EP0173427A2 - Korrosionsverhütung - Google Patents

Korrosionsverhütung Download PDF

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Publication number
EP0173427A2
EP0173427A2 EP85304467A EP85304467A EP0173427A2 EP 0173427 A2 EP0173427 A2 EP 0173427A2 EP 85304467 A EP85304467 A EP 85304467A EP 85304467 A EP85304467 A EP 85304467A EP 0173427 A2 EP0173427 A2 EP 0173427A2
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EP
European Patent Office
Prior art keywords
corrosion
ferrous
aqueous system
formula
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP85304467A
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English (en)
French (fr)
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EP0173427A3 (de
Inventor
Orin Hollander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BetzDearborn Europe Inc
Original Assignee
Betz Europe Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Betz Europe Inc filed Critical Betz Europe Inc
Publication of EP0173427A2 publication Critical patent/EP0173427A2/de
Publication of EP0173427A3 publication Critical patent/EP0173427A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention relates to the inhibition of corrosion of metal parts in contact with an aqueous system and compositions therefor.
  • benzotriazole as corrosion or tarnish or staining inhibitors for copper and copper alloys is well known. In addition to the use of this compound for aesthetic purposes, it together with tolyltriazole have found widespread use in the water treatment industry and in particular in the cooling water industry.
  • the present invention provides a method of inhibiting the corrosion of non-ferrous metals in contact with an aqueous system, which comprises adding to the aqueous system a sufficient amount for the purpose of a water soluble compound having the formula: wherein R is a hydrocarbon group containing from 3 to about 8 carbon atoms.
  • the present invention further provides a method of inhibiting the corrosion of metal parts in contact with an aqueous system, the metal parts being composed of both ferrous and non-ferrous metals, which comprises adding to the aqueous system a sufficient amount for the purpose of a corrosion inhibitor composition for the ferrous metal, and also adding to the aqueous system an effective amount for the purpose of a corrosion inhibitor for the non-ferrous metal, the corrosion inhibitor for the non-ferrous metal comprising a compound represented by the formula: wherein R is a hydrocarbon group containing from 3 to about 8 carbon atoms.
  • the present invention still further provides a composition effective for inhibiting the corrosion of metallic parts or systems composed of both ferrous and non-ferrous metals in contact with water, which composition comprises a corrosion inhibiting composition for the ferrous metals, and a corrosion inhibitor for the non-ferrous metals, comprising a compound of the formula: wherein R is a hydrocarbon group containing about 3 to about 8 carbon atoms.
  • the compounds used in the present invention may be added to the system or applied to the copper surfaces either alone or in conjunction with other treatment agents.
  • benzotriazole compounds are used for the treatment of cooling water systems, they may be added individually as an aqueous solution, or may be combined with the well known corrosion inhibiting compositions designed to protect the ferrous structures of the cooling water system.
  • these compounds may be formulated in the proper amount (sufficient that when the total product is added to the cooling water, there is a sufficient amount of the present compound(s) to perform the function and provide the protection) with such well known treatments.
  • Such treatments include: the Dianodic II treatments which are directed to the use of an acrylic acid hydroxyalkylacrylate/orthophosphate to provide corrosion protection.
  • the compounds used in the present invention would appear to be utilizable with any ferrous metal protective system whether it be by the passivation technique or the barrier protection technique.
  • the compounds have the formula
  • the atoms comprising the structure are numbered in order to lend greater specificity to the particular compounds which have been found to be unexpectedly superior, i.e., the 4 or 5 butyl- benzotriazoles.
  • R group has earlier been described as having C 3 to C 8 groups, the compounds are more specifically represented as follows: and the like, where the 4 or 5 position is preferred. It is also possible to substitute additional function groups both on the hydrocarbon group and in the ring at the 6 and/or 7 positions. Such groups as alkyl, haloalkyl, halo, amino, alkoxyl, and carboxamido groups might be useful.
  • the compounds used in the present invention should be used, obviously, in an amount sufficient for the purpose, but more specifically can be added to the aqueous system in an amount of from about 0.1 to 200 .(preferably 0.1 to 100) parts per million of water in the aqueous system.
  • the experiments are performed by placing an electrode (the working electrode) of the metal alloy of interest in a suitable medium (a conductive liquid) along with a suitable reference electrode (results reported herein are referenced to the Saturated Calomel Electrode [SCE]), and by means of various types of electronic devices (generally referred to as potentiostats) controlling either the electrostatic potential (voltage) or current, and -simultaneously measuring the resultant current or potential.
  • SCE Saturated Calomel Electrode
  • the rate of corrosion expressed as an average penetration rate, is given by:
  • the polarization technique involves perturbing the system electrically well away from the corrosion potential so as to effectively suppress one of the current components, thereby allowing a determination of the other component.
  • a positive potential the cathodic reaction is suppressed, allowing measurement of anodic currents.
  • Applying negative potentials accomplishes the opposite process.
  • suitable mathematical treatment of the data the corrosion , current can be determined.
  • detailed analysis of the current-potential relationships reveals mechanistic details. For example, comparison of the shapes of the anodic and cathodic curves with and without inhibitors can reveal the principal mode of inhibition. In the attached data, showing such tests, it can be seen that the cathodic reduction of oxygen is most significantly affected by the inhibitor molecules, and that butylbenzotriazole exhibits the greatest degree of cathodic reaction retardation.
  • Tafel Polarization One drawback of Tafel Polarization is that the passage of significant currents through the sample and solution causes permanent changes in the system. Repeated measurements are precluded as the results cannot be related to a known state of the system. Typical changes are solution pH, .lution composition, and surface structure of the test specimen. Linear polarization solves this problem by using very small perturbation currents so that any changes in the state of the system remain negligible. The non-linearity of system response, however, creates complications with respect to the treatment of the data. Various algorithms are available for such treatment and are employed in computer programs used for this purpose.
  • a measurement of the instantaneous slope of the current-potential curve at the corrosion potential has units of ohms, or electrical resistance bnits.
  • this polarization resistance value is inversely proportional to the corrosion rate. Thus, the greater the resistance the lower the corrosion rate.
  • This technique has the advantage of allowing repeated measurements on the same system, but sacrifices the mechanistic details obtainable by Tafel polarization.
  • the attached linear polarization data shows a significant and completely unexpected improvement for butylbenzotriazole over tolyltriazole and benzotriazole.
  • test equipment is designed to simulate a wide range of potential operating conditions, and additionally, provision is made for the insertion of test specimens. These specimens may then be studied visually, electrochemically or gravimetrically as is desired.
  • the two principal tests employed for the current studies are spinners and recirculators (RTU's).
  • a 17 liter tank is provided in which the test water is placed. Provision is made for maintaining constant temperature in the range of room temperature to 100° C (212° F ); additionally, air saturation of the test solution is maintained. Cleaned, weighed metal samples in the form of coupons (metal strips of varying dimension based on the alloy) are affixed to the periphery of a mandrel. The coupons are then immersed in the test solution and rotated around a vertical axis at constant speed. The rim velocity is maintained at 48.77cm/sec. (1.6 feet/second).
  • test coupons Following exposure for a predetermined period (typically 3-7 days) the test coupons are removed and inspected, cleaned, dried and weighed. From these data corrosion rates are calculated.
  • test procedure is conceptually similar to the spinner test, but rather than rotate the test specimens in a stationary liquid the test specimens are stationary and the liquid is circulated at a fixed but adjustable velocity. Additionally, means are provided to replenish the test solution at a fixed, adjustable rate and to regulate pH to within ⁇ 0.2 pH units. Provision is made for conducting electrochemical corrosion measurements in the flowing stream. Furthermore, a test specimen can be inserted into the flowing stream to which a constant heat flux may be applied via an internal resistance heating device in order to regulate the surface temperature of the specimen.
  • Copper electrodes were placed in the test vessel containing 0.1N sodium sulfate adjusted to pH 7.0 and are air saturated. A control had no treatment, and subsequent tests incorporated one part-per-million (ppm) of either benzotriazole (BZT), tolyltriazole (TTA), or butylbenzotriazole (b-BZT).
  • BZT benzotriazole
  • TTA tolyltriazole
  • b-BZT butylbenzotriazole
  • Figure 2 is a cathodic-only sweep which further illustrates the increase in cathodic inhibition of b-BZT over that of TTA.
  • the decrease in cathodic current at equal potential is tenfold for b-BZT versus TTA.
  • the electrodes were placed in holders in the test rack of an RTU.
  • the data show that the new material (rightmost column) is 10 to 30 times as inhibitive as TTA or BZT. Fluctuations in the data are due to slight oscillations of the pH over time.
  • results are as follows: The results indicate an inhibitive effect for the new material on the average of five times that of TTA. Of greater significance is the failure of the TTA film after 190 hours whereas the film formed by b-BZT was still more inhibitive than the average TTA film for an additional 150 hours at least as seen in Figure 3.
  • Figure 4 is a plot of resistance vs. time. Again the results indicate a significant increase in the inhibitory power and film longevity for b-BZT.
  • the b-BZT was tested against TTA at three concentration levels.
  • the corrosion rates of Admiralty brass were as follows:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP85304467A 1984-06-26 1985-06-24 Korrosionsverhütung Withdrawn EP0173427A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62465384A 1984-06-26 1984-06-26
US624653 1984-06-26

Publications (2)

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EP0173427A2 true EP0173427A2 (de) 1986-03-05
EP0173427A3 EP0173427A3 (de) 1986-09-17

Family

ID=24502806

Family Applications (1)

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EP85304467A Withdrawn EP0173427A3 (de) 1984-06-26 1985-06-24 Korrosionsverhütung

Country Status (6)

Country Link
EP (1) EP0173427A3 (de)
JP (1) JPS6156288A (de)
KR (1) KR920002412B1 (de)
AU (1) AU582750B2 (de)
IN (1) IN164301B (de)
NZ (1) NZ212126A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258021A1 (de) * 1986-08-22 1988-03-02 Betz Europe, Inc. Verfahren zur Inhibierung der Korrosion von Kupfer in wässerigen Systemen
EP0397454A1 (de) * 1989-05-08 1990-11-14 Calgon Corporation Höhere Alkylbenzotriazole als Korrosionsinhibitoren für Kupfer und Kupferlegierungen
EP0462809A1 (de) * 1990-06-20 1991-12-27 Calgon Corporation Verfahren zur Korrosionsinhibierung von Kupfer und Kupferlegierung mit Alkylbenzotriazol enthaltenden Zusammensetzungen
US5141675A (en) * 1990-10-15 1992-08-25 Calgon Corporation Novel polyphosphate/azole compositions and the use thereof as copper and copper alloy corrosion inhibitors
US5156769A (en) * 1990-06-20 1992-10-20 Calgon Corporation Phenyl mercaptotetrazole/tolyltriazole corrosion inhibiting compositions
EP0397450B1 (de) * 1989-05-08 1993-01-07 Calgon Corporation Korrosionsinhibitoren für Kupfer und Kupferlegierungen
US5219523A (en) * 1989-05-08 1993-06-15 Calgon Corporation Copper and copper alloy corrosion inhibitors

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990010732A1 (en) * 1989-03-09 1990-09-20 Ici Australia Operations Proprietary Limited Benzotriazole based corrosion inhibiting compositions
WO2005038853A1 (ja) * 2003-10-17 2005-04-28 Kabushiki Kaisha Toshiba Ｘ線装置
US9028747B2 (en) * 2012-12-28 2015-05-12 Ecolab Usa Inc. Corrosion and fouling mitigation using non-phosphorus based additives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950676A1 (de) * 1969-10-08 1971-04-22 Bayer Ag Kavitationsinhibitoren
FR2114466A5 (de) * 1970-11-13 1972-06-30 Ciba Geigy Ag
EP0068061A1 (de) * 1981-06-25 1983-01-05 Ashland Oil, Inc. Verfahren zum Verhindern des Auslaugens von Kobalt und Nickel aus Metalloberflächen und ein in diesem Verfahren verwendetes Konzentrat

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075483A (en) * 1980-03-12 1981-11-18 Ici Ltd Corrosion inhibitors and compositions containing them
CA1159246A (en) * 1980-07-21 1983-12-27 Edwin J. Latos Corrosion inhibitors
EP0088724B1 (de) * 1982-02-26 1988-05-18 Ciba-Geigy Ag Benzotriazolgemische, Verfahren zu deren Herstellung und ihre Verwendung als Metallpassivatoren

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950676A1 (de) * 1969-10-08 1971-04-22 Bayer Ag Kavitationsinhibitoren
FR2114466A5 (de) * 1970-11-13 1972-06-30 Ciba Geigy Ag
EP0068061A1 (de) * 1981-06-25 1983-01-05 Ashland Oil, Inc. Verfahren zum Verhindern des Auslaugens von Kobalt und Nickel aus Metalloberflächen und ein in diesem Verfahren verwendetes Konzentrat

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258021A1 (de) * 1986-08-22 1988-03-02 Betz Europe, Inc. Verfahren zur Inhibierung der Korrosion von Kupfer in wässerigen Systemen
EP0397454A1 (de) * 1989-05-08 1990-11-14 Calgon Corporation Höhere Alkylbenzotriazole als Korrosionsinhibitoren für Kupfer und Kupferlegierungen
EP0397450B1 (de) * 1989-05-08 1993-01-07 Calgon Corporation Korrosionsinhibitoren für Kupfer und Kupferlegierungen
US5219523A (en) * 1989-05-08 1993-06-15 Calgon Corporation Copper and copper alloy corrosion inhibitors
EP0462809A1 (de) * 1990-06-20 1991-12-27 Calgon Corporation Verfahren zur Korrosionsinhibierung von Kupfer und Kupferlegierung mit Alkylbenzotriazol enthaltenden Zusammensetzungen
US5156769A (en) * 1990-06-20 1992-10-20 Calgon Corporation Phenyl mercaptotetrazole/tolyltriazole corrosion inhibiting compositions
US5746947A (en) * 1990-06-20 1998-05-05 Calgon Corporation Alkylbenzotriazole compositions and the use thereof as copper and copper alloy corrosion inhibitors
US5141675A (en) * 1990-10-15 1992-08-25 Calgon Corporation Novel polyphosphate/azole compositions and the use thereof as copper and copper alloy corrosion inhibitors

Also Published As

Publication number Publication date
NZ212126A (en) 1988-05-30
AU582750B2 (en) 1989-04-13
AU4319385A (en) 1986-01-02
EP0173427A3 (de) 1986-09-17
KR920002412B1 (ko) 1992-03-23
JPS6156288A (ja) 1986-03-20
IN164301B (de) 1989-02-11
KR860000416A (ko) 1986-01-28

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