CN100390323C - Semiconductive corrosion and fouling control apparatus, system, and method - Google Patents

Semiconductive corrosion and fouling control apparatus, system, and method Download PDF

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CN100390323C
CN100390323C CNB2003801014887A CN200380101488A CN100390323C CN 100390323 C CN100390323 C CN 100390323C CN B2003801014887 A CNB2003801014887 A CN B2003801014887A CN 200380101488 A CN200380101488 A CN 200380101488A CN 100390323 C CN100390323 C CN 100390323C
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filter
parameter
metal
corrosion
zinc
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CN1705771A (en
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大卫·B·道林
法尔塞德·霍拉米
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APPLIED SEMICONDUCTOR INTERNAT
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Abstract

An apparatus, system, method and computer program product directed to controlling corrosion of a conductive structure in contact with a corrosive environment and coated with a semiconductive coating, where the corrosion is controlled by a controllable filter (898) and a corresponding electronic control unit (899) configured to process at least one stored or measured parameter.

Description

Semi-conductor corrosion and pollution control equipment, system and method
The cross reference patent documentation of being correlated with
This application and No. the 6th, 325,915, United States Patent (USP), No. the 6th, 402,933, United States Patent (USP) and be 09/887,024 relevant in the unsettled US application serial No. of application on June 25 calendar year 2001, for reference at this full content of quoting each.
Technical field
The present invention relates to be used to control the protection against corrosion of based semiconductor and the operating device of anti-pollution system, system and method.
Background technology
According to the title by the industrial nineteen ninety-five issue of the special rolling-mill section of Battelle and North America is the report of " EconomicEffects of Metallic Corrosion in the United States ", the annual expense Da Yuewei $3000 hundred million that is used for metallic corrosion is for reference at this full content of quoting this report in America's economy.By anti-rotten material of widespread use from be designed into maintenance and the best anticorrosion process of application, about 1/3rd cost of corrosion (hundred million) can be avoided and save to this report estimation.Scientist's Battle partial update in the exploratory development of being undertaken by Battelle and national standard and Institute for Research and Technology obtains this estimation, this research title is " Economic Effects of Metallic Corrosion in the United States ", and it is for reference to quote its full content at this.Original work in 1978 comprises an estimation, and in 1975, owing to used best method at that time, metallic corrosion expended 82,000,000,000 dollars (gross national products 4.9%), and about 33,000,000,000 dollars is evitable.
For aviation, corrode the numerical value of the expense relevant and be the problem that global aircraft manufacturing company, airline and passenger are concerned about most the influence of safety with it.Singly in North America, the aircraft industry corrosion expends 1 year above 13,000,000,000 dollars.This influence equally also is huge for government's aircraft, and for example the annual cost of United States Air Force surpasses 8,000 hundred million dollars and is used for aircraft corrosion control and repairing.Corrosion is that aircraft is less than the fundamental factor that just be eliminated and scrap life.FAA will prevent that aircraft structure from damaging the problem that improves aircraft and the override consideration of passenger safety institute of classifying as.The aircraft corrosion has relation with a lot of disasters, accident and air crash.The tragedy that loses the human life is foreclosed, and it is 2,700,000 dollars that the currency that FAA has calculated the passenger of every unexpected death expends.The integrity of remaining undiscovered and/or untreated corrosion failure aircraft has increased upkeep cost and has strengthened risk for passenger safety.
For marine vessel, the pollution on the corrosion of inside and outside hull and exterior hull surface is the principal element that influences boating business cost and ship's life.The fuel spending accounts for the 35%-50% of total running cost.Owing to realize and keep the required increase power demand of the normal travel speed of boats and ships to cause burn into to pollute reaching other 50% with these costs surface resistance instalment with relevant exterior hull is coarse.Working life of ship to its cumulative effect of structural integrity and the cost of repairing rather than the boats and ships age topmost deciding factor that is Condemnation of Ship, and may be shortened significantly in corrosion damage interned ship surface.
For water tower, nearly 150 in the U.S., 000-200,000 municipal water tower.Average water tower has 23,000 square feet surface area (inside and outside) and holds 310,000 gallons.Because the caused excessive condensation of storage cold water, these water towers are very easy to be corroded.In order to keep structurally surveying water tower, approximately per 6 years municipalities will change tank in the coastland, and change in per interiorly 7 years to 9 years, and the average cost of each water tower is above 100,000 dollars.
For bridge, listed 575,413 vehicular bridges in American National bridge catalogue, there wherein have 199,277 vehicular bridges to be described on the structure till 1992 to be damaged or discarded.Through transport ground transport efficient bill in 1991 has been ratified 16,100,000,000 dollars in 6 years, be used for highway bridge and replace and the trimming plan.21 century communications rights and interests bill signature in 1998 continues this plan, has ratified 20,300,000,000 dollars and be used for bridge recovery and replacement in next 6 years.Federal Highway management and Study of Transportation Along will apply 1,000 hundred million square feet bridge surface estimated every year.Owing to remove and seal, limited the squared length of annual paint based on the paint of lead required cost and time.As a result, many situations have been incured loss through delay the maintainability paint of bridge, and 1,500 steel bridge beam is only painted in annual estimation.Because current coating only continues 10-12, so the backlog of the recoat of bridge continues to increase.
For the automobile of being concerned about, the etching problem that influences vehicle safety is automobile factory and buyer's a subject matter.According to the statistics of national highway safety management of traffic office, 1975 and calendar year 2001 between, surpass 25,000,000 vehicle in the U.S. and formally recalled because of the relevant safety problem of corrosion.Singly in 1998, Ford Motor Company just recalled 2,000 because of relating to safe etching problem, more than 000 car, and expense budget has surpassed 200,000,000 dollars.
Researched and developed in the several centuries in the past and be used to control the corrosive the whole bag of tricks, especially focused on the method for life of the metal construction of prolongation under corrosive environment.These methods typically comprise supercoat, these coatings be mainly used in raising as the steel the ferrous metal and the erosion resistance of some non-ferrous metals as aluminium and do not need to use more expensive alloy.Therefore, they have all improved performance and have reduced cost.But this supercoat typically has several defectives, comprises not being suitable for the nonmetal structure that is corroded or pollute.
Supercoat can be divided into two big classes.Maximum class is such as the local coating of paint in this two class, plays the physically-isolated effect with environment.Second class is made up of erosion shield (sacrificial coating), such as zinc or cadmium, is designed to its preferential corrosion so that the protection base metal is not corroded.
Cathodic protection and coating all are to have the engineering method that alleviates and prevent the corrosive main purpose.Every kind of process is different: the cathodic protection method suppresses normal galvanic corrosion and reacts and prevent that corrosion, coating from then being to form the blocking layer to prevent that corrosion current or electronics are between the positive pole of Lock-in and negative pole or flow in galvanic couple by introduce electric current from external power source.Every kind of process all obtains limited success.Up to the present, the anti-corrosion method that coating representative is the most general No. the 4.219th, 358, United States Patent (USP) (see also people such as people's such as Leon No. the 3.562nd, 124, United States Patent (USP) and Havashi).But, cathodic protection be used to protect bury or soaking conditions under the pipeline and the Large Area Steel surface of gigameter.
Cathodic protection becomes by the anode dissolution rate that provides enough cathodic currents to make it to the metallic surface and can ignore the corrosion that reduces the metallic surface and (for example, see also the United States Patent (USP) the 3rd, 574,801 of Prvor; The United States Patent (USP) the 3rd, 864,234 of Wesson; The United States Patent (USP) the 4th, 381,981 of Maes; People's such as Wilson United States Patent (USP) the 4th, 836,768; No. the 4th, 863,578, the United States Patent (USP) of Webster; And No. the 4th, 957,612, people's such as Stewart United States Patent (USP)).Cathodic protection applies the potential difference that enough current polarizing negative electrodes eliminate between local anode and the cathode surface to anode potential and works.In other words, the effect that applies cathodic current is to reduce to continue as the anodic area, rather than reduces remaining anodic corrosion speed.All when anodal when having consumed, just realized protection fully.From electrochemical viewpoint, this expression offers the metal that will protect with enough electronics, thus balance metal ionization or dissolved trend.
Found that in the work recently of research corrosive electrochemical corrosion course is obviously relevant with the random fluctuation of electrical properties such as the cell current of electrochemical systems and electropotential.These random fluctuations are called " noise " in this area.Before about 20 years, scientist finds because all electro-conductive materials of the caused electrochemical reactivity of impurity in the material just can begin to be corroded when it produces them.Found afterwards to use the electronic machine that detects the electric current that produces to monitor this reactivity, be commonly referred to " corrosion noise " now.In fact, the amplitude of this electric current is big more, and material " noise is big more " and erosion rate are fast more.For example, steel is corroded than bronze " noise is bigger " and with speed faster.The researchist has begun the noise analysis technology is applied to corrosion process in the electrochemical systems.
The US5 of Rjffe, 352,342 and US5,009,757 discloses the silicate coating based on zinc/zinc oxide, and this coating is used in combination with electronics in the corrosion protective system, and is for reference in this content of quoting these two patents.Disclosing the zinc in the coating/zinc oxide particle and had semiconductor properties, mainly is the p-n junction at zinc-zinc oxide phase boundary (phase boundary).When reverse bias, describe this p-n junction and be equivalent to diode and forbid that electronics passes this border.This constrained electronics from the position of zinc oxidation to zinc oxide surface hydrogen reduction position transfer.Between the anode of local corrosion unit (cell) and negative electrode, increased resistivity and reduced corrosion effectively.
Fifty-fifty, since with at the relevant current potential of the oxidation of the zinc of zinc surface with at the O of zinc oxide surface 2Reduction, will be reverse biased based on the knot of zinc-zinc oxide.But, the voltage fluctuation at random that occurs showing.These voltage fluctuations cause this knot to become forward bias occasionally.When forward bias, the electronics that passes knot increases, and the oxidation of zinc and O 2Reduction quicken or " bursting ".Between unitary positive pole of local corrosion and negative pole, there is short circuit and increased corrosion effectively.
The patent disclosure of Riffe in the electrochemical circuit of corrosion protective system with the electric capacity of fixed value.But, the inventor thinks, the desirable property of both not found out the degree of control capacitance is not found out yet and proposed to be used for to determine that how dynamically change effectively prevents any method of any needed capacitance of corrosion of giving fixed structure or determine the best mode of required capacitance.
For antifouling, these things must be mechanically removed in infringements such as the barnacle that in a single day marine object is enclosed, Zebra mussel.Cheaply, remove/prevent the hull bottom dirt wishes non-mechanical and environmental sound.This has caused in antifouling toxic research.Toxicologic study has been set up such fact: must definition " poison " and also doing like this in operation, and " toxicity " of compound normally defines according to the amount of the compound that causes death or disease or density.Therefore, when the relative toxicity of assessment element or compound, should consider concentration.Many metals are well known that " toxic agent ".But the metal that is designated as toxic agent also is " necessary " simultaneously.Copper, well-known sanitas belongs to this class.Do not having under the situation of copper, as far as our knowledge goes, life just can not exist.Copper is the essential part of some enzyme of playing an important role in growth, regeneration and metabolism.Regrettably, want to use the people of copper for those at least as corrosion inhibitor, by 1,000,000/lower concentration measured is a toxic agent, especially all the more so the hydrobiont among the whole liquid environment that is immersed in them of health.Tin is not a kind of metal of necessity in biological phenomena, but organo-tin compound but is fabulous stain control agent.Regrettably, the content since these organic compound of part per billion is exactly toxic agent for the nontarget organism kind.In addition, this organism in fatty tissue, accumulate and by food chain by " expansions ", so day by day to the top layer of animal chain, for example the mankind have increased adverse influence.
Zinc is metal necessary in the biological phenomena, but it is not assigned in the heavy metal class as copper.The toxicity of zinc is higher than copper significantly, and zinc can find the mode that oneself enters acceptable product and material on numerous environment.The scientist of Duke university finds and the United States Patent (USP) the 5th, 352,342 and 5,009 of Riffe that the relevant antifouling attribute of 757 coating comes from the zinc toxicity of coating.These scientists determine simultaneously: the amount that discharges zinc is so low, to such an extent as to they can be to the ocean environment toxigenicity.They are also noted that zinc is not metal extended in food chain.Therefore, can use zine ion as toxic agent, anti-marine organisms adhesive agent.
As a defective of the previous anti-corrosion method of the method for top disclosed Riffe is the ineffective relatively activity of the wherein disclosed selectable color of coating based on silicate, and only the color that can obtain easily is a grey.Though this is acceptable in most of boats and ships and structure are used, and needs corrosion protection coating, this corrosion protection coating be not corrosion and can provide a lot of colors to be used for the paint replacement thing, especially in automobile and communications.Coated semiconductor in main following patent of these and other shortcoming or the patent application overcomes with relevant system, it is the United States Patent (USP) the 6th of Bowling, 325, No. 915, United States Patent (USP) the 6th, 402, No. 933 and be 09/887,024 U.S. Patent application in the sequence number of June 25 calendar year 2001 application, it is for reference to quote full content at this.The coated semiconductor of Dowling patent and application and system can use with various conductive substrates, so that a series of interested attributes are provided.Because semi-conductor is the material that the substrate than its application is difficult for chemically reacting all the time, so coating is stablized the current potential of protected material.On the semi-conductor of electronics by the electrochemical activity generation from shielded substrate-transfer to coating, perhaps briefly, corrosion noise by from shielded material transfer to coating.
Fig. 1 is that expression is present in the electrochemical noise in the untreated metal 101, and random fluctuation voltage is measured and show (be shown as sawtooth waveform, but actual waveform may have the wide band component and be actually at random) with waveform 102.
Fig. 2 is illustrated in the metallic surface and applies the semiconductor protection coating and come protection against corrosion and antifouling effect, and its floating coat 210 comprises the material that is difficult for chemically reacting than the metal 201 that will protect.Because coating 210 is difficult for chemically reacting than metal 201, so it is included into and will be present in the electrochemical noise 211 of metal, but for coating, this result shows that 202 are intrametallic smooth waveform.Single semiconductor grain in the coating 250 is born the non-corrosibility of coating.
Fig. 3 represents stratified semiconductor/metal structures.When mixing zinc, because zinc oxidation and hydrogen reduction, the anti-corrosion capability of the semiconductor material of steel (iron alloy) causes the foundation of current potential, is called " corrosion potential ".In this, this system plays a part to suppress with the iron oxidation the common corrosion anode material of the current potential set up by the zinc oxidation.But along with the reduction of corrosion potential, the zinc oxidation in the semi-conductor shows land reduction or passivation (passivated), and this causes the extremely long life-span of coating.Passivation is in conjunction with the result of the similar variable resistance characteristics in Zn/ZnO border with the relevant wave filter ability that remains on this borderline potential difference, so that this border has high resistance.Semiconductor grain 250 is made up of two districts: p type island region 320 and N type district 310 with knot 330 form, and this knot 330 plays the variable-resistance effect of the stream of electrons 302 that has between Liang Qu.When using zinc, the zinc particle is had the various zinc oxide films that are coated with the oxidation coated particle that surrounded by electroconductive binder and is covered.The semi-conductive border of P in the coated semiconductor and N plays a part variable resistor (back to back diode), controls the stream of electrons between them.Suitably apply electric current to the coated semiconductor that is connected to the substrate that to protect, make the current potential on this border stable.This has reduced the speed of semi-conductive electronic migration from P to N, with 10 3/ one reduces its corrosion rate, and the life-span that obtains coated semiconductor prolongs, and this can surpass the life of process object.
Variable resistor (variohm) has on height nonlinear electrical properties and the function and oppositely back to back diode equivalence.In pressure limiting district, " switch region ", they only pass through leakage current.When voltage amplitude surpassed switching voltage, for example in a flash very brief, variable resistor became highly conductive.Variable resistor is normally based on zinc oxide.Fig. 4 is the graphic representation of the variable-resistance Voltammetric Relation of expression, and 1101, one axles of one of them axle expression voltage are represented electric current 1102, and the curve 1103 of the electric current in the expression expression bias voltage scope.-V b1110 and V bDomain representation voltage zone 1104 between 1107, wherein variable resistor plays switch.Indicate I along this curve L1105 point be corresponding to leakage current along the point on this curve, even just when with variable resistor biasing to work the time spent of doing of opening switch, the fractional value electric current flows through this variable resistor.Indicate V N1106 point is the point that is illustrated on the curve of switching voltage; In other words, corresponding to the high positive voltage value of variable-resistance switch region 1104.Indicate V B1107 point is represented variable-resistance voltage breakdown, greater than V BBias voltage make variable resistor be equivalent to a node.Indicate I L1108 point is illustrated in the point on the curve of bearing leakage current.Indicate-V N1109 point is illustrated in the point on the curve of bearing switching voltage; In other words, maximum negative voltage region is represented variable-resistance switch region 1104.Indicate-V B1110 point is represented negative voltage breakdown.
The patent of above-mentioned Dowling and application comprise coated semiconductor and the corrosion noise Controlling System that comprises wave filter at least at control corrosive system and equipment.In the application of unsettled Dowling, the corrosion noise Controlling System comprises adjustable filter, and it can be according to the feedback signal adjustment corresponding to the corrosion noise that exists in the coating.
The performance that corrosion noise in the patent of Dowling and the application reduces system changes along with the variation of the inside wave filter of system, and its simplest form is actually electrical condenser.The patent of Dowling and application also disclose combined semiconductor coating and various passive and active filter.In the patent and application of Dowling, coated semiconductor serves as the effect of resistor to a certain extent, and it is in parallel with the inside wave filter of system.Wave filter is discussed substantially, such as how realizing that high pass or low-pass filter are at microelectronic circuit the 4th edition, Sedra ﹠amp; Smith, the Oxford University Press finds in (1997), and it is for reference to quote its full content at this.
Fig. 5 is the graphic representation between time of corrosion potential and various wave filters.Transverse axis 401 is measured the time of every day, and the current potential with respect to semiconductor element that the longitudinal axis 402 expressions are measured by millivolt.In experiment, be that seven systems are measured at three time points at the optimum filter characteristic of determining various corrosive environments.Three sampling of current potential of the measurement of each structure of seven filter constructions of record, and with the various symbolic representations of listing in the icon.Graphic representation is presented at each result of each wave filter of seven wave filters on from 410 to 430 sampling spots of indicating.
Can schematically watch galvanic etching according to equivalent electrical circuit.Typically, semiconductor material doping zinc.Therefore, simple equivalent circuit shown in Figure 6 relates to the situation of zinc oxide.Negative reaction appears on zinc oxide anodic reaction occurring on the zinc.Please note that the Zn/ZnO border represents the variable resistor in the circuit.If by Zn/O 2The potential difference that redox couple produced stably falls in the switch region, and the high resistance by this border suppresses the oxidation of (or passivation) zinc so.But, in the past ten years, proved the electrochemical potential fluctuation that exists from producing, " electrochemistry noise " relevant with corrosion.As a result, even Zn/O 2Current potential can be in switch region, but also is likely fluctuation, thereby potential difference is encouraged paramount conduction region and allow the electronics zinc oxidation of flowing.
The inventor recognizes that this is a kind of mode of passivation zinc, so that remove or this electrochemistry noise of filtering.Remove this electrochemistry noise by wave filter, this wave filter promptly is an electric capacity with its simplest form.Filter effect remains on the current potential on the Zn/ZnO border of switch region, and reduces the zinc oxidation and prolong the life-span of coating.It should be understood that this low-pass filter can enlarge logical (or trap) wave filter of band, so that according to the material that will protect other frequency band of selectively decaying.
Fig. 6 represents the equivalent-circuit diagram of the system of the patent of Dowling and application.This figure according to the chemical property of metallic corrosion process with the characteristic of this system abstract be representational circuit.Specifically, corrosion can be modeled as the fluctuation voltage power supply, can be expressed as the internal resistance of metal, and corrosion protection coating can be modeled as variable resistor and noise filter can be modeled as electric capacity.By in schematic circuit, replacing these model components, utilize circuit analysis more clearly noise and the filter part of generalities Dowling.
Wherein representative circuit is the solution resistance 801 of internal resistance of this system of expression, it with connect corresponding to galvanic electrode (galvanic electrode) current potential of the positive pole 802 of the ionization process of zinc with corresponding to the galvanic electrode current potential of the negative pole 803 of the chemical process of generation water.That also exist and placed in-line with this circuit is two noisemakers 804, one of them noisemaker is inserted between anodal galvanic electrode current potential and the anodal Faraday impedance 805, another noisemaker is inserted between the Faraday impedance 806 of the galvanic electrode current potential of negative pole 803 and negative pole, and being connected between the Faraday impedance of positive pole and negative pole is zinc oxide varistor 807 and noise filter 808.
Variable resistor and noise filter action are so that reduce the appearance that can bring out the corrosive voltage fluctuation.Noise filter 808 can be that active part also can passive device, perhaps be active part be again passive device, by the node 810 in the circuit that select to want designated common potential, wave filter 808 high frequency in the circuit that causes owing to corrosion noise of can decaying.
The substrate of placing semiconductor layer can be conduction or nonconducting.The substrate of conduction can be a metal or nonmetal.Nonconducting substrate can be any material as isolator, such as silicon chip or other nonmetal substrate.Be perfectly clear the production process of this non-conductive or conductive substrates in semi-conductor chip manufacturing technology field of those of ordinary skill in the art.
The patent of Downing and the application in corrosion noise reduction system provide by with coated semiconductor coated with conductive structure and be connected to the coating structure that obtains passive or the active electronic wave filter so that the corrosion noise that minimizes in the coating prevents to cause corroding method to being subject to the corrosive conductive structure.This electronic filter has the filter response of the high frequency spectrum components of decay corrosion noise.This realizes that by connecting wave filter this wave filter has the impedance characteristic with the form of the low-pass filter on the material that will protect (also can increase notch filter).In addition, according to material and application, other frequency band of can selectively decaying is so that reduce corrosion and/or realize anti-fouling effect.This wave filter can be passive filter or active filter.Though that a kind of situation, this filter attenuation high-frequency voltage fluctuation.The knot that is present in the coated semiconductor then keeps reverse bias.Therefore reduced the time-averaged current that in coated semiconductor, flows into the negative pole territory from anode, and this coating of passivation effectively.
Utilize the wave filter in the equivalent electrical circuit that embeds corrosion process; as shown in Figure 7, the signal that can abate the noise, wherein metallic surface 501 is covered by the supercoat 510 that is connected to wave filter 508; like this, this metal has the noise static 502 of decay significantly.Wave filter 508 or play a part low-pass filter independently or may combine with the wave filter of the impedance with the logical and/or notch filter form of band is so that reduce high frequency corrosive noise 522.This wave filter eliminate effectively with the electrochemical noise signal in the relevant energy of high frequency.By suppressing the voltage fluctuation on the outer variable resistor of switching voltage (Vn), the high frequency spectrum components of decay electrochemical noise will reduce corrosion process significantly.
Summary of the invention
Therefore, an object of the present invention is to propose and solve above-mentioned in the conventional anti-fouling system and other defective.
Another object of the present invention provides a kind of corrosion noise and reduces system, has the coated semiconductor on electronic control unit (ECU), controllable filter (comprising the fixed passive filter alternatively) and the substrate, so that be provided to the low resistance path on ground for the high frequency corrosion noise.
Another object of the present invention is for given structure provides a kind of life-span of prolongation supercoat and equilibrated system and method between the supercoat consumption optimized, so that be equilibrated at protection against corrosion and the antifouling properties that the corrosion noise that adopts on this structure reduces system.
Realize these and other purpose by system and method for the present invention described here.The inventor recognizes: the corrosion noise of utilizing electronic control unit (ECU) and controllable wave filter to operate in to optimizing to have coated semiconductor on the substrate reduces system, so that control the operation and the voltage fluctuation of the wave filter in the conductive structure that coated semiconductor is set on it.These benefits are to realize by monitoring by the noise of described coating generation and the method for control filters; this method is the corrosion noise that produces in coating of response, based on one group of parameter predetermined and/or that measure randomly but be not limited to use adjustable filter parts and/or fixing part, thus control corrosive speed and/or the soiling protective parts of consumption are provided.This group parameter predetermined and/or that measure comprises at least one parameter of following parameters: the time limit, coating aging, coat-thickness, the surface area of coating and the shape of coating area of the instantaneous velocity of temperature, saltiness/water purity, humidity, the time limit, short-term working cycle, long-term working cycle, boats and ships, speed of the ship in metres per second history, instant geographical position, geographical position history, coating.
The objective of the invention is to aeronautic structure/aircraft; Vehicle structure/vehicle; Bridge; Boats and ships/structure; Pipeline; Electric car/structure; Steel construction; With the protection against corrosion in the basin, although also can be used for other purpose.Purpose of the present invention also is boats and ships; Marine structure; Offshore platform; The power station; And the prevention of adhering to of the marine organisms in other object.
As the inventor determines, controllable filter and controller can be used in the corrosion noise reduction system, its middle controller is dynamically adjusted the filter characteristic that corrosion noise reduces system by considering various parameters, so that the protection against corrosion of this system of balance and antifouling feature.The infinite catalogue of the example of these parameters comprises at least one parameter in the following parameter: the time limit, coating aging, coat-thickness, the surface area of coating and the shape of coating area of the instantaneous velocity of temperature, saltiness/water purity, humidity, the time limit, short-term working cycle, long-term working cycle, boats and ships, speed of the ship in metres per second history, instant geographical position, geographical position history, coating.In view of new discovery may be broken the protection against corrosion of this system and the balance between the antifouling feature, the inventor finds and is used to control system, equipment, algorithm, the method and computer program product that reduces the relevant filter operations of system with protection against corrosion/antifouling coated semiconductor and corrosion noise in this description.
Description of drawings
By with reference to the following detailed description of considering in conjunction with the accompanying drawings, obtain more complete understanding of the present invention and many bonus thereof easily, and can understand the present invention better, wherein:
Fig. 1 is the expression of not protecting intrametallic corrosion noise;
Fig. 2 is in the metal of protecting and the expression of the corrosion noise in the coated semiconductor; And
Fig. 3 is that the electric current mobile is represented between metal and semiconductor protection coating;
Fig. 4 is the graphic representation of similar variable resistor operation between metal and semiconductor protection coating;
Fig. 5 is the graphic representation between time of corrosion noise and various wave filters;
Fig. 6 is the schematic circuit that does not have the corrosion noise reduction system of electronic control unit (ECU);
Fig. 7 comprises that the corrosion noise of metal, semiconductor protection coating, wave filter and parts noisiness reduces the skeleton diagram of system;
Fig. 8 comprises the ECU of may command corrosion noise filter and the schematic circuit of ECU pilot circuit;
Fig. 9 comprises the ECU of may command corrosion noise filter and the structure iron of ECU pilot circuit;
Figure 10 A and 10B are respectively the amplitude and the phase response curves of the corrosion noise bandpass filter of a specific embodiment of the present invention;
Figure 11 A and 11B are respectively the amplitude and the phase response curves of the corrosion noise notch filter of a specific embodiment of the present invention;
Figure 12 utilizes ECU to reduce the schema of the method for corrosion noise;
Figure 13 comprises that the corrosion noise of metal, semiconductor protection coating, wave filter and parts noisiness reduces the skeleton diagram of system;
Figure 14 is the graphic representation that relatively has and do not have the zinc release rate (microgram/square centimeter) of the corrosion noise reduction system under the ECU situation;
Figure 15 is the graphic representation that relatively has and do not have the zinc release rate (%) of the corrosion noise reduction system under the ECU situation; And
Figure 16 is the skeleton diagram of the computer system used among the present invention.
Embodiment
The invention provides a kind of corrosion noise and reduce system, have the coated semiconductor on electronic control unit (ECU), controllable filter and the substrate.
Fig. 8 is the schematic circuit of a specific embodiment of the present invention, and the parts that wherein are similar to Fig. 6 still keep their previous marks.As shown in the figure, ECU 897 comprises controllable filter 898 and ECU pilot circuit 899.ECU 897 is connected in one or more local sensors 882 alternatively, and/or is connected in or comprises the device of antenna (for example supplying the usefulness of radio communication) 881 or other realization radio communication, such as optical transceiver.ECU can also visit the data that are stored in the local data archival memory (not shown) or visit the remote archive storer by antenna 881, other radio communication device and even wired connection such as network.The filter characteristic that ECU pilot circuit 899 changes controllable filter 898 is set, so that change controllable filter 898 impedance relevant with frequency according to the operator scheme of ECU pilot circuit 899.As those of ordinary skill in the Controlling System field is understood, will also be understood that the present invention is not limited to this specific structure.
Fig. 9 is the skeleton diagram of a specific embodiment of the present invention and comprises the ECU 897 that comprises controllable filter 898 and ECU pilot circuit 899.Though the wave filter that expression is made up of single electric capacity also can utilize other circuit module to realize increasing the various wave filters of low-pass filter impedance characteristic (impedance that for example, has the notch filter form).Schematically, the combination table of controllable filter 898 and ECU pilot circuit 899 is shown individual system 897, and this system is connected to another element of this etching system by conductive link 809.Controllable filter 898 can comprise the various wave filters (for example, having the wave filter of the impedance of logical or the like the form of low pass, notch filter, band) of arbitrary structures, and target high-frequency signal corresponding to corrosion noise is provided for decaying.Use can by the electric controllable switch 905 of ECU pilot circuit 899 control or by such as manual switch, plugboard or other device can automatic or manual ground, be electrically interposed in and/or from the alternate manner of circuit removing component, controllable filter 898 can selectively disconnect with this system.Controllable filter 898 can be by ECU pilot circuit 899 by opening or the mode of the control line 925 of Closing Switch 923 and 924 is controlled, open or Closing Switch 923 is connected a plurality of wave filters 920 and 921 (this comprises convertible bank of filters alternatively, different filter characteristics can be applied to corrosion noise together) of adding with 924.ECU pilot circuit 899 also is a feature of the present invention by the filter characteristic of adjustable circuit component electronic ground control/adjusting controllable filter 898, and wherein the adjustable circuit element selectively is thyrite or conversion variable capacity.ECU 950 can be connected to wireless receiver/transmitter 881, so that receive and/or send one or more control signals (alternatively by wireless electromagnetic link and/or optical link) with long-range ECU control unit.ECU pilot circuit 899 can be connected to one or more local sensors, each local sensor is set is used to monitor one or more parameters of being used by ECU pilot circuit 899, such as salinity, temperature, local location or other parameter.The information that receives from wireless receiver 881 and/or local sensor 882 can be used for regulating controllable filter 898 or it is disconnected fully by ECU pilot circuit 899.In addition, ECU pilot circuit 899 can with this locality and/or remote data base 912 interfaces so that handle the information that receives from wireless receiver/transmitter 881 and/or local sensor 882.
Have application-specific by use and need the wave filter of the frequency response characteristic select and the electrochemical noise that uses adaptive active wave filter monitor protection object and " and correspondingly regulate it and respond, usefulness that can the optimizing coated semiconductor.Be provided with and operate specific wave filter, so that eliminate corrosion noise, thereby generation more by a small margin on coated semiconductor, LF voltage.Along being provided with on the coating in one or more places of protection structure and adhering to one or more wave filters, so as in coated semiconductor or above ' high frequency ' corrosion current of forming be provided to the low resistance path on ground.' high frequency ' is the term that is used herein to the non-DC component of describing corrosion noise.In fact for typical structure, the high fdrequency component of corrosion noise is tens hertz or higher.High frequency also can comprise DC and for example transition band between 10 hertz as used herein, thereby comprises for example frequency of 1-10 hertz.Therefore, the filter characteristic of the controllable filter that the present invention adopts end (or 3 decibels of points) are generally the 1-10 hertz, but are not necessarily limited to this.Character according to corrosion noise, this filter characteristic may be suitable for the frequency that suppresses lower, such as 1/4 or 1/2 and above frequency, even be suitable for one or more specific frequency bands (one or more wave filter traps that can be had the impedance of notch filter form).
Figure 10 A and 10B are respectively the amplitude and the phase response curves of corrosion noise low-pass filter of the example of one embodiment of the invention.These Bode diagram (Bode plots) are illustrated in 3 decibels of about 10 hertz points.Perhaps; can use according to protecting materials have 5 hertz, the wave filter of the low pass impedance characteristic of 3 decibels of points of 15 hertz, 25 hertz, 100 hertz or other value; as long as can from the protection structure, remove the non-significantly DC component of spectrum energy, so that reduce the voltage fluctuation outside the switching voltage scope significantly.One or more this wave filter with low pass impedance characteristic can be electrically connected to the protection structure in one or more positions, so that remove unwanted corrosion noise energy when reducing or prevent at the structural any corrosion noise electric current of protection.One or more such low-pass filters can be controlled according to filter freguency response and/or physical connection by electronic control unit.Perhaps, can use higher order filter to change the characteristic speed of roll-offing, thereby further high-frequency energy is suppressed near 3 decibels of points.This electronic filter is for introducing the path that electronics is lost and therefore corrosive electrochemical noise signal is provided to ground.In order to reduce corrosive nature effectively, need to realize the little impedance (that is,, then realizing) of low frequency by the size that increases electrical condenser if the system filter device only is an electric capacity.
Figure 11 A and 11B are respectively amplitude and the phase response curves that is had the corrosion noise filter of low pass impedance characteristic by the notch filter enhanced of a specific embodiment of the present invention.As shown in the figure, a plurality of in the impedance of this wave filter (or only one) trap can be used in combination with the low pass impedance characteristic of Figure 10 A and 10B, so that eliminate one or more corrosion noise spectrum components.One or more this wave filters can be electrically connected to the protection structure of one or more positions, so that remove the corrosion noise energy peak when reducing or prevent at the structural any corrosion noise electric current of protection.One or more this notch filters can be controlled according to frequency response and/or physical connection by electronic control unit.Perhaps, can use higher order filter.
The control of the higher order filter that has one or more wave filters of low pass and/or trap impedance characteristic and carried out by electronic control unit can be based on one or more corrosion noise measurements that be provided by the one or more corrosion noise transmitters that monitor this protection structure.
The combination that is connected with wave filter for all wave filters; by respond a series of measurements and/or predetermined parameters the operation that ECU regulates its wave filter is set; can be on life-span of object of protection the effect of optimization coated semiconductor; above-mentioned parameter comprises following one or more parameters: the corrosion noise of measurement; temperature; salinity; humidity; the time limit of coating; the area that applies; the thickness of coating; the degeneration of coating; the shape of coating zone; the position of coating boats and ships/object (for example; the North Sea and southern China sea); boats and ships move or are static; operation history (for example, static with the time ratio that moves).
Figure 12 is a schema of representing the process of the non-limiting example used in an embodiment of the present invention.The process of this flowcharting can be used for the characteristic of control filters in ECU, so that the balance between optimizing corrosion protection result and the anti-fouling effect.In this process, system advances to supervision stage step 1202 from beginning step 1201, and wherein each input can be taken out from each watch-dog and transmitter, comprises historical or other factor of position, system of salinity, system.Then, systematic comparison monitoring value also should adopt that wave filter in two scheduled operation kenels (profile) wave filter in step 1204 and 1205 respectively in step 1203 decision.When finishing this action, system returns supervision stage step 1202 and repeats this process.In this embodiment, two wave filter kenels have been represented.In other embodiments, can select kenel more than three or three.
Controlled variable of the present invention is measured and is utilized the aspect to be used to finely tune the performance of the system of application-specific.According to controlled variable, for can determine in the whole lip-deep consistent corrosion protection of structure and the improvement system in essential wave filter attribute, even in very large structure, also be like this such as seaplane carrier or Longspan Bridge.In the present invention, when voltage peak surpasses predetermined threshold to the voltage fluctuation between each timed interval supervision coated surface and the lower noise high resistance reference electrode, pre-determined number (for example per second is 3 ten) and/or detection enhanced noise circumstance.This threshold detection technique is a mode of the standard deviation of measurement noise, and the standard deviation of noise is again measuring of noise power.Perhaps, can use the noise power of FFT or other signal processing technology measurement as frequency function.The frequency content of noise signal and its power composition can be measured by the such metering facility of picture frequency spectrometer, perhaps can carry out various signal processing technologies by the digitizing of signal and in the real-time embedded processor of ECU and measure.In addition, can use (individually or in combination) other parameter artificially or automatically regulate filter characteristic and/or wave filter work (that is conducting/disconnection) cycle.These include but not limited to predetermined parameter: the position of the shape of the thickness of the time limit of the corrosion noise of measurement, temperature, salinity, humidity, coating, the surface area of coating, coating, the degeneration of coating, coated area, the boats and ships/object of coating (for example, the North Sea is to southern China sea), boats and ships move or static, operation history (for example, static with the time ratio that moves).
In another embodiment, ECU is connected to the global positioning satellite subsystem by industrial standards or the proprietary bus as the VME bus or by radio communication device.By the geographical position of system of supervision, the relevant effect of salinity known to ECU considers according to preassigned, temperature and influence the virtual value that corrosive other factors regulate corrosion noise filter feature relevant with the geographical position of system.
Figure 13 is the expression of the effect of one embodiment of the present of invention, and the parts that wherein are similar to Fig. 7 still keep their previous marks.ECU 599 can connect and control filters 508.ECU 599 can be connected to antenna 581 receptor of other such electromagnetic energy of infrared rays or light (or such as) and/or one or more local sensor 582, so that receive the data that influence ECU 599 control filters 508.In this embodiment of the present invention, ECU control filters 508, make this wave filter have intermittent low pass impedance characteristic 577 (replacing consequently, low-pass filter is the turnover circuit) between open circuit and closed circuit, so that decay (with gate-controlled switch speed or work period) high frequency corrosion noise off and on.When wave filter is being decayed the high fdrequency component of corrosion noise, be reduced on the coating widely and the high frequency spectrum composition of the electrochemical noise of protecting materials 550; Therefore, this noise signal of filtering makes that it is slow time variant voltage (that is, not " point ") effectively.When wave filter was not eliminated corrosion noise, the noisiness of coating 550 was noisy (points), and the zinc in the indication semiconductor layer is dissipated to environment and has suffered.In this case, ECU 599 these coatings of control are moved with the protection against corrosion operation scheme.In other embodiments, ECU 599 can control filters 508, makes wave filter 508 have the amplitude of predetermined corrosion noise frequency and/or frequency is lowered and/or connect the filter characteristic of wave filter 508 off and on.The reason that wave filter is operated in " pulsation " mode is that balance is used for antifouling zinc consumption and is used for etch-proof zinc keeping.Can control spending rate by conducting/break period that pulsation is set, scope is from (conducting) more than 0% to conducting all the time (that is, 100%) only.For example, in scheduled time slot, the operator scheme of 50% conducting/disconnection pulsation will have the filter operations of 50% time during preset time, although always may not be with timed interval of equating (that is, always 50% work period).In addition, pulsed operation can cycle or control waveform generation non-period.
Figure 14 relatively has and does not have corrosion noise under the ECU situation to reduce the graphic representation of zinc release rate of the overtime measurement of system.In this graphic representation, the zinc release rate of two systems is presented on the curve, and wherein transverse axis 601 is measured elapsed time and fate, and the longitudinal axis 602 is measured the zinc release rate with the microgram of every square centimeter of zinc.In the system that uses ECU, by square 620 these results of expression.In another system, use system to reduce the zinc release rate with ECU, and by circular 610 these results of expression.This measurement is to carry out in about 300 days time cycle.The zinc that the relatively expression of two curves does not have the system of ECU to trend towards discharging in the time cycle is more than the system with ECU, thereby has the short coated semiconductor life-span.
Figure 15 is the stdn again in the result of Fig. 6 discovery, and wherein transverse axis 701 is represented the time of every day, and the per-cent that the longitudinal axis 702 discharges with total zinc is represented the release of zinc.In this graphic representation, the results that have ECU by circular 710 expressions are corresponding to result 610, and the results of square 720 expressions are corresponding to the result among Figure 14 620.
Figure 16 represent can be in an embodiment of the present invention as the computer of ECU control computer 899.This computer comprises treater 1003, primary storage 1004, ROM 1005, system bus 1002, and is connected to each user interface facilities 1010-1012, such as watch-dog and keyboard.For monitoring physical condition and other variable relevant with the operation of optimization corrosion protection of the present invention and antifouling measurement, this computer is connected to transmitter 882, such as salinity and pressure warning unit, geographic position sensors or the like.
Below ECU control computer 899 will be described in more detail.ECU control computer 899 comprises that bus 1002 or other are used to the communication agency of the information that transmits (may with wireless mode) and is connected with bus 1002 and is used to handle this information processing device 1003.ECU control computer 899 also comprises primary storage 1004, such as random-access memory (ram) or other dynamic memory (for example, dynamic RAM (DRAM), static RAM (SRAM) and synchronous dram (SDRAM), they are coupled to bus 1002 and are used to store information and the instruction of being carried out by treater 1003.In addition, primary storage 1004 can be used for storing temporary variable or other intermediate information during treater 1003 execution commands.ECU control computer 899 (for example also comprises read-only storage (ROM) 1005 or other static storage device, the read-only storage (EEPROM) of read-only storage of programmable read-only memory (prom), erasable programmable (EPROM) and electrically erasable), they are coupled to static information and the instruction that bus 1002 is used for storage of processor 1003.
ECU control computer 899 also comprises Magnetic Disk Controler 1006, be coupled to bus 1002 to control one or more memory device, stores information and instruction, such as magnetic hard disk 1007 and removable media driving mechanism 1008 (for example, floppy disk, read-only miniature disk drive, read/write miniature disk drive, mini disk planter, tape drive and removable MO drive (Magneto Optical drive)).Use suitable equipment interface (small computer system interface (SCSI) for example, the electronics of integrated equipment (IDE), enhancement type IDE (E-IDE), direct memory access (DMA) (DMA) or super-DMA), these storing devices can add computer system 950 to.
ECU control computer 899 also (for example can comprise special logic equipment, application specific integrated circuit (ASIC)) or configurable logical unit (for example, simple programmable logical device (SPLD), CPLD (CPLD) and field programmable gate array (FPGA)).
ECU control computer 899 also can comprise display control unit 1009, is coupled to bus 1002 with the indicating meter 1010 of control as the cathode ray tube (CRT), shows information to the computer user.This computer system comprises the input unit as keyboard 1011 and indicating unit 1012, and being used for provides information alternately and to treater 1003 with the computer user.Indicating unit 1012 for example can be a mouse, and tracking ball or indicator stem are used for sending treater 1003 to and be used to control cursor directional information and command selection mobile on indicating meter 1010.In addition, printer can provide the storage data of printing and/or the table of the data that produced by ECU control computer 899.
The treater 1003 be included in such as the one or more instructions of the one or more sequences in the such storer of primary storage 1004 is carried out in response, and ECU control computer 899 is carried out part or all of treatment step of the present invention.This instruction can be read in primary storage 1004 from another computer-readable medium, such as reading in from hard disk 1007 or removable media driving mechanism 1008.Can adopt the one or more treaters in the multiprocessing arrangement to carry out the instruction sequence that is included in the primary storage 1004.In another embodiment, can use hard-wired circuitry to replace or make up with software instruction.Therefore, these embodiment are not limited to the particular combinations of any hardware circuit and software.
As mentioned above, ECU control computer 899 comprises at least one computer-readable medium or storer, is used to keep instruct according to the present invention the instruction of programming and is used to comprise data structure, table, record or other data described here.The example of this computer-readable medium (for example has mini disk, hard disk, floppy disk, tape, magneto-optic disk, PROM (EPROM, EEPROM, flash eprom), DRAM, SRAM, SDRAM or other any magneticmedium, mini disk, CD-ROM) or other any optical medium, punched card, paper tape or other physical medium with hole shape, other any medium that carrier wave (narration below) or computer can read.
The included software of the present invention is kept on any one medium or is kept in the combination of computer-readable medium, the present invention includes the software that is used to control ECU control computer 899, be used for drive realizing an equipment of the present invention or a plurality of equipment and make the ECU control computer 899 can be mutual with user (for example, print production personnel).This software can include but not limited to device driver, operating system, developing instrument and application software.This computer-readable medium also comprises computer program of the present invention, is used to carry out all or part of (is dispersive if handle) of the processing that realizes that the present invention is performed.
Computer code device of the present invention can be any explainable or executable coding device, includes but not limited to script, explainable program, dynamic link libraries (DLL), java class and complete executable program.In addition, in order to have good performance, reliability and/or cost, can distribute a part of the present invention to handle.
Term " computer-readable medium " refers to any medium of the instruction that participation is provided for carrying out to treater 1003 as used herein.Computer-readable medium can adopt many forms, includes but not limited to non-volatile media, Volatile media and transmission medium.Non-volatile media for example comprises CD, disk and magneto-optic disk, such as hard disk 1007 or removable media driving mechanism 1008.Volatile media comprises dynamic storage, such as primary storage 1004.Transmission medium comprises concentric cable, copper cash and optical fiber, comprises the electric wire that constitutes bus 1002.Transmission medium can also adopt the form of sound wave or light wave, such as sound wave that produces during radiowave and infrared data communication or light wave.
One or more instructions of one or more sequences that various forms of computer-readable mediums may be used to carry out to the treater transmission.For example, instruction can be transmitted on the disk of remote computer at first.Remote computer can keep this instruction in dynamic storage, be used for long-range realization of the present invention all or part of, and use modulator-demodulator unit on telephone wire, to send this instruction.The modulator-demodulator unit of ECU control computer 899 this locality can receive the data on the telephone wire and use infrared transmitter that these data are converted to infrared signal.The infrared detector that is coupled to bus 1002 can receive data that infrared signal carries and data are placed on the bus 1002.Bus 1002 sends data to primary storage 1004, and treater 1003 is retrieved from primary storage 1004 and executed instruction.Storage can selectively be stored in storing device 1007 or 1008 by the instruction that primary storage 1004 receives before or after treater 1003 is carried out.
ECU control computer 899 also comprises the communication interface 1013 that is coupled to bus 1002.Communication interface 1013 provides the bidirectional data communication that is coupled to network link 1014, and this network link 1014 for example is connected to Local Area Network 1015 or is connected to alternative communication network 1016 such as the Internet.For example, communication interface 1013 can be the NIC that is additional to the local area network of any packet exchange.As another example, communication interface 1013 can be asymmetric DSL (ADSL) card, Integrated Service Digital Network card or modulator-demodulator unit, so that the data corresponding connection is offered the communication link of respective type.Also can implement radio link.In any this enforcement, communication interface 1013 sends and receives electricity, electromagnetism or the optical signal of the numerical data stream that carries the expression various types of information.
Network link 1014 typically offers other data equipment by one or more networks with data corresponding.For example, network link 1014 can pass through local area network 1015 (for example, LAN) or by the service supplier apparatus operating provide connection to another computer, this service supplier provides communication service by network of communication 1016.Local area network 1014 for example uses electricity, electromagnetism or the optical signal and relevant physical layer (for example, CAT 5 cables, concentric cable, optical fiber or the like) that carries numerical data stream with network of communication 1016.Signal by diverse network and network link 1014 with can realize in baseband signal or signal that by the signal of communication interface 1013 communication interface 1013 sends numerical data ECU control computer 899 to and passes numerical data back from ECU control computer 899 based on carrier wave.Baseband signal transmits numerical data as unmodulated electricimpulse, this electricimpulse is described with digital data bit stream, term " bit " digit symbol broadly wherein, and each symbol transmits one or more at least information bits.This numerical data also can be used for such as with amplitude, phase place and/or frequency shift keyed signals modulated carrier, and this carrier wave is propagated on transmission medium or transmitted by propagation medium as hertzian wave.Therefore, the communication channel by " wired " sends numerical data as unmodulated base band data, and/or sends in being different from the predetermined frequency band of base band by modulated carrier.ECU control computer 899 can transmit and receive data by network 1015 and 1016, network link 1014 and communication interface 1013, comprises program code.Network link 1014 can provide link to mobile equipment 881 by local area network 1015 in addition, such as PDA(Personal Digital Assistant), laptop computer or cellular telephone.
Coated semiconductor of the present invention can be used for various final uses.Main purpose in these final uses is the protection against corrosion of conductive structure.Be used to prevent that conductive substrates corrosive native system from comprising:
(a) coated semiconductor contacts with the part surface conduction of conductive structure at least; And
(b) device of filtering corrosion noise, wherein this device comprises electron sink, such as battery or other power supply, and the wave filter (or bank of filters) that is connected with the conductive substrates that applies, as electrical condenser.
Native system also comprises anti-corrosion method, and this method comprises:
1) outside surface of cleaning conductive structure;
2) apply outside surface with coated semiconductor of the present invention; And
3) corrosion noise in the use electronic filter minimization system.
A key of anti-corrosion method of the present invention and system is to measure the corrosion noise and the applying electronic wave filter that are produced by total system (including but not limited to substrate, coating and filter assembly) to minimize this noise.
Please refer again to Fig. 6, be (Fig. 6) that measures in 249 days trial period in effect and the total performance of the ECU on the coated semiconductor.In this test, the zinc release rate has reduced owing to coating " degeneration " under two kinds of conditions.But, use ECU to show that the reduction in the zinc release rate is big significantly, its degree depends on the work period that is used to regulate or wave filter alternately is converted into and goes out this circuit.Should be understood that being used to control the work period that zinc discharges the degree of (and toxicity) depends on several parameters (such as the corrosion noise of measuring, temperature, salinity, humidity, speed of the ship in metres per second or the like), and these parameters depend on envrionment conditions.The present invention proposes to regulate the device of these speed and relevant control algolithm by ECU.The zinc release rate is reduced to 1/250th, and is perhaps low to microgram/every square centimeter every day 0.001, far below United States Navy maximum admissible every days 15 every square centimeter of microgram speed (Office of Naval Reaserch, S.McElvany).These tests show that with respect to zinc loss (amount of every square centimeter of zinc is divided by dissolution rate), the life-span of coated semiconductor can prolong significantly when using ECU.As shown in Figure 6, the result of supervision current potential shows that the test panel that does not have ECU has quite low current potential according to the ECU value of using, and is approximately the 150-250 millivolt.Because the zinc oxidation rate depends on the amplitude of current potential exponentially, the zinc oxide current potential will increase and the zinc current potential will reduce along with the reduction of the resistance on zinc/zinc oxide border.Represent power sensitivity by Ta Feier (Tafel) constant, be assigned to zinc and be approximately 30 millivolts.The amplitude of the voltage difference of this Ta Feier constant and measurement predicts that the relative passivation that causes owing to ECU is between factor 150 and 4,000.In a word, the zinc dissolution rate is that semi-conductive work theory is consistent with potential data, and the use of ECU causes the oxidation rate of zinc to reduce, and prolongs the life-span of coated semiconductor significantly.The measurement that these benefits are used by the present invention and/or predetermined parameters will further improve, comprise one of following at least: the time limit, coat-thickness, the surface area of coating and the shape of coating area of the instantaneous velocity of temperature, saltiness/water purity, humidity, the time limit, short-term working cycle, long-term working cycle, boats and ships, speed of the ship in metres per second history, instant geographical position, geographical position history, coating.
The present invention can customize protection against corrosion and the marine anti-pollution that is used for electro-conductive material, includes but not limited to: the civil and military aircraft; Petroleum storage tanks; Municipal administration comprises highway and bridge; And naval, seashore anti-smuggling and army's engineering project; Chemical industry; Pulp and paper industry; The power station; Railroad bridge and rail car; The steel building of making is such as barn and laundry; Water tower; Boats and ships; The seashore platform; And other marine structure.Coating can also be used for the equipment relevant with nuclear power factory and/or vehicle, outer space task, volcano exploration with ECU and monitor, and the exploration of the poisonous seismic environment under the deep water.
For boats and ships, the present invention can be operated so that greatly reduce a kind of economy, durable and the environment amenable alternative that expensive hull degrades and be existing antifouling and anti-corrosion system.Coated semiconductor can be applicable on the new boats and ships between tectonic epochs and is applied on the existing ship of arranging to put into during the graving dry dock, and this carried out routine appearance when applying usually in per 2.5 years.Utilize ECU, everyone of boats and ships who has used coated semiconductor can receive the benefit that reduces fuel and upkeep cost, prolongation boats and ships hull life-span and obtain bigger total boats and ships operability and shorten annual stoppage time from high average running speed.
For tank and water tower, the corrosion noise of ECU control of the present invention reduces system and is used in removable water tank inside by the EPA approval.Reasonably use and use ECU, expect the life of this coating continuity tank.As this long-lived result, the tank owner will can not suffer the expected expense that applies again with supercoat.
Obviously, according to above-mentioned instruction, it is possible that the present invention carries out numerous modifications and variations.Therefore, should understand in the scope of appending claims, can also implement the present invention outside the specifically described content here.

Claims (48)

1. the corrosive system of the conductive structure that contacts with corrosive environment of a control comprises:
Comprise the coating that is arranged in the semiconductor grain on the described conductive structure;
Wave filter is connected to described coating and has the controllable filter characteristic; And
Control electronics, be connected to described wave filter, be included in being connected of at least one equipment in local sensor, database and the remote-control equipment, and be provided with local parameter of reading, stored parameters and the long-range aligned phase signal ground that provides and control described controllable filter characteristic; Wherein,
Described controllable filter characteristic is the impedance with low pass or notch filter form; And
Described control electronics is controlled described wave filter, makes described wave filter have the amplitude of predetermined corrosion noise frequency and/or filter characteristic that frequency is lowered and/or described wave filter is connected off and on.
One of 2. system according to claim 1, below wherein said wave filter comprises at least:
Active filter;
Can regulate passive filter; With
Fixing passive filter.
3. system according to claim 2, wherein said wave filter is a plurality of passive filters, and described controllable filter characteristic is another passive filter control that is converted to described a plurality of passive filters by a passive filter from described a plurality of passive filters.
4. system according to claim 2, wherein said wave filter is the single passive filter of regulating.
5. system according to claim 1, wherein said this locality is read parameter and is comprised one of at least following:
The corrosion noise parameter;
The salinity parameter;
Temperature parameter;
Geo-location parameter;
Time parameter;
The pure parameter of solution;
Speed parameter;
Depth parameter; With
Pressure parameter.
One of 6. system according to claim 1, below wherein said stored parameter comprises at least:
Apply the date of described object;
The object's position history parameters;
Coated semiconductor work period history parameters;
The object's position history parameters;
The form parameter of coating zone; With
The object velocity history parameters.
7. system according to claim 1, wherein said conductive structure comprises the metal of selecting from the group of being made up of ferrous metal and conduction non-ferrous metal.
8. system according to claim 7, wherein said metal is a steel.
9. system according to claim 7, wherein said metal is an aluminium.
10. system according to claim 1, wherein said conductive structure is to select from the group of being made up of boats and ships, marine structure, oil rig, power station and underwater structure.
11. system according to claim 1, wherein said coated semiconductor comprises conductive organic polymer; With one or more metals, alloy and nonmetal semiconductor material.
12. system according to claim 11, wherein said conductive organic polymer is the member who selects from the group of being made up of poly acetylene, polyphenyl, poly-furans, Polythiophene, polypyrrole, poly (arylene vinylidene), polyaniline and its spinning solution component.
13. system according to claim 11, wherein said one or more metal or alloy comprise the metal of selecting from the group of being made up of zinc, titanium, aluminium, gallium, cerium, magnesium, barium and caesium.
14. system according to claim 11, wherein said one or more metal or alloy comprise from the mixture by zinc, titanium, aluminium, gallium, cerium, magnesium, barium and caesium and one or more metals of selecting from the group that one or more metal oxides that their obtain are formed.
15. system according to claim 11, wherein said one or more metal or alloy are combinations of zinc/zinc oxide.
16. system according to claim 10, wherein said coated semiconductor also comprises one or more dyestuffs or paint.
17. a control electronics is provided with its control corrosion noise and reduces system, this system comprises controllable filter and is applied to the coated semiconductor of conductive structure that this equipment comprises:
First coupling end, setting are connected to described corrosion noise and reduce system;
Second coupling end is provided with at least one equipment that is connected in local sensor, database and the remote-control equipment; And
Control device is provided with by the control signal that sends on described first coupling end and local parameter, stored parameter and the long-range signal that provides read and consistently controls one of at least described controllable filter.
18. equipment according to claim 17, wherein said controllable filter has the controllable filter characteristic, and this characteristic is the impedance with low pass or notch filter form.
19. equipment according to claim 18, wherein said wave filter is a plurality of passive filters that impedance differs from one another, and described controllable filter characteristic is to control by another passive filter that a passive filter from described a plurality of passive filters is converted in described a plurality of passive filter.
20. equipment according to claim 18, wherein said controllable filter are the single passive filters of regulating.
Comprise one of at least following 21. equipment according to claim 18, wherein said this locality are read parameter:
The corrosion noise parameter;
The salinity parameter;
Temperature parameter;
Geo-location parameter;
Time parameter;
The pure parameter of solution;
Speed parameter;
Depth parameter; With
Pressure parameter.
One of below 22. equipment according to claim 18, wherein said stored parameter comprise at least:
Apply the date of described object;
The object's position history parameters;
Coated semiconductor work period history parameters;
The object's position history parameters;
The form parameter of coating zone; With
The object velocity history parameters.
23. equipment according to claim 18, wherein said conductive structure comprise the metal of selecting from the group of being made of ferrous metal and conduction non-ferrous metal.
24. equipment according to claim 23, wherein said metal is a steel.
25. equipment according to claim 23, wherein said metal is an aluminium.
26. equipment according to claim 18, wherein said conductive structure are to select from the group of being made up of boats and ships, marine structure, oil rig, power station and underwater structure.
27. equipment according to claim 18, wherein said coated semiconductor comprises conductive organic polymer; With one or more metals, alloy and nonmetal semiconductor material.
28. equipment according to claim 27, wherein said conductive organic polymer are the members who selects from the group of being made up of poly acetylene, polyphenyl, poly-furans, Polythiophene, polypyrrole, poly (arylene vinylidene), polyaniline and its spinning solution component.
29. equipment according to claim 28, wherein said one or more metal or alloy comprise the metal of selecting from the group by zinc, titanium, aluminium, gallium, cerium, magnesium, barium and caesium and their respective metal oxide compound and alloy composition.
30. equipment according to claim 27, wherein said one or more metal or alloy comprise from the mixture by zinc, titanium, aluminium, gallium, cerium, magnesium, barium and caesium and one or more metals of selecting from the group that one or more metal oxides that their obtain are formed.
31. equipment according to claim 27, wherein said one or more metal or alloy are combinations of zinc/zinc oxide.
32. equipment according to claim 27, wherein said semiconduction organic polymer coating also comprises one or more dyestuffs or paint.
33. the method that the conductive structure that prevents to contact with corrosive environment is corroded, described method comprises:
Electronic control unit is connected to controllable filter, the coated semiconductor under this controllable filter is connected to and is arranged on the conductive structure;
Use described controllable filter to filter corrosion noise in the described coated semiconductor;
Monitor at least one parameter relevant with the corrosion of described coated semiconductor; And
Consistently regulate the filter characteristic of described controllable filter with described at least one parameter; Wherein
Described controllable filter characteristic is the impedance with low pass or notch filter form; And
Described electronic control unit is controlled described controllable filter, makes described controllable filter have the amplitude of predetermined corrosion noise frequency and/or filter characteristic that frequency is lowered and/or described controllable filter is connected off and on.
34. method according to claim 33, wherein said wave filter is the passive filter that a plurality of described filter characteristics differ from one another, and described filter characteristic is to control by another passive filter that a passive filter from described a plurality of passive filters is converted in described a plurality of passive filter.
35. method according to claim 33, wherein said controllable filter are the single passive filters of regulating.
36. method according to claim 33, wherein said at least one parameter comprises:
The corrosion noise parameter;
The salinity parameter;
Temperature parameter;
Geo-location parameter;
Time parameter;
The pure parameter of solution;
Speed parameter;
Depth parameter;
Pressure parameter;
Apply the date of described object;
The object's position history parameters;
Coated semiconductor work period history parameters;
The object's position history parameters;
The form parameter of coating zone; With
The object velocity history parameters.
37. method according to claim 33, wherein said conductive structure comprise the metal of selecting from the group of being made of ferrous metal and conduction non-ferrous metal.
38. according to the described method of claim 37, wherein said metal is a steel.
39. according to the described method of claim 37, wherein said metal is an aluminium.
40. method according to claim 33, wherein said conductive structure are to select from the group of being made up of boats and ships, marine structure, oil rig, power station and underwater structure.
41. method according to claim 33, wherein said coated semiconductor comprises conductive organic polymer; With one or more metals, alloy and nonmetal semiconductor material.
42. according to the described method of claim 41, wherein said conductive organic polymer is the member who selects from the group of being made up of poly acetylene, polyphenyl, poly-furans, Polythiophene, polypyrrole, poly (arylene vinylidene), polyaniline and its spinning solution component.
43. according to the described method of claim 41, wherein said one or more metal or alloy comprise the metal of selecting from the group by zinc, titanium, aluminium, gallium, cerium, magnesium, barium, caesium, their respective metal oxide compound and alloy composition.
44. according to the described method of claim 41, wherein said one or more metal or alloy comprise from the mixture by zinc, titanium, aluminium, gallium, cerium, magnesium, barium and caesium and one or more metals of selecting from the group that one or more metal oxides that their obtain are formed.
45. according to the described method of claim 41, wherein said one or more metal or alloy are combinations of zinc/zinc oxide.
46. according to the described method of claim 41, wherein said semiconductive organic polymer coating also comprises one or more dyestuffs or paint.
47. the system that the conductive structure that prevents to contact with corrosive environment is corroded, described conductive structure is coated with coated semiconductor, and described system comprises:
Filter the device of the corrosion noise in the described coated semiconductor;
Monitor the device of at least one parameter relevant with the corrosion of described coated semiconductor; And
Consistently regulate the device of electronic filter with described at least one parameter.
48. according to the described system of claim 47, the wherein said device that is used to monitor comprises computer program.
CNB2003801014887A 2002-10-17 2003-10-17 Semiconductive corrosion and fouling control apparatus, system, and method Expired - Fee Related CN100390323C (en)

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