Patent Application: US-81765906-A

Abstract:
an anti - corrosive composition , comprising a combination of at least two of the following materials : vanadates , molybdates , tungstates , silicates , phosphates , borates . ce cations , y cations , la cations , eu cations , gd cations , nd cations , and reaction products thereof .

Description:
the corrosion inhibition by numerous compounds has been examined through the years with the hope of providing a chromate replacement . these compounds include molybdates , vanadium - based compounds , boron - based compounds , and rare earth salts . recently , many of these compounds have been examined for inhibitor efficacy on aerospace aluminum alloys . however , no single compound has yet demonstrated an effective corrosion inhibition power ( efficiency at specified concentration ) on these aerospace alloys that compares to chromate - based inhibitors . the present inventors have discovered an alternative to the use of a single inhibitor species is that of using synergistic combinations of two or more compounds . synergy occurs when inhibition by the combination exceeds the arithmetic sum of the inhibition by individual components . synergistic combinations of inhibitors have been examined extensively for steel in acidified and neutral aqueous environments , as well as for copper in neutral aqueous environments . examples of the present invention include 1 : 1 ratios of these materials , ratios other than 1 : 1 , and many different concentrations . additionally , the substrate may be exposed to these compounds either simultaneously or in a sequence . the predictive abilities and fundamental understanding of molecular systems with more than two different atomic species remains extremely limited , so that one is faced with an expansive matrix of experiments to identify the optimum inhibitor combination under a wide range of test conditions ( e . g . ph , t , choice of a and b , ratio of a and b , concentration of a + b , etc .). therefore , other aspects of the present invention include approaches to increase the rate of material discovery through combinatorial approaches . combinatorics , initially utilized in electronics development , has been more commonly associated with automated synthesis and high throughput screening for pharmaceuticals . in the combinatorial process , large arrays of material or chemical variables can be produced and screened to identify the optimum process or condition of interest . creation of the combinatorial library is typically straightforward . however , the identification of a rapid evaluation method that can sensitively detect changes in the relevant parameter is not to be assumed and is often the rate limiting process in rapid discovery . this idea of rapid detection of corrosion inhibitors is further complicated by the time variation in inhibitor performance . the corrosion protection properties of inhibitors can be electrochemically quantified in many different ways , however there are presently no specified electrochemical methods that can be implemented in a rapid fashion ( i . e . within minutes ) in the laboratory to predict long - term ( i . e . years ) corrosion protection . yet , the long - term desire is to screen thousands of chemical compounds with an infinite number of chemical combinations in a vast number of environmental conditions ( temperature , ph , concentration , etc .). the idea of “ screening ” for rapid discovery must be emphasized . once large numbers of materials and test conditions have been examined and promising target compounds have been identified , a more rigorous scheme of testing can then be implemented to more carefully document the inhibition properties of these targets . examples of the present invention may be made by several methods . one such method comprises the steps of providing a mixture that contains one or more of the target species described herein , or any compound or mixture derived from any other compound or mixture that contains the designated target species . for example , a component can contain one or more of the target species and will be designated by number ; 1 , 2 , 3 , etc . procedure 1 : mix component 1 with one or more additional components in a common medium ( e . g ., water , organic resin , oil , etc .) and expose the mixed components to the metal either by immersion , spray , etc . any combination of components , any concentration , and any time can be used . procedure 2 : mix component 1 in a medium ( e . g ., water , organic resin , oil , etc .). mix component 2 in a separate medium , and any other component in a separate medium . expose the metal to each mixture in series , in any order , at any concentration , and for any time duration . the compositions of the present invention may be used as coatings or within coatings as known in the art . for example , the coatings may be applied to a surface as described in u . s . pat . nos . 6 , 077 , 885 ; 5 , 866 , 652 ; and other documents cited herein . the following , and all examples herein , are specifically not intended to be limiting of the present invention . the method of this example demonstrates a method to determine potential inhibitor combinations and compare their performance in short - term testing to the performance of chromate for the mitigation of corrosion on aa2024 - t3 substrates . additionally , this example demonstrates corrosion inhibition by the synergistic combinations of the present invention . aluminum alloy 2024 wire ( california fine wire ) with a diameter of 1 . 59 mm ( 1 / 16 ″) was obtained for use as electrodes in electrochemical testing . metallography was carried out on the aa2024 wire to examine the differences in grain structure and intermetallic particle distribution between the aa2024 wire and aa2024 sheet . optical microscopy ( fig1 ) revealed that the 2024 wire microstructure was qualitatively similar to that found in 2024 sheet used on aircraft . high - throughput testing of multiple electrochemical cells was accomplished by the use of the multichannel microelectrode analyzer ( nma ) ( scribner , associates , southern pines , n . c .) in combination with an array of electrochemical cells established through the use of a conventional 8 × 12 reaction frame and fabricated top to contain the wire electrodes . the mma is a group of 10 modules of 10 zero resistance ammeters ( 100 total zra &# 39 ; s ) that can be used for current or potential measurement of electrodes . the modules may be changed out to allow measurement of different current ranges . the range used for these experiments allowed clear measurement between 1 nanoamp and 10 microamps . the mma is computer controlled and is attached to the electrodes in the reaction frame by means of an adapter . 50 cells of the conventional 8 × 12 reaction frame were used to house 50 independent chemistries . two aa2024 wire electrodes were plugged into electrical contacts contained in the fabricated top for each of the 50 cells , totaling 100 wire electrodes connected to the mna . the fabricated top is then placed on the reaction frame ( not air - tight ) containing the chemistries of interest . each module on the mma can then be set to establish a potential of one wire electrode vs . the other . a schematic of the reaction frame setup is shown in fig2 . previously , testing of a series of inhibitors was conducted by electrochemical impedance spectroscopy to obtain information on inhibitor performance on aa2024 - t3 sheet exposed to chloride . the testing was conducted by placing an aa2024 - t3 coupon in 3 . 4 mm inhibitor and 0 . 6 m nacl solution . these are very harsh conditions , but represent the type of environment in which chromates can and do perform . eis was conducted on the samples at initial exposure and exposures of 1 , 3 , 5 and 10 days . the results of the eis testing for neutral ph solutions are presented in fig3 . it can be seen in this figure that the trendlines fluctuate significantly at early times and are not at steady state even at 10 days . nonetheless , there were certain inhibitors that demonstrated consistent ordinal ranking of corrosion resistance ( polarization resistance , r p , minus the diffusional impedance , r d ) over all 10 days of testing and were selected as target data for this study . three compounds were selected for testing along with the control ( no inhibitor ): cerium chloride , yttrium chloride , and sodium metatungstate . these data are emboldened in fig3 . since earlier eis testing indicated that the corrosion resistance was a suitable indicator of inhibitor performance , initial experiments with the mma have focused on the dc acquisition of the polarization resistance . while the mma is fully capable of performing 3 - electrode potentiostatic and potentiodynamic experiments , the initial experiments performed here have focused on more simple methods that are rapid and amenable to the idea of high - throughput experimentation . a crude form of the polarization resistance was obtained through a low amplitude dc bias applied between two electrodes . two - electrode dc bias measurements were performed using two 4 . 45 cm ( 1 . 75 ″) long aa2024 wire electrodes attached to the reaction frame . this allowed 3 . 3 cm ( 1 . 3 ″) of length and 1 . 65 cm 2 ( 0 . 255 ″ 2 ) of surface area to be exposed to solution . one electrode in each cell was polarized 100 mv ( to − 425 mv she ) with respect to the other electrode , which was maintained at a potential of − 525 mv she , corresponding to the open circuit potential of the control . the resulting current between the two electrodes was measured over a time period of 9 hours . the nma device measured the current between the paired electrodes using an in - line zra . 100 mv bias was used to ensure that the nanoampere limitation on measurement would not interfere with evaluation of effective inhibitors and combinations . other potential screening methods could include a lower dc polarization , possibly 10 - 50 mv , cyclic voltammetry , or fluorometric methods of assaying corrosion product concentrations . cells of the reaction frame were filled with a solution containing 3 . 4 mm inhibitor and 0 . 6 m nacl adjusted to ph 7 to match the chemistries used in the previous eis study . the change of solution ph due to solution chemistry changes caused by electrode corrosion was not monitored . 1 . 75 ml of solution was pipetted into each test cell of the reaction frame . the experimental method listed above was modified slightly for screening of potential inhibitor synergies after the initial experiments discussed above proved promising . two - electrode dc bias measurements were performed as above but using 2 . 54 cm ( 1 ″) 2024 wires as electrodes on the reaction frame . 1 . 7 cm ( 0 . 67 ″) of the length and 0 . 85 cm 2 ( 0 . 13 ″) of surface area of the aa2024 wire were exposed to the solution in the testing cell . one electrode in each cell was again polarized 100 mv ( to − 425 mv she ) with respect to the other electrode , which was maintained at a potential of − 525 mv she , corresponding to the open circuit potential of the control . 50 cells of the reaction frame were used in each testing interval to maximize throughput in the screening for potential inhibitor synergies . again , the current established between two - wire electrodes biased 100 mv apart was measured over a time period of 9 hours . cells of the reaction frame in the synergy screening experiments were filled with 2 ml of 3 . 4 mm total inhibitor in 0 . 6 m nacl solution . forty - four inhibitor combinations were tested in this stage of the screening process and were adjusted to ph 7 by addition of hcl or naoh . screening was performed on solutions containing 0 . 2 mm ( 5 . 9 %), 0 . 7 mm ( 20 . 6 %), 1 . 2 mm ( 35 . 3 %), 1 . 7 mm ( 50 %), 2 . 2 mm ( 64 . 7 %), 2 . 7 mm ( 79 . 4 %), and 3 . 2 mm ( 94 . 1 %) of inhibitor a with the balance of the 3 . 4 mm total inhibitor comprised of inhibitor b for all 44 inhibitor combinations . one advantage of high throughput screening process of the present invention is the potential to explore numerous variables , e . g . ph , temperature , concentration , and others . in this example , the variables examined were actual inhibitor in the mixture , ratio of inhibitors , and ph . results from the dc polarization tests for the individual inhibitors were plotted to examine the current change over the course of the 9 hour test . an example of data from the 100 mv polarization high throughput screening experiments is shown in fig4 . as can be seen , the data from these polarization experiments changes significantly at early times ( 1 - 6 hours ) and tends to become more stable in overall behavior near the 7 th hour . while additional time may ( or may not ) lead to steady - state behavior , a decision was made to collect current data from each cell for 2 hours , from the 7 th hour to the 9 th hour to provide the characteristic data for any particular inhibitor . this decision was a compromise between possible increased accuracy by extending the time of measurement to more closely approach steady state and speed of data acquisition to facilitate the theme of high throughput screening . in addition to general current trendline , a more detailed observation of the current for each inhibitor showed that noise was present in all of the cells tested . this was believed to be electrochemical noise as the amount varied depending on the inhibitor chemistry of the cell . noise analysis represents yet another approach that might be examined for high throughput screening . the ordinal ranking of inhibitor performance using the 100 mv polarization screening results correlated 100 % with the ordinal ranking of the eis and statistical pit analysis for the four chemistries selected , i . e . cerium chloride & gt ; yttrium chloride & gt ; control & gt ; sodium metatungstate . comparison of 100 mv dc bias screening results and 10 day electrochemical impedance testing of 11 single corrosion inhibitors is shown in fig5 . a linear regression between 1 / r c and i corr was used to compare data collected by the two different test methods , eis ( previous tests ) and the hts . this comparison was selected due to the widely known correlation r p = b / i corr . a r 2 value of 0 . 86 was determined when the data point marked by the arrow was excluded from the regression . with respect to the present invention , synergy is said to occur , for iso - concentration comparisons , when any combination of more than one inhibitor produces a lower current than any of the chemical constituents alone . this definition of synergy differs slightly from synergy calculations of others where inhibition efficiencies are compared between exact chemical composition of each constituent and combination as shown in the formula below for chemical composition : x mm chemical a + y mm chemical b : synergy parameter ( s ab )= 1 −[( ie ( x mm a ) + ie ( y mm b ) )−( ie ( x mm a ) × ie ( y mm b ) )][( 1 − ie ( x mm a + y mm b ) ] inhibition efficiency ( i . e . )=[ 1 −( i inhibited / i uninhibited )]× 100 % with respect to the present invention , the currents measured for any and all inhibitor experiments was always compared to the same set ( n = 200 +) of pooled control ( no inhibitor ) results . efficiency is used here because good inhibitors are represented with high values . using the definition of synergy above , where the synergy is said to occur at any current lower than the best inhibitor alone , boundary lines of synergy and antagonism were created in each system . the synergy line is merely the best performing single inhibitor and the antagonism line is the worst performing single inhibitor for that system . confidence in these boundary lines is high , as the single inhibitor currents are averaged from at least 25 separate test cells for each inhibitor . the largest standard deviation for the single inhibitor values of current was 3 % of the mean current . standard deviations are shown for the remaining data points . screening of potential inhibitor synergies using the method of the present invention reveals several types of inhibitor combination behavior . some of the inhibitor combinations examined exhibit no apparent benefit of mixing the inhibitors . the current from testing of these mixtures is not lower than the better inhibitor alone at the same total inhibitor concentration or higher than the worse inhibitor alone . an example of this lack of benefit behavior may be seen in the results of testing a mixture of potassium phosphate and yttrium chloride shown in fig6 . fig6 shows that the resulting current when using any ratio of potassium phosphate and yttrium chloride falls between the current for each inhibitor alone at 3 . 4 mm total inhibitor concentration . this type of behavior was observed in approximately 20 % of the combinations tested here . another type of behavior observed in about 35 % of the inhibitor mixtures tested is the presence of both synergy and antagonism ( i . e ., the opposite of synergy ) across the ratio of concentration of the two inhibitors . an example of such a mixture is that of sodium metasilicate and yttrium chloride shown in fig7 . in fig7 , the mixtures of 0 . 2 mm ycl 3 / 3 . 2 mm na 2 sio 3 , 0 . 7 mm ycl 3 / 2 . 7 mm na 2 sio 3 , 2 . 2 mm ycl 3 / 1 . 2 mm na 2 sio 3 , and 2 . 7 mm ycl 3 / 07 mm na 2 sio 3 exhibited synergy , since the current at each mixture was lower than ycl 3 alone . interestingly , the combinations of 1 . 7 mm ycl 3 / 1 . 7 mm na 2 sio 3 and 3 . 2 mm ycl 3 / 0 . 2 mm na 2 sio 3 exhibited antagonism , where the currents at each of these combinations was higher than that of na 2 sio 3 alone . yet another type of behavior observed from the testing of mixtures is antagonism at some or all ratios of the inhibitors . the behavior of limited - range antagonism , arbitrarily defined as the occurrence of antagonism in less than half of the ratios for any given inhibitor mixture . this behavior was observed in less than 10 % of the inhibitor mixtures examined . approximately 10 % of the inhibitor mixtures examined showed antagonism at all ratios . the mixture of sodium metavanadate and cerium chloride is an example of a mixture that exhibited antagonism at all ratios of the inhibitors and is shown in fig8 . in fig8 it can be readily observed that the current from any ratio of the two inhibitors results in an increased current over either of the inhibitors alone . the behavior of this mixture is interesting because each inhibitor alone is ranked among the best of the non - chromate inhibitors for aa2024 but combined they are more detrimental to the alloy . finally , the most sought after behavior that was observed in testing of the inhibitor mixtures is the presence of synergy across some or all ratios of the inhibitors . the behavior of limited - range synergy , arbitrarily defined as having less than half of the ratios of the inhibitor mixture exhibit synergy , was observed in approximately 20 % of the forty - four inhibitor mixtures examined at ph 7 . broad - range synergy , in which synergy was demonstrated at all concentrations tested was observed in less than 10 % of the 44 mixtures tested . the mixture of sodium phosphate and sodium metavanadate is an example of a mixture that exhibited synergy at all tested ratios of the inhibitors and may be seen in fig9 . mixtures exhibiting synergy at all ratios of the combined inhibitors are considered the safest to implement in a coating system . if a non - ideal ratio of the inhibitors is released from the coating , no detrimental effects from that mixture of inhibitors should exist . a summary of the observed behavior of the forty - four inhibitor mixtures tested at ph 7 is presented in table 1 below . the percentage of points exhibiting either synergy or antagonism is based on a comparison of the current of the mixture to the constituents of the mixture alone . for example , testing of 3 . 4 mm mixtures : 0 . 2 mm of compound a balance of compound b , 0 . 7 mm of a balance of b , 1 . 2 mm of a balance of b , 1 . 7 mm of a balance of b 2 . 2 mm of a balance of b , 2 . 7 mm of a balance of b , 3 . 2 mm of a balance of b , represents 7 different mixtures to be considered . if two of these points fall below the current of the best single inhibitor present in that system , then 2 of the 7 points are said to exhibit synergy , leading to a value of 28 . 6 % of the points exhibiting synergy . a mixture current less than the control refers to a mixture where all of the ratios of that mixture exhibit inhibition , regardless of any synergy present . finally , the percentage of ratios of the mixture tested with currents under 0 . 6 microamps refers to mixtures that present more inhibition than the best non - chromate inhibitor tested here . synergy between the oxyanions of v , mo , and p is noted . molecular combinations of these oxyanions form high molecular weight supramolecular anions claimed to inhibit pitting . investigation of these alone represents ideal application of this combinatorial analysis of the present invention . combinations of navo 3 / kh 2 po 4 and navo 3 / na 3 po 4 when adjusted to neutral ph have , in principle , the same mix of vo 3 − , po 4 − 3 , hpo 4 − 2 , and h 2 po 4 − . without being bound by theory , the fact that the synergies differ suggest either the k cation influences the inhibition or kinetically determined different macromolecular species form depending on whether the neutral ph is approached from the acid side ( navo 3 : kh 2 po 4 ) or the basic side ( navo 3 : na 3 po 4 ). the latter is most likely but its investigation remains beyond the scope of this report . inhibition efficiency was calculated for all inhibitors and combinations of inhibitors using the 100 mv polarization screening data . efficiency calculations assume a uniform current density across the sample surface , but have also been applied to systems undergoing localized corrosion due to ease of calculation and need for comparison 15 , 42 - 45 . inhibition efficiency was calculated using the formula below : inhibition efficiency ( i . e . )=[ 1 −( i inhibited / i uninhibited )]× 100 % the best inhibiting efficiencies found in all of the inhibitors and binary combinations tested are shown in fig1 . the ratio with the best inhibitor efficiency was used for each combination listed . some combinations are limited - range synergies but demonstrate strong synergy at certain ratios . a significant advantage of the high throughput screening approach used here is the ability to survey inhibitor performance over a range of test conditions within a single experiment . the ideal inhibitor should perform well over a wide ph range , as well as temperatures . a 50 cell array was employed to test nine inhibitor ratios at ph 2 , 4 , 7 , 10 and 12 . an example of this large matrix of experiments is shown in fig1 for the mixture of sodium metavanadate and sodium metasilicate . fig1 shows the utility of the proposed high throughput screening method . this plot can be interpreted similarly to a phase diagram . the x axis provides information on the chemical make - up of the inhibitor . on the left side , one has a solution of 100 % compound a ; on the right side one has a solution of 100 % compound b . the points in between the left and right are proportionally different amounts of a and b . the ionic concentration in all cases is 3 . 4 mm . the initial ph of the test solution is adjusted to the ph value indicated on the vertical axis . the color designates the corrosion current under the specified conditions . so depending on the inhibitor ratio and ph , different corrosion protection performance occurs . for the inhibitor combinations tested , it is clear that synergistic ratios that exist at one ph do not necessarily hold for other phs . synergies are clearly observed in the plot of current for 1 . 7 mm ( 50 %) of each inhibitor at ph 12 , and for 3 . 2 mm sodium metavanadate , 0 . 2 mm sodium metasilicate at ph 7 . these results are repeatable and reinforce the need for high throuput experimentation for the discovery and characterization of corrosion inhibitors . evaluation of ten inhibitors for aa2024 was conducted using a 9 hour 100 mv dc bias screening method under the control of the mma . hours 7 - 9 of this test were found to exhibit stable currents that were averaged for evaluation of the inhibitors . confidence in this 100 mv screening method was established from correlating results with corrosion resistance evaluated using electrochemical impedance on aa2024 - t3 . screening of inhibitor combinations was conducted using the 100 mv dc bias screening method . four types of inhibitor combination behavior were observed using this method ; no benefit of the mixture , antagonism , synergy , and a mix of antagonism and synergy across the ratio of the mixture . some of these mixtures showed only limited range behavior where the behavior was limited to certain ratios of the inhibitors while others exhibited broad range behavior . 44 inhibitor combinations were examined at ph 7 but the 100 mv screening method has been shown capable of examining a variety of testing conditions . dc polarization between two aa2024 wire electrodes using a multiple - electrode testing system appears to be a suitable method for rapid screening of corrosion inhibitors and inhibitor combinations . comparison of single inhibitor performance between the 100 mv dc bias ( between two aa2024 electrodes ) screening method and electrochemical impedance testing on aa2024 - t3 has shown that : the ordinal correlation between short - term ( 2 hour ) and long - term ( 10 day ) electrochemical data was 100 % when using 100 mv dc polarization of aa2024 wire for the inhibitors cerium chloride , yttrium chloride , sodium metatungstate and control that were the most consistent over the long - term testing 100 mv dc bias testing of 50 cells of independent chemistries allows high throughput for screening potential synergies between inhibitors at various ratios , ph , etc . synergies between different non - chromate corrosion inhibitors at various ratios have been discovered with inhibiting efficiencies up to 93 % the inhibiting efficiency of combinations of inhibitors varies greatly depending on ph , ratio of concentration of inhibitors , overall concentration of inhibitors , etc . these simple dc polarization tests may provide one avenue for the rapid discovery of effective corrosion inhibitors using combinatorial methods . as stated above , another embodiment of the present invention is a high throughput screening method for corrosion inhibitor discovery related to cyclic voltammetry detection , including cyclic voltammetry detection of surface enhanced copper on aa2024 - t . aluminum alloy 2024 - t3 possesses a high strength to weight ratio for its use in aerospace and other commercial applications . this high strength is achieved mainly through the presence of cu , which forms with the other alloying elements to form strengthening precipitates in the alloy . though high strength is achieved , the difference in potentials of the copper rich precipitates allows galvanic cells to form between the precipitates and the aluminum rich matrix of the alloy . in particular , s - phase ( al 2 cumg ) particles have been shown to be anodic compared to the open circuit potential of the aa2024 - t3 matrix and are one of the primary sites of pitting corrosion in aa2024 - t3 . dissolution of s - phase particles proceeds by dealloying of the aluminum and magnesium , leaving behind nanoporous copper that detaches and is oxidized in solution and reduced back on the surface of the alloy by a mechanism described by buchheit et . al . observations of the dissolution of s - phase particles and localized corrosion that lead to the enrichment of copper on the surface of aa2024 - t3 have been noted by many researchers . measurement of the amount of surface copper using cyclic voltammetry has been used to assess the level of corrosion damage on aa2024 - t3 exposed to various aggressive solutions . this cyclic voltammetry method for assessing surface copper on aa2024 - t3 will be used in the present work to evaluate corrosion damage and inhibition in 0 . 6 m sodium chloride . related to this embodiment , aluminum alloy 2024 - t3 wire ( all metal sales ), with a diameter of 1 . 59 mm ( 1 / 16 ″), was obtained for use as electrodes in electrochemical testing . the wire was cut to 2 . 54 cm ( 1 ″) lengths and degreased by ultrasonic exposure to acetone and methanol respectively for 10 minutes each . the aa2024 - t3 electrodes were exposed to inhibitor solution ( 3 . 4 mm total inhibitor concentration , 0 . 6 m nacl ) by immersing 1 . 2 cm of the electrode in the solution . cells of the reaction frame were filled with 1 . 8 ml of 3 . 4 mm total inhibitor in 0 . 6 m nacl solution . forty - four inhibitor combinations were tested in this stage of the screening process and were adjusted to ph 7 by addition of hcl or naoh . screening was performed on solutions containing 0 . 2 mm ( 5 . 9 %), 0 . 7 mm ( 20 . 6 %), 1 . 2 mm ( 35 . 3 %), 1 . 7 mm ( 50 %), 2 . 2 mm ( 64 . 7 %), 2 . 7 mm ( 79 . 4 %), and 3 . 2 mm ( 94 . 1 %) of inhibitor a , with the balance of the 3 . 4 mm total inhibitor comprised of inhibitor b for all 44 inhibitor combinations . the combinations of inhibitors were comprised of the following inhibitors : sodium metavanadate , cerium chloride , barium metaborate , yttrium chloride , sodium metatungstate , potassium phosphate , lanthanum chloride , sodium metasilicate , sodium phosphate , and sodium molybdate . 96 electrodes , connected to a reaction frame lid , were immersed in 96 independent cells containing solution of a standard 8 × 12 reaction frame . the electrodes were exposed to the inhibitor solution , which was open to air for 24 hours . after the 24 hour exposure , the reaction frame lid housing the electrodes was disconnected from the reaction frame and the electrodes were rinsed with deionized water . the electrodes housed in the reaction frame lid were then placed in a special reaction frame setup containing ph 8 . 4 borate buffer ( 4 . 31 , g / l na 2 b 4 o 7 + 7 . 07 g / l h 3 bo 3 ) in the cells of the reaction frame . the bottom of the reaction frame in this setup was removed by drilling so that a borate buffer agar gel ( 4 . 31 g / l na 2 b 4 o 7 + 7 . 07 g / l h 3 bo 3 + 10 g agar ) could serve as the bottom of the reaction frame and could connect each cell to a common counter and reference electrode also placed in the borate buffer agar gel . cyclic voltammetry was performed on the 96 electrodes using a multichannel microelectrode analyzer ( mma ) ( scribner , associates , southern pines , n . c .) to control the potential and record current . the mma is a group of 10 modules of 10 zero resistance ammeters that can be used for current or potential measurement of electrodes . the modules may be changed out to allow measurement of different current ranges . the range used for these experiments allowed clear measurement between 1 nanoamp and 1 microamp . the mma is computer controlled and is attached to the electrodes in the reaction frame by means of an adapter . the mma also controls a common reference and counter electrode for potentiodynamic experiments . a saturated calomel electrode ( 0 . 241 v vs . nhe ) and platinum mesh were used as the reference and counter electrodes in this experimental setup . a schematic diagram of the experimental setup is presented in fig1 . the cyclic voltammetry was conducted by sweeping the potential from − 700 mv sce to 300 mv sce and back to − 1200 mv sce . the range of this sweep is in the range for copper oxidation / reduction but not for the corrosion of the base material . three potential sweeps were conducted and the third cyclic voltammagram was used for evaluation of the copper content on each electrode surface . prior to each sweep a potential hold at − 700 mv sce was performed ( 5 minutes prior to sweep 1 , 10 minutes prior to sweep 2 , and 20 minutes prior to the third and final sweep ). examples of the present invention include dc polarization testing of samples in parallel . to show an embodiment of this method , 1 . 8 ml of test solution was transferred or mixed in each of 50 cells of a conventional 2 ml 8 × 12 reaction frame . each cell may contain an independent test solution . two aa2024 - t3 wire electrodes were plugged into electrical contacts contained in the fabricated top for each cell , totaling 100 wire electrodes connected to the multichannel microelectrode analyzer ( mma ). the fabricated top was then placed on the reaction frame containing the chemistries of interest and the system was left open to air . half of the electrodes , one per cell , were set to a potential 100 mv above the base potential determined by the second wire electrode of the pair . the current average was calculated using measured currents from 7 to 9 hours of dc polarization . this current average was used to quantify the corrosion protection . for an example of the determination of surface copper on aa2024 - t3 for estimating corrosion damage , 1 . 8 ml of test solution was transferred or mixed in each cell ( 96 cells ) of a conventional 2 ml 8 × 12 reaction frame . each cell may contain an independent test solution . one aa2024 - t3 wire electrode was plugged into an electrical contact contained in the fabricated top for each cell , totaling 96 wire electrodes connected to the multichannel microelectrode analyzer ( mma ). the fabricated top was then placed on the reaction frame containing the chemistries of interest and the system was left open to air . after an exposure time ( e . g ., 24 hours ), the reaction frame lid holding the electrodes was removed from the reaction frame , and the electrodes were rinsed with deionized water . the electrodes , still held in the reaction frame lid , were then placed into a special reaction frame modified for conducting cyclic voltammetry on the electrodes in parallel . as an example of the setup for the special reaction frame — for this special reaction frame , a hole was drilled into the bottom of each well of a standard 8 × 12 reaction frame . the reaction frame was then partially immersed into a borate buffer agar gel ( 4 . 31 g / l na 2 b 4 o 7 + 7 . 07 g / l h 3 bo 3 + 10 g / l agar ). this gel provided ionic continuity between each well and a universal counter and reference electrode also immersed into the gel . after solidification of the agar gel , each well was filled with 1 . 2 ml of ph 8 . 4 borate buffer ( 4 . 31 g / l na 2 b 4 o 7 + 7 . 07 g / l h 3 bo 3 ). a cyclic voltammetry was conducted by sweeping the potential at a rate of 1 mv / s from − 700 mv sce to 300 mv sce and back to − 1200 mv sce . prior to each sweep , a potential hold at − 700 mv sce was performed ( 5 minutes prior to sweep # 1 , 10 minutes prior to sweep # 2 , and 20 minutes prior to the third and final sweep ). three potential sweeps were conducted , and the third cyclic voltammogram was used for quantifying the amount of copper on each electrode surface . the extent of corrosion for any given test solution was estimated by the height of the first oxidation peak ( cu → cu + ). a schematic of this embodiment is shown as fig1 . another embodiment of the present invention is related to fluorometric assessment of corrosion products , including fluorometric assessment of corrosion products of aa2024 - t3 for high throughput screening of corrosion inhibitors aa2024 - t3 consists of approximately 93 % al . al is the primary constituent involved in dissolution of the alloy in corrosive solutions . the corroded aluminum typically takes the form of aluminum oxide or aluminum hydroxide . while some of the corrosion products adhere to the surface of the alloy , the rest dissolve in the surrounding solution . detection of the amount of aluminum in solution may be carried out through the use of a fluorescent dye sensitive to the presence of aluminum . lumogallion is one such dye that is sensitive to aluminum ions and has a limited number of interferences from other ions . lumogallion has been shown to be sensitive to aluminum in solution resulting from the corrosion of aa2024 - t3 . see sibi , m . p ., zong , z ., “ determination of corrosion of aluminum alloy under protective coatings using fluorescent probes ,” progress in organic coatings 47 , 8 - 15 ( 2003 ). estimation of the extent of aluminum dissolution of an aluminum alloy in the presence of aggressive ions and corrosion inhibitor species is another high throughput screening method for determining the efficacy of inhibitor species . related to this embodiment , a spectramax m2 plate reader was used to carry out fluorescence detection of lumogallion solutions . all fluorescence detection of solutions was carried out using a 96 well , costar black clear bottom plate for optical assay . optimization of the excitation and emission was performed and the optimum values were determined to be 491 nm excitation wavelength and 610 nm emission wavelength . a 590 nm wavelength cutoff filter was employed by the instrument to reduce signal from the excitation source in the emission measurement . solutions containing different concentrations of aluminum up to 39 . 2 μm aluminum chloride , 51 . 1 μm lumogallion , and 0 . 2 m sodium acetate buffer ( ph 5 . 2 ) were tested to verify the sensitivity of lumogallion fluorescence to the presence of aluminum . sensitivity of lumogallion fluorescence to other species of interest in exposure experiments on aa2024 - t3 was then carried out . the species of interest included chloride ( aggressive ion ) and possible inhibitor species : sodium metavanadate , cerium chloride , barium metaborate , yttrium chloride , sodium metatungstate , potassium phosphate , lanthanum chloride , sodium metasilicate , sodium phosphate , sodium molybdate , europium chloride , gadolinium chloride , and neodymium chloride . solutions of 0 . 03 m nacl , 51 . 1 μm lumogallion , 0 . 2 m sodium acetate buffer ( ph 5 . 2 ), and concentrations of alcl 3 varying from 0 to 32 . 66 μm were tested for fluorescence emission . solutions of single inhibitors and binary combinations of inhibitors were tested at 0 . 17 mm total inhibitor concentration according to the following combinations : component a tested at 0 . 01 mm , 0 . 035 mm , 0 . 06 mm , 0 . 085 mm , 0 . 11 mm , 0 . 135 mm , and 0 . 16 mm with balance of the 0 . 17 mm total comprised of component b . the test solution comprised of 0 . 17 mm total inhibitor , 0 . 03 m nacl , 51 . 1 μm lumogallion and 0 . 2 m sodium acetate buffer ( ph 5 . 2 ). aa2024 - t3 electrodes were exposed to inhibitor solution ( 3 . 4 mm total inhibitor concentration , 0 . 6 m nacl ) by immersing 1 . 2 cm of the electrode in the solution . cells of the reaction frame were filled with 1 . 8 ml of 3 . 4 mm total inhibitor in 0 . 6 m nacl solution . desired ph of the solutions was obtained by addition of hcl or naoh prior to exposure . screening was performed on solutions containing 0 . 2 mm ( 5 . 9 %), 0 . 7 mm ( 20 . 6 %), 1 . 2 mm ( 35 . 3 %), 1 . 7 mm ( 50 %), 2 . 2 mm ( 64 . 7 %), 2 . 7 mm ( 79 . 4 %), and 3 . 2 mm ( 94 . 1 %) of inhibitor a with the balance of the 3 . 4 mm total inhibitor comprised of inhibitor b . the combinations of inhibitors were comprised of the following inhibitors : sodium metavanadate , cerium chloride , barium metaborate , yttrium chloride , sodium metatungstate , potassium phosphate , lanthanum chloride , sodium metasilicate , sodium phosphate , sodium molybdate , europium chloride , gadolinium chloride , and neodymium chloride . 96 electrodes , connected to a reaction frame lid , were immersed in 96 independent cells containing solution of a standard 8 × 12 reaction frame . the electrodes were exposed to the inhibitor solution , which was open to air , for 24 hours . after the 24 hour exposure , the reaction frame lid housing the electrodes was disconnected from the reaction frame and the remaining solution was acidified to ensure dissolution of any aluminum containing deposits that had precipitated from solution during the exposure period . the resulting test solution was then mixed with acetate buffer and lumogallion to obtain the desired fluorometric assay solution . 0 . 1 ml of the test solution was added to 1 . 8 ml 0 . 2 m sodium acetate buffer ( ph 5 . 2 ) and 0 . 1 ml 1 . 02 mm lumogallion . the resulting solution was 0 . 17 mm total inhibitor , 0 . 03 m nacl , 0 . 19 m sodium acetate buffer , 51 . 1 μm lumogallion and an unknown concentration of aluminum that was 5 % of that resulting from the previous exposure . 200 μl of this fluorometric solution was then transferred into our fluorometric assay plate for quantification of emission from the solution . as an example of the determination of aluminum concentration for estimating corrosion damage in aa2024 - t3 samples tested in parallel , 1 . 8 ml of test solution was transferred or mixed in each cell ( 96 cells ) of a conventional 2 ml 8 × 12 reaction frame . each cell may contain an independent test solution . one aa2024 - t3 wire electrode was plugged into an electrical contact contained in the fabricated top for each cell , totaling 96 wire electrodes connected to the multichannel microelectrode analyzer ( mma ). the fabricated top was then placed on the reaction frame containing the chemistries of interest and the system was left open to air . after an exposure time ( e . g ., 24 hours ), the reaction frame lid holding the electrodes was removed from the reaction frame , and the test solutions contained in the reaction frame were each dosed with hcl drop wise . the resulting test solution was mixed with acetate buffer and fluorescent dye ( lumogallion or morin ) to obtain the desired fluorometric assay solution . typical test solutions were diluted by taking 100 μl test solution and adding to it 100 μl 1 . 02 mm lumogallion or 200 μl 510 μm morin and the balance 0 . 2 m sodium acetate buffer to reach 2 ml of total solution . the resulting solution was 0 . 17 mm total inhibitor , 0 . 03 m nacl , 0 . 19 m sodium acetate buffer , 51 μm lumogallion or morin and an unknown concentration of aluminum that was 5 % of that resulting from the previous exposure . further dilutions included 5 μl , 25 μl , and 50 μl test solution with the remainder of the 100 μl added in 0 . 6 m nacl to maintain a consistent [ cl − ] of 0 . 03 m in the fluorescence assay . 200 μl of this fluorometric solution was then transferred into a fluorometric assay plate for quantification of emission from the solution . the emission of lumogallion fluorometric solutions was determined using a 491 nm excitation wavelength , a 590 nm cutoff filter , recording at a 610 nm emission wavelength . the emission of morin fluorometric solutions was determined using a 418 nm excitation wavelength , a 495 nm cutoff filter , recording at a 517 nm emission wavelength . aluminum concentration was determined by calculation from the emission and the calibration curves for each fluorescent dye . standard deviations in the aluminum concentrations were estimated by taking the positive standard deviation in the emission value and determining the aluminum concentration at that value . another embodiment of the present invention is methods of coating a substrate with the materials described herein in sequential order . examples of this embodiment are shown in fig1 - 24 . the sequenced exposure of a metal to the relevant chemical species can provide even greater benefit and even more unexpected results that their simultaneous combination . that is , if compound a is placed in one container and compound b ( and c , etc . ) is placed in another container , and then the metal is exposed to compound a and then b , or b and then a , or exposed multiple times , a very beneficial results can be obtained . in fig1 , 21 , and 23 , aa2024 - t3 samples were exposed to cerium ions and metavanadte ions in either a simultaneous fashion where the ions existed together in the same bath , or sequentially where cerium ions were in one bath and metavanadate ions were in another . in the simultaneous experiments , the total molar concentration was always maintained to 3 . 4 mm . in the sequenced exposure , again , the molar concentration always totaled 3 . 4 mm . if the cerium content was 1 . 7 mm , then the metavanadate concentration was 1 . 7 mm . the horizontal axis of the figures is the mole percent of cerium in the mixture . the vertical axis is the measured quantity to determine the extent of corrosion . fig1 shows the result for aluminum ions released . fig3 shows the amount of surface copper . fig2 shows the dc current passed upon 100 mv polarization . in each case , larger values indicate more corrosion . as can be seen in fig1 , 21 , and 27 , the sequenced exposure of aa2024 - t3 to cerium and metavanadate shows dramatic improvement in the corrosion protection provided by these materials . the sequenced exposure is synergistic at all conditions . more importantly , this result is unpredictable , since the simultaneous combination of these compounds results in an antagonistic interaction , just the opposite of what is observed by the sequenced exposure . in fig2 , 22 , and 24 , aa2024 - t3 samples were exposed to lanthanum ions and molybdate ions in either a simultaneous fashion where the ions existed together in the same bath , or sequentially where lanthanum ions were in one bath and molybdate ions were in another . in the simultaneous experiments , the total molar concentration was always maintained to 3 . 4 mm . in the sequenced exposure , again , the molar concentration always totaled 3 . 4 mm . if the lanthanum content was 1 . 7 mm , then the molybdate concentration was 1 . 7 mm . the horizontal axis of the figures is the mole percent of lanthanum in the mixture . the vertical axis is the measured quantity to determine the extent of corrosion . fig2 shows the result for aluminum ions released . fig4 shows the amount of surface copper . fig2 shows the dc current passed upon 100 mv polarization . in each case , larger values indicate more corrosion . as can be seen in fig2 , 22 , and 24 , the sequenced exposure of aa2024 - 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( 2004 ) d . a . little and j . r . scully , “ the effect of alloy composition and pretreatment on the under - paint corrosion of copper bearing aluminum alloys ,” in proceedings of the 2003 tri - service corrosion conference , organized by afosr / afrl ( tri - services committee on corrosion , u . s . department of defense ), las vegas , nev ., nov . 17 - 21 , 2003 . d . a . little , m . a . jakab , and j . r . scully , “ the effect of pretreatment on the under - paint corrosion of aa2024 - t3 at various temperatures ,” corrosion , ( submitted ). m . a . jakab , f . presuel - moreno , and j . r . scully , “ critical concentrations associated with cobalt , cerium , and molybdenum inhibition of aa2024 - t3 : delivery from al — co — ce (— mo ) alloys ,” corrosion ( in press ). the invention thus being described , it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention . all such modifications and variations are included in the scope of this invention . as one specific example , aluminum alloy 2024 is discussed for exemplary purposes only , and should not be construed as being limiting of the present invention . unless otherwise indicated , all numbers expressing quantities of ingredients , properties such as reaction conditions , and so forth used in the specification and claims are to be understood as being modified in all instances by the term “ about .” accordingly , unless indicated to the contrary , the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be determined by the present invention . notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations , the numerical values set forth in the experimental or example sections are reported as precisely as possible . any numerical value , however , inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements .