of using the conductive structure that contains silver economically, these structures are at base material, particularly finish in employing silk screen printing on glass, till up to now, adopt known anticorrosive measure, perhaps abandon these structures, it also is like this utilizing the applications of other terms of settlement (for example optics behind the sheet glass or capacity transducer).The provide protection that applies voltage just consumes considerably less energy, so just causes the additional working cost of ignoring.Use＜10 μ A/cm 2Limited current density, interruptive current appears in this passivation mode, the permissible value 1.5mA in these current ratio automotive fields hangs down several magnitude.
Might in automotive field,, on the window glass outside, make the uncoated conductive structure that contains silver for other application in transmitter or the moist position from now on.In buildings, glass is for example installed the rainwater of printing or is damaged transmitter on the dormer window outside.Comparatively speaking, use the power supply cost of the structure of protection voltage to reduce.
If necessary, may need this print structure of roasting, common like this physical strength and the chemoresistance that is considered to improve them.So also make employing other base material except that glass, for example reach simplification with the sheet glass that synthetic materials is made.
If change running voltage of transmitter or measuring voltage are fully essential in the passivation voltage range, then can be advantageously the structure function and the electric passivation of transmitter be combined.Here this relation of mentioning was not also considered by the people up to today, utilized common available electronic installation to supply with the voltage of about 3V for these transmitters.But this voltage is without any the passivation protection effect.Similarly, the common frequency of these alternating voltages is positioned at below the optimum frequency.By testing definite passivation scope is the magnitude of voltage that is starkly lower than 3V.Use the sinusoidal voltage curve to determine and statistical confirmation optimal results (minimum corrosion current) is arranged for 1.1V and 3000Hz frequency.
Just in the time can measuring the optimum voltage value in man-to-man mode, do not have to get rid of the provide protection that relates to frequency, this is a kind of similarly provide protection separately of corrosion current of some reductions that also occur when being higher than the frequency of 3kHz.
At first, use, prepare test,, measured the passivation scope of this material like this by battery of tests particularly according to the salt spray test of DIN 50021 towards reality to corroding the very sensitive structure that the printing conductive surface is arranged.For this reason, make a series of test electrodes, on these electrodes, adopted silk screen printing on base material, to be coated with skim surface tissue material.The silk screen printing glaze by as the frit of base material, as the silver of conductive metallic material and if necessary, tinting material is formed, wherein Yin ratio is 80%.
Following known structure own is used to the electrokinetic potential test:
Measuring chamber comprises the container that 5% sodium chloride salt solution is housed.With the working electrode for the treatment of that test materials is made, counter electrode and the reference electrode (silver electrode/silver chloride electrode) made with platinum are immersed in this solution, use the Haber-Luggin kapillary that the electromotive force of reference electrode is raise.Use suitable instrument to carry out volts DS and alternating voltage test (for volts DS is potentiostat, is function generator for alternating voltage).Use metering computer and appropriate software to carry out signal research at last.
Be immersed in the effect that sample in this measuring chamber at first is subjected to 0-4V volts DS (between test electrode and counter electrode).
At first need definite suitable time by described voltage range.Under the situation by described voltage range (2 hours) very apace, when the small reduction that has confirmed corrosion current appears at about 2V=really, but do not form any tangible passivation scope.On the contrary, in 48 hours time, before reaching passivation, corrode and just carrying out like this, but this material is destroyed as to no longer include its passivation scope of energy measurement.
When the time of the voltage range by 0-4V=was 12 hours, the obvious passivation scope of this analyzed material was found to be between the about 0.75-1.8V of volts DS at last.
Then, in the low passivation scope of 0.75-1.8V, analyzed the corrosive nature when adopting the alternating voltage operation.
If the sample with the same manner preparation is done the time spent because of can be considered to the identical mesh voltage (alternating voltage and volts DS stack) that is subjected in the industrial production field, these corrosion currents obviously increase in principle.But it changes opposite when having found frequency 3000Hz.
Can confirm this point by the supplementary test of using pure alternating voltage.Here confirmed that pure alternating voltage can guarantee better protecting in principle, promptly obviously reduced corrosion current than volts DS or mesh voltage.
Just because of this reason, then use real manufacturing sample to carry out these tests, promptly be printed on the humidity sensor of the comb poles on the sheet glass, during salt spray test, its humidity sensor applied the alternating voltage of 1.1V, 3kHz for some have been installed.
In process of the test, structure-sample extent of corrosion constantly increases.Even after stopping 240 hours, corrosion process never stopped.But the capacity that can prove comb poles is very big for operating sensor, is not reduced to reach the value that can not use.The usage period that this means conductive structure will be satisfied the requirement under severe weather and actual service conditions usually fully, and the external corrosion of visible hardly of pipe electrode is not how.

Claims (7)

1. protection is deposited on the structure that contains metal on the base material; particularly conductive structure is avoided corrosive attack; particularly electrocorrosion erosive method is characterized in that applying passivation voltage at least provisionally this structure, and this passivation voltage is in the passivation scope of relevant electro-conductive material.
2. method according to claim 1 is characterized in that passivation voltage simultaneously as the measuring voltage of transmitter, especially as the measuring voltage of the humidity sensor that plays a role with capacitive way.
3. the described method of each claim in requiring according to aforesaid right is characterized in that using the alternating voltage of sinusoidal oscillation as passivation voltage.
4. method according to claim 3, the amplitude that it is characterized in that passivation voltage is 0.75-1.75V, particularly 1.1V.
5. according to claim 3 or 4 described methods, it is characterized in that the frequency of passivation voltage is higher than 2000Hz, preferably 2000-4000Hz.
6. the application of the described method of each claim in containing the structure of metal in requiring according to aforesaid right, described structure example is humidity sensor, damage detector, antenna and thermal conductor in this way.
7. application according to claim 6 is characterized in that described structure is deposited on sheet glass or the synthetic materials plate.
CNA2004800019553A 2003-01-09 2004-01-07 Method for protecting metal-containing structures deposited on substrates against corrosion Pending CN1723298A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10300388A DE10300388B4 (en) 2003-01-09 2003-01-09 A method of protecting a weathered metal-containing structure applied to a surface of a substrate against corrosive attack and methods of operating a moisture sensor disposed on a surface of a substrate facing the weather
DE10300388.6 2003-01-09

Publications (1)

Publication Number Publication Date
CN1723298A true CN1723298A (en) 2006-01-18

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ID=32519717

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Application Number Title Priority Date Filing Date
CNA2004800019553A Pending CN1723298A (en) 2003-01-09 2004-01-07 Method for protecting metal-containing structures deposited on substrates against corrosion

Country Status (7)

Country Link
EP (1) EP1581670A1 (en)
JP (1) JP2006518458A (en)
KR (1) KR20050097939A (en)
CN (1) CN1723298A (en)
DE (1) DE10300388B4 (en)
MX (1) MXPA05007048A (en)
WO (1) WO2004070084A1 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3752348A (en) * 1971-08-30 1973-08-14 Ford Motor Co Motor vehicle electrically heated windshield and backlight system
CS199051B1 (en) * 1975-04-28 1980-07-31 Josef Polak Method of polarizing potential measuring of constructions from carbon steel placed in electrolyte in electric current field and device for making this method
US4409080A (en) * 1981-06-18 1983-10-11 Texaco Inc. System for monitoring a cathodically protected structure
US6114863A (en) * 1998-04-29 2000-09-05 General Electric Company Method for determining the presence of water in materials
WO2000045145A2 (en) * 1999-01-27 2000-08-03 Wenman Richard A Method and device for measuring insulating fluids
AU7138200A (en) * 1999-07-22 2001-02-13 Infrastructure Repair Technologies, Inc. Method of treating corrosion in reinforced concrete structures by providing a uniform surface potential
DE10015430C1 (en) * 2000-03-28 2001-05-10 Preh Elektro Feinmechanik Capacitive sensor for detecting surface condensation, has passivation layer covering metallized capacitor electrodes covered by hydrophilic layer

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Publication number Publication date
WO2004070084A1 (en) 2004-08-19
JP2006518458A (en) 2006-08-10
MXPA05007048A (en) 2005-08-18
KR20050097939A (en) 2005-10-10
DE10300388B4 (en) 2005-08-11
DE10300388A1 (en) 2004-07-22
EP1581670A1 (en) 2005-10-05

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