US3895910A - Method of protecting tin-packaging against corrosion and making them glossy - Google Patents

Method of protecting tin-packaging against corrosion and making them glossy Download PDF

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US3895910A
US3895910A US405659A US40565973A US3895910A US 3895910 A US3895910 A US 3895910A US 405659 A US405659 A US 405659A US 40565973 A US40565973 A US 40565973A US 3895910 A US3895910 A US 3895910A
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tin
water
nitrite
packings
pasteurization
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Romuald Juchniewicz
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Politechnika Gdanska
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Politechnika Gdanska
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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

Definitions

  • the invention relates to protecting tin packings against corrosion and rendering them glossy.
  • the known method of protecting tin packings against corrosion consists mainly in coating the packings, after sterilization or pasteurization thereof, with temporary protective agents in the form of an emulsion, a grease layer or a paraffin layer.
  • a disadvantage of these methods is the fact that they provide insufficient protection against corrosion since, in spite of the presence of the layer of inhibiting agent, the corrosion process which is initiated during sterilization or pasteurization continues while the tin-packing is stored.
  • the object of the present invention is the provision of a method of protecting tin-packings, particularly for tinned foods, against corrosion and for making them glossy.
  • the method according to the present invention is based on the fact that a mixture of inorganic and organic corrosion inhibitors having a common anion produces a synergistic effect in preventing corrosion and with the cooperation of washing and brightening agents, the mixture causes a strong anodic polarization in the steel tin coating cell.
  • the mixture of inhibitors forms a stable complex which, by being absorbed on the surface of the metal, decreases the binding force of the metal with the passivating oxygen, maintains the potential of the packing below the critical value at which pit formation occurs and deepens the passivating properties of the solution.
  • the processes occuring in the cell cause an anodic dissolution of steel and its immediate passivation. Under such conditions, the surface of the packing undergoes electropolishing and glossing.
  • the electrochemical process of precipitation in the pores of the coating and the process of coagulation of some colloids proceed simultaneously, thus sealing the tin coating on the steel.
  • the purpose of the present invention is to protect tinplate packings against corrosion and to make them glossy during the sterilization or pasteurization process.
  • This purpose has been achieved by using a mixture of chemical compounds of a strictly determined qualitative and quantitative composition in which the process of protecting against corrosion and that of imparting a gloss to the packing proceed jointly with the sterilization or pasteurization process.
  • an inhibitor mixture consisting of an inorganic inhibitor, an organic inhibitor having a common anion, a washing agent and a brightener, is dissolved in water and added with continuous stirring.
  • the water contained in the pasteurization tank or autoclave which is filled with packings for sterilization.
  • the mixture is placed in the form of a paste in a perforated container in the autoclave at the steam inlet.
  • the bottom of the autoclave is strewn with the mixture or the mixture may be placed in a perforated container near the steam or water inlet.
  • the inorganic inhibitors there are included. disodium phosphate, sodium hexametaphosphate, water glass, sodium nitrite, and borax.
  • the organic inhibitors having a common anion and which together with the other additives produces a synergistic effect there are, for example, the phosphates: triethanolamine phosphate, hexamethylenetetramine phosphate, p-nonylphenol phosphate, styrophene phosphite; the silicates: 4-phenoxysilane, 4-butoxysilane, calcium silanolate, aminoalkylpolysiloxane; the nitrites: guanidine nitrite, diisobutylamine nitrite, piperidine nitrite, dicyclohexylamine nitrite; the borates: hydrated cyclohexylamine borate, triethanolamine borate, boric acid triphenyl ester.
  • washing agents there are used water glass, sodium dodecylbenzenesulphonate, ethoxylized anhydrosorbite oleate, ethoxylized pentaerythrite monooleate, ethoxylized pnonylphenol; and as the brightener there is used sodium perborate.
  • the amount of the inhibitor mixture is determined in relation to the amount of water used for pasteurization or sterilization of the tin-packings. It is also dependent on the chemical composition and hardness of the water, as well as on the kind of sheet metal used.'The amount is usually 0.05-O.6% by weight; the percent share of the individual components of the mixture is as follows:
  • inorganic inhibitors 40 60% organic inhibitors having a common anion l5 45% washing agents 10 20% brightener 5 20%
  • the solutions based on phosphate inhibitors have a pH of about 9, nitrite solutions always are above pH 6.5, silicate solutions are up to pH 7, and borate solutions about pH 7.
  • the modulus of the water glass should be about 2 4.
  • the dried or wiped packing is passed, without any necessity of using an additional preservative, to storage, where the packings are isolated from one another by means of plates which are saturated with a mixture of inhibitors of which one may be a volatile corrosion inhibitor.
  • disodium phosphate 100 g of triethanolamine phosphate 100 g of sodium dodecylbenzencsulfonate I00 g of sodium perborate 250 g of water glass.
  • the above is a homogeneous inhibitor solution having a pH value of about 9, and the sterilization is carried out therein.
  • the cans after being dried or wiped free of the superficial water layer, are directed, without any additional preservation, to storage where they are separated from one another by means of plates saturated on both sides with sorbate monooleate. The thus secured packings do not corrode at all during a two year period of storage.
  • the above is a homogeneous inhibitor solution having a pH value of about 8.5 and pasteurization is carried out therein.
  • the dried packings are separated from each other by means of plates saturated on both sides with ethoxylized pentaerythrite monooleate. Thus secured packings do not corrode within up to two years of storage.
  • EXAMPLE lll ln a steam pressure autoclave, at the steam inlet, there is suspended a perforated container containing an inhibitor mixture of paste consistency and composed of:
  • the steam jet breaking against the container becomes saturated with the inhibitors.
  • the dried cans are directed, without any additional preservation, to storage where the cans are separated from each other by means of plates saturated on both sides with a 1:1 mixture in paraffin oil of sorbate monooleate and pentaerythrite oleate.
  • the above is a homogeneous inhibitor solution having a pH value of about 7 and the pasteurization is carried out therein.
  • the cans after being dried or wiped free of superficial water are directed, without any additional preservation, to a storage area where they are separated from each other by means of plates saturated on both sides with a mixture of sorbate monooleate and pentaerythrite monooleate with an addition of dicyclohexylamine nitrite. These packings do not corrode even after 2 years of storage.
  • borax 100 g of triethanolamine borate g of ethoxylized pentaerythrite monooleate 75 g of sodium perborate.
  • the above is a homogeneous inhibitor solution having a pH value of about 7.5 and sterilization in a pressure autoclave is carried out using said solution.
  • the cans, after being dried or wiped free of the superficial water layer are directed, without any additional preservation, to storage, where they are separated from each other by means of plates saturated on both sides with paraffin oil, to which 50% of pentaerythrite monooleate has been added.
  • the thus treated packings do not corrode, even after two years of storing.
  • the cans, dried or wiped free of the superficial water, are directed to storage. If two autoclaves are operating in parallel, the inhibitors are to be introduced during three sterilization operations and the fourth operation is carried out without inhibitors.
  • the invention finds application in various fields of the food industry producing tinned preserves.
  • the serviceable and technical advantages resulting from the use of the present invention consist in the elimination of corrosion of packings during the production and storage, improvement of the external appearance, preventing corrosion of the autoclaves, vehicles and equipment used in the sterilization or pasteurization process.
  • the packings need no grease or emulsion coating, thus creating better labeling conditions and improving the external appearance of the packings, since the labels have no fat drippings. Also. the costs of cleaning the packings are decreased.
  • a method for preventing corrosion and imparting glossiness to tin-packings during the sterilization or pasteurization thereof with water comprising adding to the water used in said sterilization or pasteurization, a mixture comprising (a) water glass; (b) an organic derivative having an anion in common with water glass; (c) a washing agent and (d) a brightening agent, the organic derivative being at least one organic silicate selected from the group consisting of 4-phenoxysilane, 4-butoxysilane, calcium silane, and amino-a1kylpolysiloxanes.
  • a method for preventing corrosion and imparting glossiness to tin-packings during the sterilization or pasteurization thereof with water comprising adding to the water used in said sterilization or pasteurization, a mixture comprising (a) sodium nitrite; (b) an organic derivative having an anion in common with sodium nitrite; (c) a washing agent and (d) a brightening agent, the organic derivative being at least one organic nitrite selected from the group consisting of dicyclohexylamine nitrite. diisobutylaminc nitrite piperidine nitrite and guanidine nitrite.

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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)

Abstract

Tin-packings, i.e. tin-cans for food are protected against corrosion and made glossy at the same time by a method in which a tin-packing is treated with a mixture of inorganic and organic corrosion inhibitors having a common anion and having a synergistic effect together with washing and brightening agents.

Description

United States Patent 21/57, 2; 134/2, 25 R, 25 A; 252/389 R, 389 A Juchniewicz July 22, 197 5 METHOD OF PROTECTING [56] References Cited TIN-PACKAGING AGAINST CORROSION UNITED STATES PATENTS AND MAKING THEM GLOSSY 2.643.177 6/1953 Wachter et a1 21/27 R ux [75] Inventor; Romuald Juchniewicz, Gdansk, 2.675.351 4/1954 U1mer et a1. 2.1/2.7 R Poland 2.815.328 12/1957 Grcen ct a1. 252/389 R x 2.817.636 12/1957 Barker 252/389 R X 1 3] Assign t hnika Gdanska. Gdansk, 2.901.438 8/1959 Rogers 252/389 A x Poland 2.943.909 7/1960 Wachter et a1. 21/2.7 R 3.046.230 7/1962 Berger 252/389 R X [221 111 1973 3.234.144 2/1966 Morehousc 252/389 R [211 App! NO: 405 59 3,240.707 3/1966 Du1at 252/389 R X 3,445.179 5/1969 Jansen 21/27 R Related US. Application Data 3,510,436 5/1970 Silverstein et al 2l/2.7 R X [60] Division of Ser. No. 267,983, June 30, 1972, Pat. No.
3,822,998, which is a continuation of Ser. No. Primary E,mminer Barry S. Richman 7 1969, abandoned- Attorney, Agent. or FirmWaters, Schwartz & Nissen \[30] Foreign Application Priority Data ABSTRACT Oct. 10, 1968 Poland 129973 Tin-packings, 1.6. tin-cans for food are protected 52 us. 01 21/2.7 R; 21/2; 21/27 A; against Corrosion and made glossy at the same time y 57; 154 2; 34 25 252 3 9 R a method in which a tin-packing is treated with a mix- 5 hm C231? 11/12; C23]: 1 ture of inorganic and organic corrosion inhibitors hav- 3 11/18 ing a common anion and having a synergistic effect 158 Field of Search 21/2.7 R, 2.7 A, 2.5 A, mgeher with Washing and brightening agents- 2 Claims, N0 Drawings METHOD OF PROTECTING TIN-PACKAGING AGAINST CORROSION AND MAKING THEM GLOSSY CROSS-REFERENCE TO RELATED APPLICATIONS:
This application is a division of Ser. No. 267,983 filed June 30, 1972 and now US. Pat. No. 3,822,998, which in turn is a continuation of Ser. No. 872,748 filed Oct. 30, 1969 and now abandoned.
BACKGROUND OF THE INVENTION:
1. Field of the Invention:
The invention relates to protecting tin packings against corrosion and rendering them glossy.
2. Prior Art:
The known method of protecting tin packings against corrosion consists mainly in coating the packings, after sterilization or pasteurization thereof, with temporary protective agents in the form of an emulsion, a grease layer or a paraffin layer.
A disadvantage of these methods is the fact that they provide insufficient protection against corrosion since, in spite of the presence of the layer of inhibiting agent, the corrosion process which is initiated during sterilization or pasteurization continues while the tin-packing is stored.
In the literature Applicant has found no method for protecting against corrosion and imparting a gloss to tin-plate packings which involve the introduction of a mixture of inhibitors into the water used during the sterilization and pasteurization processes. On the other hand, there are a number of patents disclosing the use of inorganic and organic inhibitor mixtures with various additives causing a synergistic effect for many industrial applications. These mixtures, mainly empirically arrived at, are not based on the theoretical considerations involved in the present invention.
DETAILED DESCRIPTION OF THE INVENTION:
The object of the present invention is the provision of a method of protecting tin-packings, particularly for tinned foods, against corrosion and for making them glossy.
The method according to the present invention is based on the fact that a mixture of inorganic and organic corrosion inhibitors having a common anion produces a synergistic effect in preventing corrosion and with the cooperation of washing and brightening agents, the mixture causes a strong anodic polarization in the steel tin coating cell. The mixture of inhibitors forms a stable complex which, by being absorbed on the surface of the metal, decreases the binding force of the metal with the passivating oxygen, maintains the potential of the packing below the critical value at which pit formation occurs and deepens the passivating properties of the solution. The processes occuring in the cell cause an anodic dissolution of steel and its immediate passivation. Under such conditions, the surface of the packing undergoes electropolishing and glossing. The electrochemical process of precipitation in the pores of the coating and the process of coagulation of some colloids proceed simultaneously, thus sealing the tin coating on the steel.
The purpose of the present invention is to protect tinplate packings against corrosion and to make them glossy during the sterilization or pasteurization process.
This purpose has been achieved by using a mixture of chemical compounds of a strictly determined qualitative and quantitative composition in which the process of protecting against corrosion and that of imparting a gloss to the packing proceed jointly with the sterilization or pasteurization process.
According to the chemical composition of the water and its hardness, as well as to the kind of sheet metal used for the packings, an inhibitor mixture, consisting of an inorganic inhibitor, an organic inhibitor having a common anion, a washing agent and a brightener, is dissolved in water and added with continuous stirring. to the water contained in the pasteurization tank or autoclave which is filled with packings for sterilization. In steam autoclaves, the mixture is placed in the form of a paste in a perforated container in the autoclave at the steam inlet. In horizontal autoclaves the bottom of the autoclave is strewn with the mixture or the mixture may be placed in a perforated container near the steam or water inlet.
Among the inorganic inhibitors there are included. disodium phosphate, sodium hexametaphosphate, water glass, sodium nitrite, and borax. Among the organic inhibitors having a common anion and which together with the other additives produces a synergistic effect, there are, for example, the phosphates: triethanolamine phosphate, hexamethylenetetramine phosphate, p-nonylphenol phosphate, styrophene phosphite; the silicates: 4-phenoxysilane, 4-butoxysilane, calcium silanolate, aminoalkylpolysiloxane; the nitrites: guanidine nitrite, diisobutylamine nitrite, piperidine nitrite, dicyclohexylamine nitrite; the borates: hydrated cyclohexylamine borate, triethanolamine borate, boric acid triphenyl ester. As the washing agents, there are used water glass, sodium dodecylbenzenesulphonate, ethoxylized anhydrosorbite oleate, ethoxylized pentaerythrite monooleate, ethoxylized pnonylphenol; and as the brightener there is used sodium perborate.
The amount of the inhibitor mixture is determined in relation to the amount of water used for pasteurization or sterilization of the tin-packings. It is also dependent on the chemical composition and hardness of the water, as well as on the kind of sheet metal used.'The amount is usually 0.05-O.6% by weight; the percent share of the individual components of the mixture is as follows:
inorganic inhibitors 40 60% organic inhibitors having a common anion l5 45% washing agents 10 20% brightener 5 20% The solutions based on phosphate inhibitors have a pH of about 9, nitrite solutions always are above pH 6.5, silicate solutions are up to pH 7, and borate solutions about pH 7. The modulus of the water glass should be about 2 4.
After the pasteurization or sterilization process, the dried or wiped packing is passed, without any necessity of using an additional preservative, to storage, where the packings are isolated from one another by means of plates which are saturated with a mixture of inhibitors of which one may be a volatile corrosion inhibitor.
The method according to the present invention is more fully explained in the following Examples.
EXAMPLE I To I000 liters of technological water of of German hardness, which are used for the sterilization of 1000 0.5 kg cans made of electrolytic tin-plate. there are added with constant stirring, a solution consisting of the following previously dissolved in water:
250 g of disodium phosphate 100 g of triethanolamine phosphate 100 g of sodium dodecylbenzencsulfonate I00 g of sodium perborate 250 g of water glass.
The above is a homogeneous inhibitor solution having a pH value of about 9, and the sterilization is carried out therein. The cans, after being dried or wiped free of the superficial water layer, are directed, without any additional preservation, to storage where they are separated from one another by means of plates saturated on both sides with sorbate monooleate. The thus secured packings do not corrode at all during a two year period of storage.
EXAMPLE II To 500 liters of technological water of 2 of German hardness used for the pasteurization of 500 l kg packings made of hot tin-plate. the following is added with continuous stirring, after being previously dissolved in water;
200 g of sodium nitrite 90 g of diisohutylamine nitrite 75 g of ethoxylized pentaerythrite monoleate 75 g of sodium perborate 250 g of water glass.
The above is a homogeneous inhibitor solution having a pH value of about 8.5 and pasteurization is carried out therein. The dried packings are separated from each other by means of plates saturated on both sides with ethoxylized pentaerythrite monooleate. Thus secured packings do not corrode within up to two years of storage.
EXAMPLE lll ln a steam pressure autoclave, at the steam inlet, there is suspended a perforated container containing an inhibitor mixture of paste consistency and composed of:
250 g of water glass 250 g of sorbate monooleate 150 g of sodium perborate 250 g of disodium phosphate 50 g of hexamethylenetetramine phosphate.
The steam jet breaking against the container becomes saturated with the inhibitors. After the sterilization process the dried cans are directed, without any additional preservation, to storage where the cans are separated from each other by means of plates saturated on both sides with a 1:1 mixture in paraffin oil of sorbate monooleate and pentaerythrite oleate. Thus secured packings do not corrode even after two years.
EXAMPLE IV To 500 liters of technological water of of German hardness, used for the pasteurization of 500 1 kg packings made of electrolytic tin-plate there are added with continuous stirring, previously dissolved in water:
250 ml of water glass of a modulus of 2-4 100 g of 4-butoxysilane g of ethoxylized anhydrosorbite oleate 70 g of sodium perborate.
The above is a homogeneous inhibitor solution having a pH value of about 7 and the pasteurization is carried out therein. The cans, after being dried or wiped free of superficial water are directed, without any additional preservation, to a storage area where they are separated from each other by means of plates saturated on both sides with a mixture of sorbate monooleate and pentaerythrite monooleate with an addition of dicyclohexylamine nitrite. These packings do not corrode even after 2 years of storage.
EXAMPLE V To 500 liters of technological water of 14 of German hardness, used for the sterilization of 500 0.5 kg packings made of hot tin-plate, there is added with continuous stirring to an autoclave, a water solution of:
200 g of borax 100 g of triethanolamine borate g of ethoxylized pentaerythrite monooleate 75 g of sodium perborate.
The above is a homogeneous inhibitor solution having a pH value of about 7.5 and sterilization in a pressure autoclave is carried out using said solution. The cans, after being dried or wiped free of the superficial water layer are directed, without any additional preservation, to storage, where they are separated from each other by means of plates saturated on both sides with paraffin oil, to which 50% of pentaerythrite monooleate has been added. The thus treated packings do not corrode, even after two years of storing.
EXAMPLE Vl in a horizontal autoclave, the bottom of the auto clave is strewn with a mixture consisting of the following inhibitors:
300 g of water glass 250 g of disodium phosphate g of p-nonylphenol phosphate 75 g of ethoxylized pentaerythrite monooleate 100 g of sodium perborate Then there are placed into the autoclave 3 baskets filled with 2000 0.25 kg packings. The packings are covered with about 1000 liters of water and sterilization is carried out according to the conventional technological requirements.
After the sterilization process the cans, dried or wiped free of the superficial water, are directed to storage. If two autoclaves are operating in parallel, the inhibitors are to be introduced during three sterilization operations and the fourth operation is carried out without inhibitors.
The invention finds application in various fields of the food industry producing tinned preserves. The serviceable and technical advantages resulting from the use of the present invention consist in the elimination of corrosion of packings during the production and storage, improvement of the external appearance, preventing corrosion of the autoclaves, vehicles and equipment used in the sterilization or pasteurization process. Furthermore, the packings need no grease or emulsion coating, thus creating better labeling conditions and improving the external appearance of the packings, since the labels have no fat drippings. Also. the costs of cleaning the packings are decreased.
What is claimed is:
l. A method for preventing corrosion and imparting glossiness to tin-packings during the sterilization or pasteurization thereof with water, said method comprising adding to the water used in said sterilization or pasteurization, a mixture comprising (a) water glass; (b) an organic derivative having an anion in common with water glass; (c) a washing agent and (d) a brightening agent, the organic derivative being at least one organic silicate selected from the group consisting of 4-phenoxysilane, 4-butoxysilane, calcium silane, and amino-a1kylpolysiloxanes.
2. A method for preventing corrosion and imparting glossiness to tin-packings during the sterilization or pasteurization thereof with water, said method comprising adding to the water used in said sterilization or pasteurization, a mixture comprising (a) sodium nitrite; (b) an organic derivative having an anion in common with sodium nitrite; (c) a washing agent and (d) a brightening agent, the organic derivative being at least one organic nitrite selected from the group consisting of dicyclohexylamine nitrite. diisobutylaminc nitrite piperidine nitrite and guanidine nitrite.

Claims (2)

1. A METHOD FOR PREVENTING CORROSION AND IMPARTING GLOSSINESS TO TIN-PACHINGS DURING THE STERILIZATION OR PASTEURIZATION THEREOF WITH WATER SAID METHOD COMPRISING ADDING TO THE WATER USED IN SAID STERILIZATION OR PASTEURIZATION, A MIXTURE COMPRISING (A) WATER GLASS, (B) AN ORGANIC DERIVATIVE HAVING AN ANION IN COMMON WITH WATER GLASS (C) A WASHING AGENT AND (D) A BRIGHTENING AGENT THE ORGANIC DERIVATIVE BEING AT LEAST ONE ORGANIC SILICATE SELECTED FROM THE GROUP CONSISTING OF 4PHENOXYSILANE 4-BUTOXYSILANE CALCIUM SILANE AND AMINOALKYLPOLYSILOXANES.
2. A METHOD FOR PREVENTING CORROSION AND IMPARTING GLOSSINESS TO TIN-PACKINGS DURING THE STERILZATION OR PASTEURIZATION THEREOF WITH WATER SAID METHOD COMPRISING ADDING TO THE WATER USED IN SAID STERILZATION OR PASTEURIZATION A MIXTURE COMPRISING (A) SODIUM NITRITE (B) AN ORGANIC DERIVATIVE HAVING AN ANION IN COMMON WITH SODIUM NITRITE, (C) A WASHING AGENT AND (D) A BRIGHTENING AGENT THE ORGANIC DERIVATIVE BEING AT LEAST ONE ORGANIC NITRITE SELECTED FROM THE GROUP CONSISTING OF DICYCLOHEXYLAMINE NITRITE DIISOBUTYLAMINE NITRITE PIPERIDINE NITRITE AND GUANIDINE NITRITE.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265780A (en) * 1979-02-15 1981-05-05 Nippon Paint Co., Ltd. Process for cleaning of tin-plated steel cans
US4717497A (en) * 1984-03-10 1988-01-05 Amchem Products, Inc. Tin-plate degreasing detergent
US5424007A (en) * 1988-03-29 1995-06-13 Buckman Laboratories International, Inc. 1-methyl-3,5,7-triaza-1-azoniatricyclodecane compounds, a method for preparing these compounds, their use in the control of microorganisms in aqueous systems, and their use in the inhibition of corrosion
US6623695B2 (en) 1997-12-04 2003-09-23 Steris Corporation Chemical modification of electrochemically activated solutions for improved performance
WO2006065239A1 (en) 2003-12-15 2006-06-22 Smithkline Beecham Corporation Cleanser compositions comprising a sensory signal

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US2901438A (en) * 1956-10-25 1959-08-25 Union Carbide Corp Corrosion inhibitors
US2943909A (en) * 1957-08-26 1960-07-05 Shell Oil Co Corrosion- and fungus-inhibiting composition
US3046230A (en) * 1959-08-19 1962-07-24 Cities Service Res & Dev Co Antifreeze composition
US3234144A (en) * 1962-03-26 1966-02-08 Union Carbide Corp Process for inhibiting corrosion
US3240707A (en) * 1960-06-21 1966-03-15 United States Borax Chem Corrosion inhibitor compositions for aqueous liquids
US3445179A (en) * 1964-12-15 1969-05-20 Stork & Co Nv Method and device for inhibiting corrosion in sterilizers
US3510436A (en) * 1968-10-31 1970-05-05 Betz Laboratories Corrosion inhibition in water system

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US2643177A (en) * 1946-05-07 1953-06-23 Shell Dev Vapor phase corrosion inhibition of metals
US2675351A (en) * 1950-03-27 1954-04-13 Drew & Co Inc E F Method for preventing corrosion and scale
US2817636A (en) * 1954-10-04 1957-12-24 Gulf Research Development Co Permanent type antifreeze composition
US2815328A (en) * 1955-02-25 1957-12-03 Nat Aluminate Corp Corrosion inhibitor composition for aqueous liquids
US2901438A (en) * 1956-10-25 1959-08-25 Union Carbide Corp Corrosion inhibitors
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US4265780A (en) * 1979-02-15 1981-05-05 Nippon Paint Co., Ltd. Process for cleaning of tin-plated steel cans
US4717497A (en) * 1984-03-10 1988-01-05 Amchem Products, Inc. Tin-plate degreasing detergent
US5424007A (en) * 1988-03-29 1995-06-13 Buckman Laboratories International, Inc. 1-methyl-3,5,7-triaza-1-azoniatricyclodecane compounds, a method for preparing these compounds, their use in the control of microorganisms in aqueous systems, and their use in the inhibition of corrosion
US6623695B2 (en) 1997-12-04 2003-09-23 Steris Corporation Chemical modification of electrochemically activated solutions for improved performance
WO2006065239A1 (en) 2003-12-15 2006-06-22 Smithkline Beecham Corporation Cleanser compositions comprising a sensory signal

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