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Title:
WATER DISPERSIBLE CORROSION INHIBITOR
Document Type and Number:
WIPO Patent Application WO/2002/052066
Kind Code:
A2
Abstract:
An environmentally benign and water dispersible corrosion inhibitor is disclosed. The corrosion inhibitor comprises a combination obtained by combining at least one of water dispersible polymers, water soluble silicates, water, additives, among other components.

Inventors:
TAYLOR DONALD W
SCRIVENS TODD W
Application Number:
PCT/US2001/046634
Publication Date:
July 04, 2002
Filing Date:
November 08, 2001
Export Citation:
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Assignee:
DENOVUS LLC (US)
International Classes:
C08L31/04; C08L29/04; C09D5/00; C09D129/04; C09D131/04; C23F11/00; C23F11/173; C23F11/18; C08L83/02; C08L83/04; (IPC1-7): C23F11/00
Domestic Patent References:
WO1996012770A11996-05-02
Foreign References:
US3717599A1973-02-20
US5974779A1999-11-02
Other References:
DATABASE WPI Section Ch, Week 198041 Derwent Publications Ltd., London, GB; Class A82, AN 1980-72231C XP002203569 & JP 55 110169 A (NIPPON KOKAN KK), 25 August 1980 (1980-08-25)
PATENT ABSTRACTS OF JAPAN vol. 004, no. 034 (C-003), 22 March 1980 (1980-03-22) & JP 55 008406 A (MATSUOKA HIDEO), 22 January 1980 (1980-01-22)
Attorney, Agent or Firm:
Boyer, Michael K. (MO, US)
Download PDF:
Claims:
THE FOLLOWING IS CLAIM
1. ED : 1) A composition comprising a combination comprising at least one water dispersible polymer selected from the group consisting of vinyl acetate, vinyl acetate copolymers, vinyl acetate emulsion, polyvinyl acetate and polyvinyl alcohol, water and at least one additive.
2. A composition comprising a combination comprising polyvinyl alcohol, at least one silicon containing foam suppressant, water, and sodium chloride.
3. The composition of Claim 1 wherein the water comprises naturally occurring salt containing water.
4. The composition of Claim 2 wherein the water comprises naturally occurring salt containing water.
5. The composition of Claim 1 further comprising at least one water soluble silicate.
6. The composition of Claim 2 further comprising at least one water soluble silicate.
7. The composition of Claim 1 wherein said composition has a basic pH.
8. The composition of Claim 2 wherein said composition has a basic pH.
9. The composition of Claim 1 wherein said water dispersible polymer comprises at least one of vinyl acetate and copolymers thereof.
10. The composition of Claim 1 wherein said water dispersible polymer comprises at least one vinyl acetate emulsion.
Description:
WATER DISPERSIBLE CORROSION INHIBITOR The subject matter disclosed and claimed herein claims benefit of prior filed U. S. Patent Application Serial No. 60/246, 886, filed on November 08,2001; the disclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION The field of the invention relates to corrosion inhibitors for reducing the corrosion rate of metallic surfaces.

BACKGROUND OF THE INVENTION It is well know in this art to apply one or more inhibitors upon a metallic surface to reduce the corrosion rate. Conventional corrosion inhibitors typically contain components that are environmentally desirable. Such components are partiuarally undesirable when employed in applications wherein the components may be released upon water or other environmentally sensitive areas.

SUMMARY OF THE INVENTION The instant invention solves problems associated with conventional methods by providing an environmentally benign and water dispersible corrosion inhibitor. The inventive corrosion inhibitor comprises a combination obtained by combining at least one of water dispersible polymers, water soluble silicates, water, additives, among other components. The inventive composition is typically employed in applications were relatively short term (depending upon the application) corrosion inhibition is desired. The inventive composition and process can also be employed for increasing the effective life of metallic surfaces previously treated to impart relatively long term corrosion protection, e. g., painted metallic surfaces.

DETAILED DESCRIPTION The instant invention relates to compositions, and method for applying the composition to reduce dusting and/or corrosion of a metallic surface. The metallic surface can comprise an anchor chain such as that used on commercial and military boats and ships. The chain can

comprise detachable links such as those described in U. S. Patent No. 5,974,779, issued Nov. 02, 1999 in the named of Orscheln et al. ; hereby incorporated by reference.

While the inventive composition can comprise a wide range of components, normally the composition is substantially free of toxic components and those leaving a film or sheen upon water.

By"substantially free"it is meant that the composition comprises less than about 10 wt. % and normally about 0 wt. % of such components.

The inventive method can be employed to apply the inventive composition (s) in order to: 1) Use silicates and salt water for corrosion inhibition of metal on ocean vessels or platforms, 2) Use polyvinyl alcohol or silicate blends for corrosion control, 3) Use polyvinyl alcohol as a rust binder for anchor chain or other metal structure, 4) Use silicates as rust binder for anchor chain or other metal structures, 5) Use silicate solutions as deck or platform wash using salt water diluent, among other applications wherein it is desirable to inhibit corrosion.

In one aspect of the invention, the inventive composition comprises at least one of polyvinyl alcohol, ethylene vinyl acetate (and copolymers) thereof, among other water soluble or dispersible and non-toxic polymeric compounds, and water. Normally, the polymeric compound comprises, polyvinyl alcohol. The amount of water in the inventive composition normally ranges from about 70 to at least 90 wt. %. If desired, the water can comprise salt water including naturally occurring brackish and ocean/sea water (e. g., water comprising about 5 to at least 7 wt. % sodium chloride).

The composition of this aspect of the invention is particularly effective at controlling release of dust and debris from a corroded or rusted surface. If desired, the inventive composition can further comprise at least one de-foaming compound, e. g., a silicon modified dispersion of olefinic solids.

The inventive composition can be applied upon an anchor chain (e. g., as the chain is being hoisted and placed into a storage locker upon a boat or ship), in order to reduce, if not eliminate, rust and debris from being released into the air when the anchor is redeployed from the storage locker.

In a second aspect of the invention, the inventive composition comprises at least one water soluble silicate, e. g., sodium silicate, potassium silicate, among other water dispersible silicates, and water. Normally, the water soluble silicate comprises sodium silicate (e. g., density ratio 3: 22).

The amount of water in the inventive composition normally ranges from about 70 to at least 90 wt. %. If desired, the water can comprise salt water including naturally occurring brackish and salt water (e. g., water comprising about 5 to at least 7 wt. % sodium chloride). The composition has a relatively high pH that ranges from about 8 to about 12, e. g., normally about 11. In general, the higher the pH the greater the effectiveness of the composition at reducing corrosion. If desired at least one pH modifying compound can be added to the composition, e. g., sodium hydroxide. The

composition of this aspect of the invention is particuarally effective at controlling release of dust and debris from a corroded or rusted surface as well as reducing the rate of continued corrosion.

The inventive composition can be applied upon an anchor chain (e. g., as the chain is being hoisted and placed in a storage locker), in order to reduce corrosion during storage and reduce, if not eliminate, rust and debris from being released into the air when the anchor is redeloyed from the storage locker.

The inventive composition can further comprise at least one additive such as defoaming agents, anti-microbial, surfactants, anti-freeze, dyes, thickeners, among other components.

Examples of a suitable anti-freeze materials are proplyene glycol, methanol, among others. Using environment friendly materials is desirable for applications wherein the composition directly contacts water. An example of suitable defoaming agent comprise silicone based agents.

The inventive composition can be prepared by combining the components by using any suitable method. Examples of suitable methods comprise hand mixing, agitation, spray mix heads, among other methods known in the art. The combination rate can be enhanced by heating, e. g., 180 F for a period of about 30 minutes. In some cases, the composition forms an emulsion.

The inventive composition can be applied upon a desired surface by using any suitable method. Examples of suitable methods comprise dipping, immersing, spraying, wiping, among other delivery methods known in this art. In some cases, it is desirable to prepare a concentrate or an intermediate comprising all components of the inventive composition except water (e. g., salt water). The intermediate is then combined with a readily available source of water (e. g., ocean water in the case of a marine vessel or structure), and applied upon the desired surface. If desired, the intermediate comprises all of the components wherein only a portion of the water (e. g., tap or potable water) is present and remainder of the water (e. g., salt water) is added in situ prior to usage.

While the above description has emphasized using the inventive composition on marine applications, the compositions can be employed on piers (e. g., as a wash and protectant for concrete), pipe flanges and joints before or after welding, as water blast additive for pipe or flange cleaning and repair, temporary coatings during shipment of metallic articles and intermediates (e. g., coil steel, rod used for making wire rope and strand, among others), anchor chain lockers, wash for off-shore structures (e. g., oil rigs), among other applications.

EXAMPLES

The following Examples are provided to illustrate certain aspects of the instant invention and shall not limit the scope of any claims appended hereto. The following Table lists the components that were used to prepare the aspects of the inventive composition test below.

Trade Name Chemical Composition Supplier PQ GRADE G Sodium silicate solid PQ Corporation PQ GRADE N Sodium silicate liquid PQ Corporation AIRFLEX 500BP Vinyl acetate emulsion Air Products AIRVOL 203S Polyvinyl alcohol Air Products VINAC RP 710 Polyvinyl acetate Air Products DAPRO U-99 Anionic/non surfactant blend Elementis DAPRO DF 3163 Modified polyol foam suppressor Elements DAPRO DF 1161 Silicon modified olefinic solids Elements dispersion foam suppressor FORMULATION 1 MATERIAL AMOUNT AIRVOL 203S101.5g H20TAP 405cc Preparation: MIXED ON HOTPLATE STIRRER @ 185°F FOR 30 MINUTES FORMULATION 2 MATERIAL AMOUNT PQ GRADE G 10g H20 TAP 390cc Preparation: MIXED ON HOTPLATE STIRRER @ 190°F FOR 30 MINUTES FORMULATION 3 MATERIAL AMOUNT AIRVOL 203S 150g H20 TAP 350cc Preparation: MIXED ON HOTPLATE STIRRER @ 190°F FOR 30 MINUTES FORMULATION 4 MATERIALAMOUNT PQ GRADE G 20g H20 TAP 400cc MIXING : MIXED ON HOTPLATE STIRRER @ 208°F FOR 30 MINUTES The following Table describes the Testing Parameters for the Formulations DESCRIPTION : Anchor chain coating for marine applications with the primary purpose of

eliminating/reducing the iron oxide dust generated when anchor is dropped PARAMETERS : 1. Spray applied during conventional anchor wash down procedures that are employed when anchor is hoisted 2. Non-flammable.

3. Water based to allow coating to be incorporated into the current wash down equipment.

4. Can not leave oily film or sheen on water as the coating will likely go overboard during anchor wash down.

5. Can not leave long duration foam on water.

6. After coating dries, it must dissolve in salt water to prevent coating build up which could lead to flakes or debris floating on water when anchor is deployed or debris clogging chain locker drains.

7. No environmental hazards or impact.

8. Coating concentrate must be able to be diluted to working solution strength using sea water as this is what the Navy uses for wash down.

9. Coating can be applied using commercially available equipment.

TESTING PARAMETER DESCRIPTIONS 1. FOAMING : This was a visual observation of foaming characteristics when spray applying the coating/protectant.

2. DISSOLUTION TEST: Formula being tested was applied to a bare steel panel and dried. Pigments and tension modifiers can be added to allow for a uniform coating (bare steel having a different surface tension than corroded steel) and to give a visual indication if coating dissolves. Coated panel was partially immersed in a 5% salt water solution. After 2 hours, coating was checked to see if it is or has dissolved. The water was also checked for film, flakes or oily sheen on the surface.

3. RUB TEST: 10 light double rubs with a white paper towel on a dry anchor chain link. The amount of rust on paper towel is rated from 0 to 5.0 = no rust evident. 5 = rust on paper towel same as amount of rust rubbed off uncoated anchor chain (control).

4. SALT FOG: Bare clean chain was coated, allowed to dry and placed into salt fog chamber. The type of chain, coating method, and time in chamber will be noted. Results were compared against uncoated chain of same type (control). Rating is from 1 to 5.1 = more corrosion than control, 2 = slightly more, 3 = same as control, 4 = slightly less, 5 = less than control 5. HUMIDITY: Bare clean chain was coated, allowed to dry and placed in a 100F oven onto a perforated plastic shelf that is directly above a pan of water. Results were compared against uncoated chain of same type (control). Rating is from 1 to 5.1 = more corrosion than control, 2 = slightly more, 3 = same as control, 4 = slightly less, 5 = less than control FORMULATION EVALUATION TABLE A <, Trial Nlmber 001 002 003 004 COMPONENTS ,. aoi o02 08 004 PQ GRADE G 15 AIRFLEX 500 BP 50 AIRVOL 203S 15 VINAC RP710 15 Ha0 DISTILLED 100 Hz0 TAP 50 100 100 HOT 5% SALT WATER TESTS TESTS DlSSoLuTION TEST i I DISSOLVED, NO FLAKES, FILM OR OILY SHEEN ON WATER FOAMING FOAMS ON SPRAYING RUST RUB OFF MIXING STIRRED BY HAND STIRRED BY HAND MIXED ON STIRRED BY HAND HOTPLATEJSTIRRER. HEAT SETTING = 2. 5 SPEED=6 FOR 30 MINUTES APPLICATION-P COAT, HANGER CHAIN DIP COAT, HANGER CHAIN DUSTTEST-COATING APPLIED USING GARDEN SPRAYER SET TO , aOZ/GALLON DISSOLUTION-FOAM BRUSH, STEEL PANEL FORMULATION EVALUATION TABLE B :: OFL : ON, /\""% rM '" um erz ria AIRFLEX 500 BP 0. 3 AIRVOL 203S A! RFLEX 500 BP03 VINAC RP710 Formulation 1 20 2 80 Formulation 2 1 20 Formulation 3 100 DAPRO U-99 0 07 DAPRO DF 3163. 25 0. 07 1 0. 5 H20DISTILLED H20 TAP 10 5%SALT WATER : TESTS" DISSOLUTION TEST NO DISSOLUTION FOAMING FOAMS BUT DISSIPATES QUICKLY RUST RUB OFF BETTER THAN CONTROL BUT POOR-SAME AS CONTROL NOT RATED BUT NOT RATED MIXI MIXED BY HAND ALL INGREDEINTS ADDED TO MIXED BY HAND MIXED BY HAND TEST TUBE AND SHAKEN 8Y RAND . :' : ApPjr'&TtfM GARDENSPRAYERSETAT FOAMBRUSH. BARESTEEL GARDEN SPRAYER SET AT SARDEN SPRAYER SET AT ""', i''; :': d ; : s :',,. (, ; : 80Z/GALLON. eOZtGALLON. SALTWATER 80ZtGALLON. SALTWATER SOAKED RUSTED ANCHOR SOAKED RUSTED ANCHOR 1 CHAIN. COATED WHILE STILL CHAIN. COATED WHILE WET STILLWET NO SUBSTRATE COATED, MIXTURE IS STABLE. THIS BETTER THAN CONTROL ON RELATIVELY HIGH !;.:;,, ) Vp; j,; a.. FOAM! NGOBSERVAT) ONONLY WASTOTESTTHESTABtDTY RUBTESTBUTNOTASGOOD FOAMINGSOOBP ION ONLYPVASSOLUT THE S ABILITY RUS NGST00UT000T ALONE. AND IF IT ALSO AFFECTED THE WHEN BODI-0005 ONLY WAS COATING SOLUBILITY APPLIED THE SAME METHOD AS ABOVE WAS USED FORMULATION EVALUATION TABLE C 14 u'T MPONENL PVA (PolyVinyl Alcohol) PVA RATIO STUDY PVA RATIO STUDY RATIO STUDY PQ GRADE G AIRFLEX 500 BP AIRVOL 203S 100 VINACRP710 Formulation 1 NEAT 10 10 Formulation 2 Formulation 3 DAPROU-99 DAPRO DF 3163 DAPRO DF 1161 2 H20DISTILLED H20 TAP 300 10 20 5% SALT WATER TESTS RUST RUB OFF MODERATE, BETTER THAN 008 RATING=0 RATING=0 RATING=1 BUT NOT AS GOOD AS USING BOOt-0005IN A 80Z/GALLON RATO. NOT RATED. RATIO, NOT RATED. MIXING MIXED ON HOTPLATE STIRRER NO MIX, APPLIED NEAT MIXED BY HAND MIXED BY HAND aD190°F FOR 30 MIN. . APPLICATION DILUTED WITH WATER TO GIVE FOAM BRUSH APPLIED TO A FOAM BRUSH APPLIED TO A FOAM BRUSH APPLIED TO A A 9g PVA PER GALLON DRY RUSTED ANCHOR CHAIN DRY RUSTED ANCHOR CHAIN DRY RUSTED ANCHOR DILUTED 009 WAS PLACED LINK. DRIED USING HEAT GUN LINK. DRIED USING HEAT CHAIN LINK. DRIED USING INTO A GRACO SPRAY GUN GUN HEAT GUN AND SPRAYED ONTO A W ET ANCHOR CHAIN THAT HAD BEEN IMMERSED IN A 3% SALT WATER SOLUTION SOLUTION HAS THE SAME STUDY TO DETERMINE THE STUDY TO DETERMINE THE STUDY TO DETERMINE THE COMMENTS RATIO THAT WAS ATTEMPTED AMOUNT OF PVA NEEDED TO AMOUNT OF PVA NEEDED TO AMOUNT OD PVA NEEDED WITH 008 IN THE 80ZIGALLON PRODUCE AN ACCEPTABLE PRODUCE AN ACCEPTABLE TO PRODUCE AN SPRAYER.. COATING. B001-0005 NEAT COATING. lOg OF B001-0005 ACCEPTABLE COATING.. EQUATES TO 2g PVA J 8cc Hz0 DILUTED W ITH l0cc OF HZO t Og OF B001-D005 DILUTED EQUATES TO 2g OF PVA TO WITH 20cc OF H20 EQUATES l8cc H20 TO 2 OF PVA TO 28cc H20 FORMULATION EVALUATION TABLE D ; OR fSS. a. - PVA RATIO STUDY 010 Oil 012 PQ GRADE G AIRFLEX 500 BP AIRVOL 203S 40 40, 40 VINACRu710 Formulation 1 10 Formulation2 Formulation 3 Formulation 4 300 DAPROU-99 DAPRODF 3163 DAPRO DF 1161 H20 DISTILLED H20TAP 52 300 300 5% SALT WATER TSTu. i s g : i, ;, RUST RUB OFF RATING = t RATING = t RATING = 1 SALT FOG16HOURS. RATtNG-3 SALT FOG 16 HOURS, RATING = S MIXED BY HAND MIXED ON HOTPLATE STIRRER MIXED ON HOTPLATE MIXED ON HOTPLATE MIXIN -' !""'"'A. Dtai'tr'TtfM''"*'.'"SSRnmppnE" ? " *R ! ! ? 7* ! FnTSn"" T ! rn7E ? ? ppT ! nG*' 5T*"" MIN DRY RUSTED ANCHOR CHAIN APPLIED USING A PRESSURE A PRESSURE SPRAYER TO A :', i S DRY RUSTED ANCHOR CHAIN APPLIED USING A PRESSURE A PRESSURE SPRAYER TO A LINK. DRIED USING HEAT GUN SPRAYER TO A WETRUSTED WETRUSTED ANCHOR ANCHOR CHAIN LINK THAT CHAIN LINK THAT HAD BEEN E ; : HAD BEEN IMMERSED IN A 3% IMMERSED IN A 3% SALT SALT WATER SOLUTION. WATER SOLUTION. CHAIN CHAIN WAS ALLOWED TO AIR WAS ALLOWED TO AIR DRY. DRY. SALT FOG-DILUTED AND DIP APPLIED TO BARE CLEAN HANGER CHAIN AND ALLOWED TO DRY THEN PLACED INTO SALT FOG ALONG WITH AND UNCOATED HANGER CHAIN CO M M ENTS ß STUDY TO DETERMINE THE DILUTED W ITH 900ce H20 DILOTED W ITH 900cc OF 5% AMOUNT OF PVA NEEDED TO EQUATES TO 1 g OF PVA TO SALT WATER. THIS IS THE PFtODUCE AN ACCEPTABLE 30cc N20. THE RUB TEST) S SAME BATCH AS 010 BUT COATING.. 10g OF B001-OO05 ACCEPTABLE.. SALT WATER IS USED AS THE DILUTED WITH 52cc OF H2O DILUENT TO CHECK IT EQUATES TO 1 g OF PVA TO EFFECT ON SOLUTION 30cc H20 STABILITY AND COATING PERFORMANCE. SOLUTION IS STABLE AND PERFORMANCE IS SAME AS 010.

FORMULATION EVALUATION TABLE E FORMULATION Trial Number COMPONENT 013 014 PQ GRADE G PQ GRADE N (liquid) 100 300 AI RVOL 203S VINAC RP710 Formulation1 Formulation 2 Formulation 3 Formulation 4 DAPRO U-99 DAPRO DF 3163 DAPRO DF 1161 H20DISTILLED H20 TAP 5% SALT WATER 300 1BJ'\\S- ? &F K'-'""--M RUST RUB OFF RATING = 0 RATING =1 SALT FOG RATING =1 MIXING NONE, USED NEAT MIXED BY HAND A, LICATION RUSTED ANCHOR CHAIN, PRESSURE SPRAYER TO A DRIED WITH HEAT GUN WET RUSTED ANCHOR CHAIN LINK THAT HAD BEEN IMMERSED IN A 3% SALT WATER SOLUTION. CHAIN WAS ALLOWED TO AIR DRY. SALT FOG-APPLIED USING A PRESSURE SPRAYER TO CLEAN BARE HANGER CHAIN AND ALLOWED TO DRY COMMENT ANCHOR CHAIN HAS SURFACE DILUTED WITH SALT WATER ;'COb FiE>lTS ; ANCHOR CHAIN HAS SURFACE DILUTED WiTH SALT WATER <","";, > ! ;, << <""i >. ; CORROSION AND PITTING BUT LITTLE SCALE. COATINGS , SEEM TO SOAK INTO THIS TYPE OF SURFACE..