EP0609342A1 - Composition for stabilizing inorganic peroxide solutions. - Google Patents
Composition for stabilizing inorganic peroxide solutions.Info
- Publication number
- EP0609342A1 EP0609342A1 EP92922319A EP92922319A EP0609342A1 EP 0609342 A1 EP0609342 A1 EP 0609342A1 EP 92922319 A EP92922319 A EP 92922319A EP 92922319 A EP92922319 A EP 92922319A EP 0609342 A1 EP0609342 A1 EP 0609342A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- composition
- treatment
- stabilizing
- inorganic
- 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.)
- Granted
Links
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
- C23G1/08—Iron or steel
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Definitions
- the present invention relates to a composition having high stabilizing properties, and this, more particularly in the case of inorganic peroxides used in the context of industrial applications. It relates more particularly to a stabilizing composition of inorganic peroxides used in the pickling baths of metal surfaces.
- Stripping baths of the type mentioned generally contain nitric-hydrofluoric mixtures or mixtures of sulfuric-nitric and hydrofluoric acids, to which process correctors which may be surfactants have been added, in order to improve their wetting characteristics or inhibitors to standardize the chemical action.
- pickling baths have recently been proposed. which provide an alternative solution to traditional processes.
- the auxiliary mechanical action normally provides for the creation of turbulence in the pickling solution, either by stirring the liquid or by blowing air into the baths so as to promote the detachment of the oxides from the metal surfaces.
- the absence of nitric acid in these baths is compensated for by the presence of inorganic peroxides such as hydrogen peroxide.
- inorganic peroxides not only replaces the oxidizing action of nitric acid, but it also promotes pickling and passivation of the metal surface.
- nitric acid-free pickling baths allow on the one hand to solve the problem of pollution due to the development of nitrogen oxide during the pickling action and the problem caused by the presence of nitrates in Landfill, however, it requires the use of specific, expensive equipment that requires periodic maintenance.
- control of the peroxides present in the baths should normally be carried out using redox measuring instruments which, as is known, are not only very expensive to purchase, but also have a limited longevity when they are used for this specific purpose.
- the baths containing peroxides also offer limited stability, due to the presence of metals which catalyze the decomposition of the peroxides.
- an important objective of the present invention is to produce a composition having high stabilizing properties, and this, more particularly with regard to the inorganic peroxides used in the context of industrial applications, this composition having to be able to stabilize peroxides while avoiding undesirable decompo ⁇ sitions of these same peroxides in the presence of metals, even in high concentrations, and more specifically in the context of acid pickling processes replacing nitric mixtures.
- another important objective of the present invention is to provide a composition offering high stabilizing properties and capable of increasing the oxidation action of peroxides, more particularly hydrogen peroxide in contact with metal surfaces, through an oxidation-dissolution action of oxides which is extremely rapid, even at room temperature.
- Another important objective of the present invention consists in producing a composition offering high stabilizing properties and which is capable of providing a pickling system which would replace the nitric acid baths currently used, without however the need to modify the equipment used and without it is necessary to reduce, at equal temperature, the duration of treatment.
- Another objective - and not least - of the present invention is to provide a composition with high stabilizing properties which makes it possible to eliminate the heating of the solutions and to eliminate their agitation as well as the permanent control of the level of peroxides contained in the baths.
- composition with high stabilizing properties and more particularly for inorganic peroxides used in the context of industrial applications, characterized in that it comprises at least one activating agent having cyclic, aromatic amino compounds, imidazole and carboxy-imidazole derivatives as well as aliphatic amines making it possible to increase the oxidation-dissolution action, at room temperature, of the oxides and, at the same time, slowing the decomposition of inorganic peroxides on contact with metal surfaces.
- activating agent having cyclic, aromatic amino compounds, imidazole and carboxy-imidazole derivatives as well as aliphatic amines making it possible to increase the oxidation-dissolution action, at room temperature, of the oxides and, at the same time, slowing the decomposition of inorganic peroxides on contact with metal surfaces.
- the invention relates to a stabilizing composition for inorganic peroxides, more particularly hydrogen peroxide, intended for baths for the surface treatment of metal parts, according to which it comprises at least one activating agent selected from cyclic or aromatic amino compounds, triazoles, imidazole or carboxyimidazoles or their derivatives, and aliphatic amines. Good results have been obtained with triazoles, imidazole, carboxy ⁇ imidazoles, their derivatives and mixtures of these compounds.
- inorganic peroxides is intended to denote hydrogen peroxide, inorganic peracids and their salts, more particularly perboric, perphosphoric and persulfuric acids and their alkali or alkaline earth metal salts, as well as the peroxides of alkaline and alkaline metals. earthy such as sodium, calcium and magnesium peroxides.
- hydrogen peroxide or inorganic peracids are used. Very good results have been obtained with hydrogen peroxide.
- surface treatment of metal parts is intended to denote the treatment of metal parts using a bath comprising one or more acid compounds and one or more oxidizing compounds, in particular with a view to stripping them by removing the oxides. covering their surface, or passivating them or improving the surface finish, more particularly polishing them and / or performing a polishing treatment.
- the composition is intended to be incorporated into the surface treatment baths of metal parts. It generally does not itself contain peroxide, which is added to the treatment bath independently.
- the stabilizing action of peroxides and their capacity to accelerate deoxidation depend on the composition of the baths in which the traditional standard nitric-hydrofluoric mixture is replaced, as regards the nitric part, by oxygenated water in the molar proportion H2O2-HNO3 of 1/2 to 2/1 but preferably 1/1, while the acid part of the nitric acid is replaced by sulfuric acid in the molar proportion HNO3-H2SO4 of 1 / 2 to 2.5 / 1, but preferably 1 / 1.3.
- the acid part with regard to sulfuric acid may be replaced, in whole or in part, by inorganic acids of phosphoric, sulfamic or other type, insofar as they do not cause a negative interaction with the stabilizer of the hydrogen peroxide or peroxide.
- the hydrofluoric part can for its part comprise at least one compound chosen from fluorinated acids or fluorinated salts and the percentage is maintained within the usual standard values that are known.
- the bath thus obtained requires the presence of a stabilizing agent reading peroxide in the proportion of 1/100 to 1/1, but preferably from 1/30 to 1/2, depending on the peroxide used.
- the stabilizing agent used for the baths of these compositions and which constitutes the object of the present invention may comprise, in addition to the activating agent at least, another compound chosen from stabilizing agents, the solvent compounds of the agent stabilizer, oxidation catalysts, wetting agents capable of resisting in an oxidizing acid environment, optionally phosphates or phosphonates as co-adjuvants for precipitation and deactivation of dissolved metals, and finally, inorganic acids and / or organic as product standardizers.
- the composition also comprises at least one stabilizing agent.
- the stabilizing agent in particular, it may comprise one or more aromatic or cyclic rings or one or more aliphatic chains. It can also contain at least one group chosen from hydroxyl, carboxylic, sulfonate and phosphate groups.
- the term “sulfonate and phosphate groups” is intended to denote here both the sulfonic and phosphoric groups and their salts. It can also contain at least one group chosen from esters, ethers, dienes, azoles, mercapto-azoles or combinations thereof.
- the stabilizing agent may comprise at least one compound selected from mono or polycyclic aromatic or alicyclic compounds and aliphatic compounds substituted by at least one group chosen from the groups hydroxyls, carboxyls, sulfonates, phosphates, esters, ethers, dienes, azoles and mercapto-azoles. Good results have been obtained with compounds substituted by sulfonate (or sulfonic) groups and phosphates (or phosphoric) groups or mixtures thereof. P-Toluene sulfonic acid is well suited.
- compositions according to the invention can comprise at least one solvent compound for the stabilizing agent.
- the solvent compound also called dissolving part of the stabilizing agent described above can include alcohols, glycols, polyethers, dimethylformamide, N-methylpyrrolidone, ketones, polyglycols, esters, low-weight condensates molecular or organic groups characterized by a reasonable solubility in water, resistant in an acidic environment and having a good dissolving power of the organic components used as stabilizing agents and having zero or low solubility in water or in inorganic acids at use concentrations.
- the solvent compound of the stabilizing agent preferably comprises at least one compound selected from alcohols, glycols and polyglycols.
- the solvent compound may also contain, in admixture with said alcohols, glycols and / or polyglycols at least one adjuvant chosen from dimethyl ⁇ formamide and N-methylpyrrolidone.
- the solvent compound can include polyesters, ketones, esters, low molecular weight condensates or organic groups with good water solubility and resistance in an acidic medium.
- the activating agent which can also be used independently of the stabilizing agents or solvent compounds mentioned above, comprises cyclic, aromatic amine components, derivatives of imidazoles and / or carboxy-imidazoles, and / or aliphatic amines.
- compositions according to the invention can also contain at at least one compound chosen from oxidation catalysts made up of metals and wetting agents resistant in an oxidizing acid medium.
- the oxidation catalysts can comprise at least one metal belonging to the first, second, third or fourth group. These are present in a percentage varying from 2 to 20,000 ppm and preferably from 10 to 3,000 ppm.
- group is meant a group which corresponds to a family represented in the same column of the periodic table of the elements.
- the metals of group 3 have proved to be interesting and good results have been obtained with aluminum.
- the composition may also comprise at least one wetting agent stable in oxidizing acid medium, that is to say an agent capable of modifying the surface tension at the solid / liquid interface in order to improve the wetting of metal parts by the treatment bath.
- This wetting agent should be selected from those which are chemically inert in the presence of an acidic and oxidizing aqueous solution and, in particular, the acidic aqueous solutions of peroxides.
- wetting agents capable of withstanding in an oxidizing acid environment consist of nonionic, anionic, araphoteric or cationic condensates or of fluorinated derivatives, or of a mixture of these. Good results have been obtained with fluorinated anionic surfactants and ethylene glycol condensates with alkylphenols and their mixtures.
- the pickling bath constituted in this way and having the stabilizing agent described above can operate from a pH equal to 2.5 and up to a pH of 0.0, but usually it operates at a pH below 1.3.
- the pickling bath can operate at pH values equal to or less than 0.3.
- the stabilizing composition reduces the oxidation potential of the iron / nickel / chromium sub-oxides and catalyze their oxidation, thereby promoting the transformation into soluble oxides.
- composition according to the invention makes it possible to carry out pickling in a time and at extremely competitive temperatures compared to the baths currently used.
- precipitation additives and, consequently, deactivation of the dissolved metals originating from the dissolution of the oxides or from the surface part of the metal part under the action of the treatment bath.
- Such adjuvants can be soluble inorganic or organic salts whose anion combines with the cation of the metal or metals dissolved in the bath to form a salt whose solubility product is very low under the conditions prevailing in the bath, for example less than 10 ⁇ ⁇ gram ion.
- the composition can also comprise at least one compound chosen from phosphates and phosphonates as co-adjuvants for precipitation and deactivation of dissolved metals and inorganic and organic acids as treatment-leveling agents. These are used to standardize the product.
- the precipitation co-adjuvants can be chosen from phosphates and phosphonates of all types. Pyrophosphates are well suited. Finally, as agents allowing a uniform result to be obtained over the entire surface of the metal part to be treated, it is also possible to add to the bath one or more inorganic and / or organic acids. Organic acids are preferred. Examples of such organic acids are picric acid and citric acid.
- the stripping action obtained through the use of the composition having high stabilizing properties and which is the subject of the present invention normally does not require any agitation of the baths or of the elements which are immersed therein.
- ultrasound which is normally associated with the pickling bath or, preferably , during the rinsing phases, which makes it possible to obtain a synergy of the result.
- the use of ultrasound in fact makes it possible to considerably reduce the duration of pickling and this, up to 1/6 of the time which would have been necessary in the absence of the use of ultrasound.
- the invention therefore therefore also relates to methods for treating metallic surfaces, more particularly stainless steel surfaces in the presence of the stabilizing compositions described above using at least one inorganic peroxide at acid pH. This treatment is then followed by at least one rinsing. During at least one of the treatment or rinsing phases, agitation of the bath can be obtained using ultrasound.
- variable doses of the various active compounds and in particular of acid, of inorganic peroxides and of stabilizing composition according to the invention can be used. It is thus possible to use 0.1 to 5 moles and preferably 0.5 to 3 moles of peroxide compound per liter of solution.
- the amount of acid is added to maintain the pH at the desired values.
- the acids which can be used for this purpose mention may be made of sulfuric acid which is particularly suitable. It can be used in combination with fluorides and for example with hydrofluoric acid in variable ratios. In this case, the sulfuric acid / hydrofluoric acid weight ratios generally do not exceed 500 and, more often than not, 100. Likewise these ratios are generally not less than 0.1 and, most often, not less than 1.
- the invention also relates to the use of the composition described above for the preparation of a pickling, passivating, polishing and / or polishing bath for metals.
- Example 1 By way of illustration, the following example is reported of a typical composition of a pickling bath for steels such as austenitic steels. This example is in no way intended to limit the scope of the invention.
- a typical composition includes: 98% sulfuric acid from 4 to 300 g / 1 hydrogen peroxide at 100 X from 0.2 to 100 g / 1 hydrofluoric acid from 0.5 to 10 g / 1 stabilizing composition from 0.2 at 30 g / 1 where the standard stabilizing composition consists of:
- Test 4 result similar to test 1 after a period of 45 minutes-
- Test 5 result similar to test 1 after 30 minutes Weight loss in H2O2 Test 2 ⁇ 24 hours after the test, there are 8 g of H2O2 by 1.
- Test 3 24 hours after the test, there are 32 g of H2O2 by 1.
- Test 4 24 hours after the test, there remain 28 g of H2O2 by 1.
- Test 5 24 hours after the test, there remain 33 g of H2O2 by 1.
- Test 2 2 g of H2O2 by 1.
- Test 3 28 g of H2O by 1.
- Test 4 20 g of H2O2 by 1.
- Test 6 1 g / 1
- Test 7 5 g / 1
- Test 8 10 g / 1
- composition of the invention having high stabilizing properties and more particularly in the case of inorganic peroxides used in the context of industrial applications, offers many advantages of all kinds.
- the temperatures of use of pickling baths appear to be equal to or really lower than the temperatures which are those of baths based on nitric and hydrofluoric acid and therefore, highly polluting.
- composition having important stabilizing properties, object of the present invention there is no emission of nitrous vapors, and the emission of acids, for example fluorides, is itself extremely reduced .
- the elimination of intergranular corrosion is also obtained and the process can be adapted to different types of stainless steels such as, for example, steels of the AISI 400 series (the pickling of which is generally quite difficult with systems. traditional) or still, the steels of the AISI 300 series. It is understood that the compositions according to the invention are also well suited for the treatment of other types of stainless steels.
- the use of the stabilizing composition described above makes it possible in particular to considerably reduce the consumption of inorganic peroxide, more particularly hydrogen peroxide, while allowing equal or really lower pickling times. , even up to 50%, compared to the stripping times required in the case of traditional baths.
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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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Detergent Compositions (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Composition stabilisante des peroxydes inorganiques et du peroxyde d'hydrogène destinée aux bains de traitement de surface des pièce métalliques comprenant au moins un agent activant sélectioné parmi les composés aminés cycliques ou aromatiques, les dérivés des triazoles, de l'imidazole et des carboxy-imidazoles et les amines aliphatiques. Procédé pour le traitement des surfaces métalliques à l'aide de la composition à pH acide en présence de peroxyde inorganique. Utilisation de la composition pour la réalisation d'un bain de décapage, de brillantage ou de polissage des métaux.Stabilizing composition for inorganic peroxides and hydrogen peroxide intended for surface treatment baths of metal parts comprising at least one activating agent selected from cyclic or aromatic amine compounds, derivatives of triazoles, imidazole and carboxy-imidazoles and aliphatic amines. Process for the treatment of metal surfaces using the composition at acidic pH in the presence of inorganic peroxide. Use of the composition for producing a bath for pickling, brightening or polishing metals.
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI91284 | 1991-10-25 | ||
ITMI912845A IT1251431B (en) | 1991-10-25 | 1991-10-25 | COMPOUND WITH HIGH STABILIZING CHARACTERISTICS, PARTICULARLY FOR INORGANIC PEROXIDES USED IN INDUSTRIAL APPLICATIONS |
PCT/EP1992/002442 WO1993008317A1 (en) | 1991-10-25 | 1992-10-23 | Composition for stabilizing inorganic peroxide solutions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0609342A1 true EP0609342A1 (en) | 1994-08-10 |
EP0609342B1 EP0609342B1 (en) | 1996-05-08 |
Family
ID=11360958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92922319A Expired - Lifetime EP0609342B1 (en) | 1991-10-25 | 1992-10-23 | Composition for stabilizing inorganic peroxide solutions |
Country Status (11)
Country | Link |
---|---|
US (1) | US5538152A (en) |
EP (1) | EP0609342B1 (en) |
JP (1) | JPH07500378A (en) |
KR (1) | KR100249061B1 (en) |
BR (1) | BR9206668A (en) |
CA (1) | CA2121691A1 (en) |
DE (1) | DE69210622T2 (en) |
ES (1) | ES2089573T3 (en) |
FI (1) | FI100727B (en) |
IT (1) | IT1251431B (en) |
WO (1) | WO1993008317A1 (en) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
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ATE300630T1 (en) * | 1994-09-26 | 2005-08-15 | Steris Inc | ACID TREATMENT OF STAINLESS STEEL |
BR9712070A (en) * | 1996-09-18 | 2002-01-15 | Metrex Res Corp | Aqueous anti-corrosive disinfectant and sterilizing composition and processes for forming the same, and for disinfecting a surface |
US5958147A (en) * | 1997-05-05 | 1999-09-28 | Akzo Nobel N.V. | Method of treating a metal |
US6068879A (en) * | 1997-08-26 | 2000-05-30 | Lsi Logic Corporation | Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing |
EP0945527A1 (en) * | 1998-03-24 | 1999-09-29 | Henkel Corporation | Aqueous liquid deoxidizing compositions methods of preparing them and processes for deoxidizing-etching aluminum therewith |
JP4866503B2 (en) * | 1998-12-28 | 2012-02-01 | 日立化成工業株式会社 | Metal polishing liquid material and metal polishing liquid |
US6117250A (en) * | 1999-02-25 | 2000-09-12 | Morton International Inc. | Thiazole and thiocarbamide based chemicals for use with oxidative etchant solutions |
US6444140B2 (en) | 1999-03-17 | 2002-09-03 | Morton International Inc. | Micro-etch solution for producing metal surface topography |
US20040099637A1 (en) * | 2000-06-16 | 2004-05-27 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
US20030178391A1 (en) * | 2000-06-16 | 2003-09-25 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
ATE404498T1 (en) * | 2001-04-09 | 2008-08-15 | Ak Steel Properties Inc | METHOD AND DEVICE FOR REMOVING HYDROGEN PEROXIDE FROM PICKLING SOLUTIONS |
ATE343663T1 (en) | 2001-04-09 | 2006-11-15 | Ak Properties Inc | METHOD FOR PICKLING STAINLESS STEEL USING HYDROGEN PEROXIDE |
JP4180925B2 (en) | 2001-04-09 | 2008-11-12 | エイケイ・スティール・プロパティーズ・インコーポレイテッド | Silicon-containing electrical steel grade hydrogen peroxide pickling |
TW591089B (en) * | 2001-08-09 | 2004-06-11 | Cheil Ind Inc | Slurry composition for use in chemical mechanical polishing of metal wiring |
US6953389B2 (en) * | 2001-08-09 | 2005-10-11 | Cheil Industries, Inc. | Metal CMP slurry compositions that favor mechanical removal of oxides with reduced susceptibility to micro-scratching |
DE10156624B4 (en) * | 2001-11-17 | 2005-10-27 | Robert Bosch Gmbh | Method and pickling solution for cleaning deposits of a steel workpiece |
KR20030050026A (en) * | 2001-12-18 | 2003-06-25 | 백운규 | Slurry for chemical mechanical polishing, method of fabricating the same and method of manufacturing using the same |
DE10346192B4 (en) * | 2003-10-02 | 2009-08-06 | Thyssenkrupp Presta Teccenter Ag | Method for rust removal of molded parts and use of the method |
KR100795364B1 (en) * | 2004-02-10 | 2008-01-17 | 삼성전자주식회사 | Composition for cleaning a semiconductor substrate, method of cleaning and method for manufacturing a conductive structure using the same |
KR20050110470A (en) * | 2004-05-19 | 2005-11-23 | 테크노세미켐 주식회사 | Composition for cleaning a semiconductor substrate, method for cleaning a semiconductor substrate and method for manufacturing a semiconductor device using the same |
EP1793016A1 (en) * | 2005-12-01 | 2007-06-06 | Elpochem AG | Polishing and deburring composition for workpieces of carbon steel and method of chemical polishing and deburring |
CA2767805A1 (en) * | 2009-07-06 | 2011-01-13 | Prestone Products Corporation | Methods and composition for cleaning a heat transfer system having an aluminum component |
GB2508827A (en) * | 2012-12-11 | 2014-06-18 | Henkel Ag & Co Kgaa | Aqueous compositions and processes for passivating and brightening stainless steel surfaces |
WO2018142810A1 (en) * | 2017-01-31 | 2018-08-09 | 三菱瓦斯化学株式会社 | Hydrogen peroxide aqueous solution for disinfection |
US11678433B2 (en) | 2018-09-06 | 2023-06-13 | D-Wave Systems Inc. | Printed circuit board assembly for edge-coupling to an integrated circuit |
US11647590B2 (en) | 2019-06-18 | 2023-05-09 | D-Wave Systems Inc. | Systems and methods for etching of metals |
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-
1991
- 1991-10-25 IT ITMI912845A patent/IT1251431B/en active IP Right Grant
-
1992
- 1992-10-23 BR BR9206668A patent/BR9206668A/en not_active Application Discontinuation
- 1992-10-23 DE DE69210622T patent/DE69210622T2/en not_active Expired - Fee Related
- 1992-10-23 EP EP92922319A patent/EP0609342B1/en not_active Expired - Lifetime
- 1992-10-23 CA CA002121691A patent/CA2121691A1/en not_active Abandoned
- 1992-10-23 JP JP5507462A patent/JPH07500378A/en active Pending
- 1992-10-23 ES ES92922319T patent/ES2089573T3/en not_active Expired - Lifetime
- 1992-10-23 WO PCT/EP1992/002442 patent/WO1993008317A1/en active IP Right Grant
- 1992-10-23 KR KR1019940701353A patent/KR100249061B1/en not_active IP Right Cessation
- 1992-10-23 US US08/211,964 patent/US5538152A/en not_active Expired - Fee Related
-
1994
- 1994-04-22 FI FI941893A patent/FI100727B/en active
Non-Patent Citations (1)
Title |
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See references of WO9308317A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2121691A1 (en) | 1993-04-29 |
KR100249061B1 (en) | 2000-04-01 |
US5538152A (en) | 1996-07-23 |
DE69210622D1 (en) | 1996-06-13 |
JPH07500378A (en) | 1995-01-12 |
ITMI912845A0 (en) | 1991-10-25 |
BR9206668A (en) | 1995-10-24 |
ES2089573T3 (en) | 1996-10-01 |
EP0609342B1 (en) | 1996-05-08 |
FI941893A (en) | 1994-06-01 |
WO1993008317A1 (en) | 1993-04-29 |
DE69210622T2 (en) | 1996-11-28 |
FI100727B (en) | 1998-02-13 |
FI941893A0 (en) | 1994-04-22 |
IT1251431B (en) | 1995-05-09 |
ITMI912845A1 (en) | 1993-04-25 |
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