Classifications

• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
  • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions

Definitions

• the present invention is concerned with improved, acid-based corrosion, grease removal and polishing compositions for treating metallic surfaces and objects. More particularly, it is concerned with such compositions which are compounded so as to substantially prevent oxidation-reduction reactions that would normally take place at a metallic surface, and allow only acid attack of the oxides on the metal.
• the compositions hereof may include polyvinyl pyrrolidone as a viscosity control agent and inhibitor, a derivative of hydrogen tated tallow as an emulsifier, and an N-substituted oxazolidine as an acid inhibitor.
• compositions for removing corrosion from metallic surfaces and objects have long been available.
• corrosion metal oxides
• Such materials are acid based, i.e., they rely upon an acidic attack in order to remove corrosion.
• compositions of the present invention overcomes the problems noted above, and provides greatly improved, flowable, aqueous, highly penetrating compositions of acidic pH which are effective for polishing and removal of corrosion from metallic surfaces, and also to degrease the same.
• the compositions of the present invention may include respective quantities of an acid, an organic compound having a nitrogen, oxygen or sulfur atom therein, an alcohol or other organic solvent, water and at least one emulsifier.
• the acid component is selected from the group consisting of hydrochloric, sulfuric, phosphoric, acetic, citric, nitric, boric and mixtures thereof.
• the acid is further preferably present at a level of from about 2% to 95% by weight, and more preferably from about 5% to 37% by weight.
• the organic compound is advantageously selected from the group consisting of N-substituted oxazolidines (most preferably N-(2-hydroxyethyl) oxazolidine), the p-alkyl benzyl pyridine chlorides, phenylthiourea, 2-mercaptobenzothiazole, di-orthotolyl-thiourea, pyridine, quinoline, decylamine, the dibenzyl sulf oxides, 2-butyne-1, 4-diol, 1-hexyne 3-ol, 4-ethyl-1-octyne-3-ol, decyclamine, soyaamine, octadecylamine, trimethylsoyaammonium chloride, trimethyloctadecylammonium chloride, trimethyldodecyl ammonium chloride, trimethyltallowammonium chloride, N-coco-1, 3-diaminopropane, the
• Such compounds should be used at a level of from about 0.01% to 20% by weight, and more preferably from about .5% to 5% by weight.
• the alcohol component is most preferably 1-pro ⁇ anol, but other alcohols could also be employed.
• other alcohols refers to an alcohol having an alkyl group with from about 1 to 10 carbon atoms, inclusive.
• the alcohol should be used at a level of up to 40% by weight, and most preferably at a level of about 1 to 8% by weight.
• the water should be present at a level of from about 30% to 80% by weight, and most advantageously at a level of from about 50% to 80% by weight.
• the most preferred emulsifiers for use in the invention are selected from the group consisting of the derivatives of hydrogenated tallow (e.g., N, N', N'-tris (2-hydroxy- ethyl)-N-tallow-1, 3-diaminopropane or amine acetate hydrogenated tallow), polyoxyethylene ethers, polyoxyethylene ester alcohols, polyoxyethylene esters of mixed fatty and resin acids and mixtures thereof, although other specific types referred to hereinafter also have utility.
• the total amount of emulsifier present in the composition should be from about 0.1% to 15% by weight, and more preferably from about .5% to 5% by weight.
• a viscosity control agent can also be used in the compositions hereof to give variations in viscosity.
• Such viscosity control has heretofore proved to be difficult or impossible to obtain in acidic compositions, inasmuch as most conventional thickeners tend to flocculate at low pH.
• the control agents of the invention should be selected from the group consisting of polyvinylpyrrolidone and the allylamine emulsion polymers.
• the pyrrolidone is preferred, however, inasmuch as it also acts as a corrosion inhibitor on metallic surfaces.
• the viscosity control agent should be used at a level of up to about 35% by weight, and most preferably at a level of from about 0.5% to 5% by weight.
• a synergistic effect is observed by the use of the mixture of polyvinyl pyrrolidone, Ethoduomeen T/13, and N-(2-hydroxyethyl)-oxazolidine as a corrosion inhibitor in preventing base metal attack, inasmuch as the attack with the preferred mixture is less than that of any of the individual corrosion inhibitors.
• a mild abrasive such as activated silica gel (at a level of up to about 10% by weight) can be employed.
• Perfumes and coloring agents can be added as desired.
• the system can be modified for corrosion removal on metal surfaces having a heavy grease or oil coating by preparing a two-phase emulsified system fay the addition of toluene or related organic solvents.
• the single feature is a graphical representation depicting the extent of base metal attack when using a commercially available corrosion remover, 10% HCl, and the preferred corrosion removing composition of the invention.
• the most preferred rust removal compositions in accordance with the present, invention contain commercial hydrochloric acid, commercial phosphoric acid, 1-propanol, N-(2 hydroxyethyl) oxazolidine, water, a thickening agent, and N,N', N'-tris (2-hydroxyethyl)-N-tallow-1, 3-diaminopropane as an emulsifier.
• the following table sets forth the single most preferred rust removal composition, as well as ranges of use of the above identified components.
• the oxazolidine base metal inhibitor component of Table I is prepared by slowly adding, with mixing, 435.7 grams of formaldehyde to a beaker containing 564.3 grams of diethanolamine. After all formaldehyde is added, the mixture should be stirred for an additional hour.
• a base metal inhibitor component can be produced as the reaction product of a lower aldehyde (i.e., containing from about 1-4 carbon atoms) and an alkanolamine (containing one or more alkyl group each having from about 2-8 carbon atoms).
• a lower aldehyde i.e., containing from about 1-4 carbon atoms
• an alkanolamine containing one or more alkyl group each having from about 2-8 carbon atoms
• a beaker containing 590 grams of water is provided.
• Ten grams of the Ethoduomeen T/13 hydrogenated tallow emulsifier, 270 grams hydrochloric acid, 40 grams phosphoric acid, and 50 grams of 1-propanol are all added to the beaker, with continual mixing.
• the mixture is then heated to 50° C.; and 30 grams polyvinylpyrrolidine is slowly added thereto. Mixing is continued until all of the polymer has dissolved.
• the drawing graphically illustrates the inhibition against base metal attack provided with the preferred composition of Table I.
• a commercially available corrosion remover sold under the designation "Naval Jelly” was tested, along with a solution of 10% hydrochloric acid, and the preferred composition hereof.
• testing conditions were identical, and the extent of attack on a base metal substrate was measured.
• the extent of such attack is very high with the Naval Jelly and hydrochloric acid, but is significantly lower with the preferred inhibitor composition of the invention.
• emulsifier As noted above, a number of different materials can be employed for the various components. With respect to the emulsifier (s), surfactants available from ICI Americas, Inc., Wilmington, Delaware, and Armak Chemicals Division, Chicago, Illinois, can be employed in lieu of or in addition to the preferred tallow based emulsifiers. An exemplary list of such surfactants is provided in Table III.
• compositions of the invention are effective to remove corrosion from base metallic surfaces while substantially preventing oxidation-reduction reactions with the metal itself.
• grease removal is enhanced by virtue of the presence of a single phase, aqueous system.
• Use of the preferred single phase system also enhances the penetration of corrosion where the latter is present.
• Representative metals which can be cleaned and/ or degreased using the compositions hereof include iron and steel, bronze, brass, copper, monel, nickel, chromium plated metals and aluminum.
• a cleaner for tubes of boilers may also be provided by incorporting in the formulation a high foaming agent plus thickeners such as polyvinylpyrrolidone to improve wall adherence.
• An additive such as Arlatone G may also be included as desired to help prevent surface rerusting.
• This type of corrosion remover is advantageous in that a small amount will cover a large surface area and does not require heating to permit the corrosion removal action to take place. Also, since all components are water soluble, removal of the corrosion remover can be performed by flushing water through the system.
• An exemplary formulation of a- composition containing at least one foaming agent and a thickener is as follows:
• the preferred boiler tube cleaner is prepar ed in the same manner as the rust remover and cleaner/ polisher descr ibed above .
• the Arlatone G component is added initially with the HCl , oxazolidine and Ethoduomeen .
• An additional use and formulation for the removal of carbonate deposits and scales for the application of salts to non-metallic surfaces can be made by using the above formulations with the deletion of the base metal corrosion inhibitor .
• This formulation enhances surface deposit removal without penetration to the base .
• An exemplary formulation of a composi tion containing at least one degreasing agent and a thickener is as follows: Other acids such as sulfuric, nitric, phosphoric, acetic, citric, boric, or mixtures thereof can be substituted as well as other salts such as sodium perborate, tri-sodium phosphate, ammonium acetate, sodium chloride, etc.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

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• 1983
  • 1983-07-06 JP JP50270583A patent/JPS60501817A/ja active Pending
  • 1983-07-06 DE DE8383902583T patent/DE3381414D1/de not_active Expired - Lifetime
  • 1983-07-06 WO PCT/US1983/001014 patent/WO1985000379A1/en active IP Right Grant
  • 1983-07-06 EP EP19830902583 patent/EP0151114B1/de not_active Expired

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