WO2012100146A1 - Methods of removing rust from a ferrous metal-containing surface - Google Patents
Methods of removing rust from a ferrous metal-containing surface Download PDFInfo
- Publication number
- WO2012100146A1 WO2012100146A1 PCT/US2012/022004 US2012022004W WO2012100146A1 WO 2012100146 A1 WO2012100146 A1 WO 2012100146A1 US 2012022004 W US2012022004 W US 2012022004W WO 2012100146 A1 WO2012100146 A1 WO 2012100146A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- acid
- weight
- containing surface
- ferrous metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
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- 239000002184 metal Substances 0.000 title claims abstract description 28
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
Definitions
- the present invention relates to, among other things, methods for removing rust from a ferrous metal-containing surface.
- a metal oxide layer i.e., rust
- a ferrous metal surface a metal oxide layer
- steel such as mild steel used in the manufacture of various articles. Accordingly, it is often desirable to remove the metal oxide layer. Conventionally, this removal has been accomplished by treating the rusted metal surface with a strong acid, such as nitric, sulfuric, hydrochloric, or phosphoric acid. These highly acidic, corrosive and caustic chemicals are, however, often undesirable from an environmental and safety standpoint.
- the ferrous metal to be treated is oriented in a substantially vertical fashion such as can be the case with, for example, large structures, such as storage tanks, ships and other vehicles, and bridges, among many others.
- sprayable products are often desired for convenience and efficiency of use.
- the present invention is directed to methods for removing rust from a ferrous metal-containing surface.
- the methods comprise contacting the surface with a composition comprising: (a) a carboxylic acid; (b) a synthetic hectorite clay; and (c) water.
- the present invention also relates to, inter alia, ferrous metal-containing surfaces treated by the foregoing methods. DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
- any numerical range recited herein is intended to include all sub-ranges subsumed therein.
- a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
- the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise.
- the use of "or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
- certain embodiments of the present invention are directed to methods for removing rust from a ferrous metal-containing surface.
- rust refers to a coating or film formed on a metal by oxidation or corrosion.
- the rust that is removed in the methods of the present invention is "red rust” which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air and/or moisture, that comprises iron (II) oxide (FeO, wustite), alpha phase iron (III) oxide (a-Fe 2 0 3 , hematite), beta phase iron (III) oxide (P-Fe 2 0 3 ), gamma phase iron (III) oxide (Y-Fe 2 0 3 , maghemite), epsilon phase iron (III) oxide (s-Fe 2 0 3 ), iron (II) hydroxide (Fe(OH) 2 ), iron (III) hydroxide
- the iron oxide that is removed in the methods of the present invention is of a type that is often referred to as "mill scale" which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air, moisture, and/or heat, that comprises iron(II,III) oxide (Fe 3 0 4 , magnetite), alpha phase iron (III) oxide (a-Fe 2 0 3 , hematite), iron(II) hydroxide Fe(OH) 2 , (III) hydroxide (Fe(OH) 3 , bernalite), and/or hydrated forms and combinations of any of the foregoing.
- mill scale which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air, moisture, and/or heat, that comprises iron(II,III) oxide (Fe 3 0 4 , magnetite), alpha phase iron (III) oxide (a-Fe 2 0 3 , hemati
- Metal surfaces that may be treated in the methods of the present invention include, but are not limited to, surfaces constructed of cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvanealed steel, and steel plated with zinc alloy.
- Surfaces constructed of mild steel may be treated in the methods of the present invention. Mild steel, as used herein, refers to low carbon steel containing less than 0.25% by weight carbon.
- the metal surface is contacted with a composition comprising a carboxylic acid.
- the carboxylic acid selected for use in the compositions described herein has a water solubility of > 1 g/L at 20°C.
- Carboxylic acids suitable for use in the compositions used in the methods of the present invention include, for example, monocarboxylic acids, such as formic acid, acetic acid, propionic acid, methylacetic acid, butyric acid, ethylacetic acid, n- valeric acid, n-butanecarboxylic acid, acrylic acid, propiolic acid, methacrylic acid, palmitic acid, stearic acid, oleic acid, linolic acid, and linolenic acid; dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, lepargilic acid, sebacic acid, maleic acid, and fumaric acid; aliphatic hydroxy acids, such as glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, citramalic acid,
- the carboxylic acid is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 10 percent by weight, or, in some cases, at least 15 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the carboxylic acid is present in the composition used in the methods of the present invention in an amount of no more than 50 percent by weight, such as no more than 30 percent by weight, or, in some cases, no more than 25 percent by weight, with the weight percents being based on the total weight of the composition.
- the composition that is contacted with the ferrous metal-containing surface also comprises a synthetic hectorite clay.
- a synthetic hectorite clay in the presently described compositions produces a thickened composition with a highly shear thinning, thixotropic rheology.
- the composition is sprayable using typical spray devices (including those mentioned below) and yet, it has been discovered, remains on the ferrous metal-containing surface, even if the surface is oriented substantially vertically, for a sufficient time to effect rust removal.
- substantially vertically means substantially perpendicular (i.e., within + 20% from perpendicular) to the ground or other surface upon which the ferrous metal-containing surface is disposed.
- ambient conditions refers to 23°C and atmospheric pressure.
- Synthetic hectorite clays that are suitable for use in the compositions described herein include, for example, LAPONITE RD, LAPONITE RDS, and LAPONITE JS, including combinations thereof. As will be appreciated, each of these is a layer- structured hydrous magnesium silicate according to the chemical formula Na0 3 (Mg, Li) 3 Si 4 0io(F, OH) 2 .
- LAPONITE RD is a free flowing synthetic layered silicate having a bulk density of 1,000 kg/m 3 , a surface area (BET) of 370 m 27g, a pH of a 2% suspension in water of 9.8, wherein the composition on a dry basis by weight is 59.5% Si0 2 , 27.5% MgO, 0.8% Li 2 0, and 2.8% Na 2 0.
- LAPONITE RDS is also a free flowing a free flowing synthetic layered silicate having a bulk density of 1,000 kg/m 3 , a surface area (BET) of 330 m 2 /g, a pH of a 2% suspension in water of 9.7, wherein the composition on a dry basis by weight is 54.5% Si0 2 , 26.0% MgO, 0.8% Li 2 0, 5.6% Na 2 0, and 4.1% P 2 0 5 .
- the particle size of the synthetic hectorites, such as those described above, is typically 1 to 30 nanometers in average diameter.
- the synthetic hectorite clay is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the synthetic hectorite clay is present in the composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 6 percent by weight, or, in some cases, no more than 5 percent by weight, with the weight percents being based on the total weight of the composition.
- the composition used in the methods of the present invention further comprises a source of chloride ions.
- a source of chloride ions can be particularly beneficial when the removal of mill scale is required or desired.
- Suitable chloride sources include, for example, hydrochloric acid, calcium chloride, sodium chloride, ammonium chloride, and potassium chloride, among many others.
- the chloride source is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the chloride source is present in the
- composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 8 percent by weight, or, in some cases, no more than 6 percent by weight, with the weight percents being based on the total weight of the composition.
- the composition used in the methods of the present invention further comprises an organic solvent, such as a water miscible organic solvent.
- organic solvents include monoalkyl or dialkyl ethers of ethylene glycol or diethylene glycol, or a mono-, di-, or trialkyl ether of triethylene glycol and the acetate derivatives thereof.
- the alkyl group often ranges from 1 to 4 carbon atoms. Suitable examples are saturated glycols containing at least four carbon atoms or a compound containing Formula I:
- Exemplary solvents are Cellosolve (trademark for monoethyl ether of ethylene glycol), methyl Cellosolve, butyl Cellosolve, isobutyl Cellosolve, hexyl Cellosolve, Carbitol (trademark for monoethyl ether of diethylene glycol), butyl Carbitol, hexyl Carbitol, monobutyl ether of propylene glycol, monopropyl ether of propylene glycol, monomethyl ether of propylene glycol, monomethyl ether of dipropylene glycol, butoxytriglycol C 4 H 9 0(C 2 H 4 -0) 3 H, methoxytriglycol
- Suitable water miscible alcohols that may be employed in the present invention have from 1 to 8 carbon atoms, such as methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, methylamyl alcohol and the like.
- Suitable water miscible aliphatic ketones that may be employed in the present invention are acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methoxy acetone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, ethyl butyl ketone, diisobutyl ketone, isophorone, acetyl acetone (2,4-pentane dione), diacetone alcohol (CH 3 ) 2 C(OH)CH 2 C(0)CH 3 .
- the organic solvent is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition.
- the chloride source is present in the
- composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 8 percent by weight, or, in some cases, no more than 6 percent by weight, with the weight percents being based on the total weight of the composition.
- compositions used in the methods of the present invention may also comprise any of a variety of optional ingredients, such as colorants, surfactants, corrosion inhibitors, preservatives, fillers, abrasives, buffers, fragrances, and the like.
- the remainder of the composition used in the methods of the present invention is typically water, such as, for example, deionized water.
- the compositions used in the methods of the present invention are substantially free, or completely free, of strong acids that produce a by-product that is environmentally undesirable, such as phosphoric acid and/or sulfuric acid.
- substantially free when used with reference to the absence of a strong acid in the compositions described herein means that the composition includes less than 1% by weight, such as less than 0.1 % by weight, of the strong acid.
- completely free means that there is no strong acid in the composition at all.
- the composition used in the methods of the present invention has a low shear viscosity (As used herein, "low shear viscosity” refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle for 70 seconds at a shear rate of 0.01s ( 1) and at 23 °C.) of at least 1,000 Pa- s, such as at least 2,000 Pa- s, or, in some cases, at least 4,000 Pa- s or at least 5,000 Pa- s.
- a low shear viscosity refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle for 70 seconds at a shear rate of 0.01s ( 1) and at 23 °C.
- the composition used in the methods of the present invention has a high shear viscosity (As used herein, “high shear viscosity” refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle at a shear rate of 10 (4) s ( 1) for 5 seconds at 23°C.) of no more than 0.50 Pa- s, such as no more than 0.1 Pa s, or, in some cases, no more than 0.01 Pa s.
- a high shear viscosity refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle at a shear rate of 10 (4) s ( 1) for 5 seconds at 23°C.
- the composition used in the methods of the present invention has a pH of no more than 6.0, such as 2.0 to 5.0, or, in some cases, 3.0 to 4.0.
- the composition is contacted with the metal containing surface by any of a variety of methods, such as by brushing, spraying, or dipping, among many other methods.
- the compositions described herein are particularly suitable for spray application using conventional pressure pot equipment or HVLP equipment. Because of the thixotropic nature of the compositions described herein, the methods of the present invention can be suitable for use with substantially vertically oriented ferrous metal-containing surface, such as can be the case with, for example, large structures, such as storage tanks, bridges, ships and other vehicles, among many others.
- the composition is allowed to remain on the metal containing surface to remove rust to the extent desired or required.
- Contact time often ranges from at least 5 minutes to several hours, often at least 30 minutes, in some cases at least 3 or 4 hours, depending on the severity of the rust and the temperature at which the cleaning is conducted.
- the derusted surface may then be washed with water to remove the composition described herein, the loosened rust and dissolved rust. In some cases, more than one application of the composition described herein may be desired. Mechanically removing loose rust and scale, by wire brushing for example, prior to application of the composition described herein, may also be desired.
- the present invention also relates to, inter alia, metal surfaces treated by the methods of the present invention.
- Example 1 Laponite RD is commercially available from Southern Clay Products, Inc.
- Example 1A the Laponite RD was incorporated into the water following the manufacturer's recommendations. The citric acid was then slowly added while stirring the solution.
- Klucel M is a hydroxyl propyl cellulose (M w of about 850,000) available from Hercules Inc.
- M w of about 850,000
- Example IB the Klucel M material was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
- Klucel H is a hydroxyl propyl cellulose (M w of about 1,150,000) available from Hercules Inc.
- M w of about 1,150,000
- Example 1C the Klucel H material was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
- the polyvinylpyrrolidone commercially available from Sigma- Aldrich Co., had an average M w of about 1,300,000.
- Example ID the polyvinylpyrrolidone was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
- Example IE The gelatin is commercially available from Sigma-Aldrich Co.
- Example IE the gelatin was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
- Rusty panels were prepared as described in Example 1. The three solutions were spray applied using a garden sprayer to the panels which were disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed.
- Example 2A Approximately 100% of the rust was removed with the solution of Example 2A, while neither Examples 2B and 2C showed any rust removal.
- Rusty panels were prepared as in Example 1. The three solutions were applied to the panels disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed. Approximately 100% of the rust was removed with all three solutions.
- Rusty panels were prepared as in Example 1. The three solutions were applied to the panels disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed. Approximately 100% of the rust was removed with all three solutions.
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Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013550611A JP5693754B2 (ja) | 2011-01-21 | 2012-01-20 | 鉄金属含有表面から錆を取り除く方法 |
AU2012207164A AU2012207164B2 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
BR112013018680A BR112013018680A2 (pt) | 2011-01-21 | 2012-01-20 | método para remover ferrugem de uma superfície contendo metal ferroso |
NZ613553A NZ613553B2 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
CA2825284A CA2825284A1 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
EP12706349.3A EP2665845B1 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
MX2013008465A MX2013008465A (es) | 2011-01-21 | 2012-01-20 | Metodos para retirar herrumbre de una superficie que contiene metal ferroso. |
KR1020137021700A KR20130117853A (ko) | 2011-01-21 | 2012-01-20 | 철 금속 함유 표면으로부터 녹의 제거 방법 |
CN201280010699.9A CN103415651B (zh) | 2011-01-21 | 2012-01-20 | 从含铁类的表面除锈的方法 |
SG2013055413A SG192055A1 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
PL12706349T PL2665845T3 (pl) | 2011-01-21 | 2012-01-20 | Sposoby usuwania rdzy z powierzchni zawierającej metal żelazny |
ES12706349.3T ES2666452T3 (es) | 2011-01-21 | 2012-01-20 | Métodos para eliminar el óxido de una superficie que contiene metal ferroso |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/011,151 US20120189485A1 (en) | 2011-01-21 | 2011-01-21 | Methods of removing rust from a ferrous metal-containing surface |
US13/011,151 | 2011-01-21 |
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WO2012100146A1 true WO2012100146A1 (en) | 2012-07-26 |
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PCT/US2012/022004 WO2012100146A1 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
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US (1) | US20120189485A1 (ja) |
EP (1) | EP2665845B1 (ja) |
JP (1) | JP5693754B2 (ja) |
KR (1) | KR20130117853A (ja) |
CN (1) | CN103415651B (ja) |
AU (1) | AU2012207164B2 (ja) |
BR (1) | BR112013018680A2 (ja) |
CA (1) | CA2825284A1 (ja) |
ES (1) | ES2666452T3 (ja) |
MX (1) | MX2013008465A (ja) |
PL (1) | PL2665845T3 (ja) |
SG (1) | SG192055A1 (ja) |
TR (1) | TR201807940T4 (ja) |
WO (1) | WO2012100146A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021249879A1 (en) * | 2020-06-10 | 2021-12-16 | Chemetall Gmbh | Phosphonate-free, aqueous pickling compositions and their use |
Families Citing this family (6)
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US8852357B2 (en) | 2011-09-30 | 2014-10-07 | Ppg Industries Ohio, Inc | Rheology modified pretreatment compositions and associated methods of use |
CN103898529B (zh) * | 2014-04-22 | 2017-02-15 | 东北大学 | 一种除锈方法 |
JP6727019B2 (ja) * | 2016-04-22 | 2020-07-22 | ショーボンド建設株式会社 | 鋼材の下地処理方法、および下地処理剤 |
CN109628940B (zh) * | 2019-01-21 | 2021-11-12 | 常熟理工学院 | 一种多羟基苯甲酸型水基中性除锈剂 |
KR102166122B1 (ko) | 2020-04-13 | 2020-10-15 | 케이알건설 주식회사 | 강 교량의 녹 또는 페인트 제거방법 |
JP7426641B1 (ja) | 2023-09-18 | 2024-02-02 | スズカファイン株式会社 | 既設鋼材の錆の除去方法 |
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2012
- 2012-01-20 EP EP12706349.3A patent/EP2665845B1/en not_active Not-in-force
- 2012-01-20 PL PL12706349T patent/PL2665845T3/pl unknown
- 2012-01-20 SG SG2013055413A patent/SG192055A1/en unknown
- 2012-01-20 TR TR2018/07940T patent/TR201807940T4/tr unknown
- 2012-01-20 CA CA2825284A patent/CA2825284A1/en not_active Abandoned
- 2012-01-20 AU AU2012207164A patent/AU2012207164B2/en not_active Ceased
- 2012-01-20 BR BR112013018680A patent/BR112013018680A2/pt not_active Application Discontinuation
- 2012-01-20 KR KR1020137021700A patent/KR20130117853A/ko not_active Application Discontinuation
- 2012-01-20 JP JP2013550611A patent/JP5693754B2/ja not_active Expired - Fee Related
- 2012-01-20 ES ES12706349.3T patent/ES2666452T3/es active Active
- 2012-01-20 WO PCT/US2012/022004 patent/WO2012100146A1/en active Application Filing
- 2012-01-20 CN CN201280010699.9A patent/CN103415651B/zh not_active Expired - Fee Related
- 2012-01-20 MX MX2013008465A patent/MX2013008465A/es unknown
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Also Published As
Publication number | Publication date |
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JP5693754B2 (ja) | 2015-04-01 |
AU2012207164B2 (en) | 2015-08-20 |
EP2665845B1 (en) | 2018-03-07 |
ES2666452T3 (es) | 2018-05-04 |
CA2825284A1 (en) | 2012-07-26 |
US20120189485A1 (en) | 2012-07-26 |
CN103415651B (zh) | 2016-10-26 |
TR201807940T4 (tr) | 2018-06-21 |
KR20130117853A (ko) | 2013-10-28 |
PL2665845T3 (pl) | 2018-08-31 |
EP2665845A1 (en) | 2013-11-27 |
MX2013008465A (es) | 2013-12-06 |
BR112013018680A2 (pt) | 2016-10-18 |
JP2014508220A (ja) | 2014-04-03 |
SG192055A1 (en) | 2013-08-30 |
CN103415651A (zh) | 2013-11-27 |
NZ613553A (en) | 2015-11-27 |
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