CA2248568A1 - Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces - Google Patents
Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces Download PDFInfo
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- CA2248568A1 CA2248568A1 CA002248568A CA2248568A CA2248568A1 CA 2248568 A1 CA2248568 A1 CA 2248568A1 CA 002248568 A CA002248568 A CA 002248568A CA 2248568 A CA2248568 A CA 2248568A CA 2248568 A1 CA2248568 A1 CA 2248568A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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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
- 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
- C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
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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
- 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
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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Abstract
A thixotropic aqueous liquid composition suitable for deoxidizing and etching aluminum substrates, even if they are vertical to local gravity and not immersed in any container, contains fluoride ions, an acid with an ionization constant greater than that of HF, a viscosity increasing agent that preferably is a modified xanthan gum, and both anionic and nonionic surfactants. Preferably the composition also contains a colorant, so that the thickness of the coating applied to a substrate may be visually estimated.
Description
CA 02248~68 l998-09-09 Wo 98/30652 PCT/US97/00006 ACID DEOXIDIZING/ETCHING COMPOSITION AND PROCESS SUITABLE
FOR VERTICAL ALUMINUM SURFACES
Field of the Invention This invention relates to an improved composition and process for etching and/ordeoxidizing aluminum and aluminum alloy surfaces that may be at any angle to the local gravitational force of the earth and are not immersed in the composition. (Hereinafter, unless the context requires otherwise, the simple term "aluminum" is to be understood as including alloys cont~ining at least 50 % by weight of aluminum.) As a result, the compositions must have sufficient viscosity at low shear rates to resist flowing off the surfaces to which they are applied under the influence of the gravitational force of the earth.
10 Discussion of Related Art Common chemical and mechanicaJ treatments of aluminum often leave the surface with an oxide coating that must be removed before subsequent surface finishing steps can be satisfactorily completed. This process is generally known in the art as "deoxidizing" or, if the oxide coating is dark colored, alternatively as "desmutting". In order to assure full removal of the undesired oxide coating, the surface is often etched, i.e., some fraction, preferably a small one, of the metal of the surface itself is removed, along with the oxide layer on it.
For aluminum objects of sufficiently small size, a deoxidizing/etching process is normally accomplished by immersing the objects in a relatively low viscosity aqueous liquid, traditionally an aqueous acid solution including hexavalent chromium. This method is generally effective, but it can not be practically applied to large aircraft, rail cars, and the like which are too large to immerse in any available container. For such substrates a composition that will cling for a sufficient time to the entire surface to be deoxidized/etched, even if all or part of the surface is vertical to the local gravitational force of the earth, is needed.
DESCRIPTION OF THE INVENTION
Objects of the Invention A major object of the invention is to provide a new type of flow resistant deoxi-CA 02248~68 l998-09-09 dizing/etching eomposition that is improved with respeet to available prior art eounter-parts in at least one of the following desiderata: (1 ) an etching rate of 2.5 + 0.5 micromet-res per hour of exposure (hereinafter usually abbreviated as "~lm/hr") on all parts of an aluminum surfaee to whieh it is applied; (2) minim:~l etch of titanium or ferriferous sur-faces, whieh are often adjacent to alurninum surfaees desired to be deoxidized and diffi-cult to protect completely against some exposure to the eomposition applied to deoxidize neighboring aluminum parts of a eomposite structure; (3) easy visual detection of the presenee of the composition on a large aluminum strueture being treated with it; (4) fac-ile removal of the composition when its desired aetion is complete by an at least predom-10 inantly aqueous rinsing liquid; (5) effective removal of any moderate amounts of organiecont;~min~nts that may be on the aluminum surface to be deoxidized; (6) facile wetting of and/or spreading over ahlminum surfaees to be treated with the eomposition; (7) uni-formity of visual appearance of the substrate surfaee after treatment with the composition; and (8) minim~l pollution from the compositions. Other objeets will be ap-parent from the deseription below.General Principles of Deseription Exeept in the elaims and the speeific examples, or where otherwise expressly in-dieated~ all numerieal quantities in this deseription indieating amounts of material or eon-ditions of reaetion and/or use are to be understood as modified by the word "about" in describing the broadest seope of the invention. Praetiee within the numerieal limits stat-ed is generally preferred, however. Also, unless expressly stated or necessarily implied h! the context to the contrary: percent, "parts of", and ratio values are by weight; the term "polymer" includes "oligomer", "copolymer", "terpolymer", and the like; the first definition or description of the meaning of a word, phrase, aeronym, abbreviation or the like applies to all subsequent uses of the same word, phrase, acronym, abbreviation or the like and applies, mutatis mutandis, to normal grammatical variations thereof; the deseription of a group or class of materials as suitable or preferred for a given purpose in eonnection with the invention implies that mixtures of any two or more of the mem-bers of the group or class are equally suitable or preferred; specifications in chemical terms of materials in compositions refer to the materials at the time of addition to any composition so specified, and do not necessarily exelude the possibility of reaction between sueh materials and other materials already present in the eomposition at the time CA 02248~68 l998-09-09 of addition of the specified materials; specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole; and any counterions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; oth-erwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects of the invention.
Summary of the Invention It has been discovered that the above stated object of the invention can be achieved with a viscous liquid composition that comprises, preferably consists essentially of, or more preferably consists of, water and:
(A) an amount of a source of dissolved fluoride ions;
(B) an amount of a source of an acid with a larger ionization constant than hydro-fluoric acid;
(C) an amount of a viscosity increasing agent that is not part of any of the previously recited components;
(D) an amount of anionic surfactant that is not part of any of the previously recited components;
(E) an amount of nonionic surfactant that is not part of any of the previously recited components; and, optionally, one or more of the following:
20 (F) a hydrotroping agent that is not part of any of the previously recited components;
(G) a coloring agent that is not part of any of the previously recited components;
(H) a biocidal agent that is not part of any of the previously recited components; and (J) an oxidizing agent that is not part of any of the previously recited components.
Another embodiment of the invention is a process comprising, preferably consist ing essentially of, or more preferably consisting of, at least steps of:
(I) forming on an aluminum substrate surface to be deoxidized/etched a coating of a viscous liquid composition according to the invention as described above;
(II) m~int~ining in place the coating formed in step (I) for a time sufficient to deoxi-dize/etch the aluminum substrate surface; and 30 (III) subsequently removing the coating of viscous liquid composition formed in step (I) from further contact with the aluminum substrate surface.
Other steps, including those conventional per se, may be included in a process according CA 02248568 l998-09-09 WO 981306~2 PCT/USg7/00006 to the invention along with these necessary steps.
Other embodiments of the invention include substrates prepared by a process ac-cording to the invention as described above, the use of such substrates in any application to which aluminum articles are adapted? and the like.
Detailed Description of the Invention~ Including Preferred Embodiments For various reasons, it is often preferred that compositions according to the inven-tion be substantially free from various constituents that can cause practical difficulties when present. More particularly, with increasing preference in the order given and with independent pl~relellce for each noted component, compositions according to the inven-10 tion preferably contain no more than 4.0, 2.2, 0.90, 0.50, 0.20, 0.12, 0.070, 0.030, 0.010,0.0050, 0.0020, 0.0010, 0.00050, 0.00020, or 0.00010 grams of constituent per kilogram of total composition (hereinafter usually abbreviated as "g/kg") of any of the following:
metal cations with a valence of 2 or higher; chloride, bromide, or iodide ions (which can cause pitting corrosive attack on aluminum); any anions containing a metallic element in a valence state of +3 or more; organic peroxides; halate or perhalate anions; and any organic molecules containing at least two but not more than twelve moieties selected from the group consisting of hydroxyl, amino, phosphino, carboxyl, and carboxylate moieties, wherein any two of said at least two but not more than twelve moieties are separated from each other by exactly 2 or 3 other atoms within the organic molecule, so that a chelate complex can readily be forrned between the organic molecules and metal ions.
Fluoride ions component (A) is preferably supplied by one or more substances selected from hydrofluoric acid and all of its water soluble salts, including fully and partially neutralized salts, and the stoichiometric equivalent as fluoride of all of these dissolved materials present in the composition is to be considered as part of component (A), irrespective of the actual extent of ionization existing in the composition. Inasmuch as "free fluoride" is needed to achieve the levels of etching speed desired, complex fluoride anions such as fluoborate, fluotitanate, fluosilicate, and fluozirconate are not considered part of component (A) if present in a composition according to the invention and preferably, at least for reasons of economy, are not present at all. Ammonium and alkali metal fluorides and/or bifluorides are preferred and arnmonium fluoride and/or bifluoride is most preferred.
CA 02248~68 l998-09-09 Irrespective of the source, the amount of fluoride ions present in a working com-position according to the invention preferably is at least, with increasing preference in the order given, 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, 14.0, 16.0, 17.0, or 18.0 grams per kilogram of total composition (hereinafter usually abbreviated as "g/kg") and independently pref-erably is not more than, with increasing prer~lence in the order given, 60, 50, 40, 35, 30,28, 26, 24, 22, 20.07 or 19.0 g/kg.
Component (B) of strong acid is, primarily for reasons of economy, preferably selected from inexpensive strong mineral acids such as sulfuric7 hydrochloric, and nitric acids, with sulfuric most preferred. Irrespective of the source, the amount of acid from 10 component (B) in a working composition according to the invention preferably is such as to provide at least, with increasing preference in the order given, 0.080, 0.15, 0.30, 0.40, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.78 moles of ionized hydrogen atoms per kilogram of total composition (hereinafter usually abbreviated as "mH/kg") and independently preferably to provide not more than, with increasing preference in the order given, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.2, 1.0, or 0.80 mH/kg. In calculating these amounts of hydrogen ions for known chemical compositions, all of the hydrogen atoms of any acid present that ionize with a larger ionization constant than hydrofluoric acid are assumed to be completely ionized. Thus, for example, both hydrogen atoms of eachdissolved H2SO4 molecule are assumed to be ionized, because the second ionization constant of sulfuric acid is 0.012 while that for HF is only 0.00072. For H3PO4, however, only its first ionization constant is greater than that for HF, so that only one hydrogen would be assumed to ionize from this molecule.
Independently of their separate amounts, the amount of ionized hydrogen ions in mH/kg preferably has a ratio to the amount of fluoride in g/kg that is at least, with in-creasing preference in the order given, 0.0040:1.0, 0.0060:1.0, 0.0080:1.0, 0.0100:1.0,0.015:1.0, 0.020:1.0, 0.025:1.0, 0.030:1.0, 0.035:1.0, 0.038:1.0, 0.040:1.0, or 0.042:1.0 and independently preferably is not more than 0.40:1.0, 0.30:1.0, 0.20:1.0, 0.15:1.0, 0.10:1.0, 0.090:1.0, 0.080:1.0, 0.070:1.0, 0.060:1.0, 0.055:1.0, 0.050:1.0, or 0.045:1Ø
A working liquid substrate coating composition according to this invention pref-erably is highly thixotropic, i.e., it preferably has a relatively high viscosity when begin-ning to be disturbed from a motionless state, but becomes relatively low in viscosity when subjected to stronger forces, so that it may readily be applied by convenient meth-CA 02248~68 l998-09-09 Wo 98/30652 PCT/US97/00006 ods such as spraying, dipping, brushing, and the like to a substrate to be protected, to form a coating that will remain in place against the influence of natural gravity without becoming thinned to an undesirable degree. The thixotropy may convenient}y be mea-sured by means of a well known type of instrument, a Brookfield viscometer, using spindle # 4. The viscosity at 25 ~C of a viscous liquid working composition according to the invention measured in this way, when measured at 0.5 revolution per minute (hereinafter usually abbreviated as "rpm") preferably is at least, with increasing preference in the order given, l O0, 200,300, 400, 500, 600, 650, 700, 750, 800, 850, 870, 890, or 910 poises (hereinafter usually abbreviated as "ps"); independently preferably is, 10 when measured at 2.5 rpm~ at least, with increasing preference in the order given, 25, 50, 75, 100, 150, 200, 250, 300, 350~ 370, 390~ or 400 ps; and also independently preferably is, when measured at 20 rpm~ not more than, with increasing preference in the order given~ 400, 350, 300, 250, 210, 170, 130, 105, lO0, 95, 90, or 86 ps.
A wide variety of natural and synthetic materials, such as natural gums and other 15 polysaccharides, various synthetic polymers, and finely divided inorganic solids such as certain clays and silica sols, are known in the art for achieving thixotropy and may be used in a composition according to the invention. The most preferred material for com-ponent (C) is xanthan gum, preferably a type of this gum which has been modified from its natural state to result in smoother flow properties at low shear rates, as described in 20 more detail in connection with the working examples according to the invention below.
For any viscosity modifying component, the amount preferably should be selected to achieve preferable values of viscosities at various measuring speeds as already specified above. For the preferred modified xanthan gum as noted above, along with other pre-ferred types and amounts of components (A) and (B), the concentration of the modified 25 xanthan gum in a viscous liquid working composition according to the invention prefer-ably is at least, with increasing preference in the order given? 2.0, 4.0, 6.0, 8.0, 10.0,12.0, 14.0, 15.0, 16.0, 17.0, 18.0, l9.0, 20.0, 21.0, or 22.0 g/kg and independently preferably is not more than, with increasing preference in the order given, 150, 125, 100, 80, 60, 50, 40, 30, 25.0, or 22.5 g/kg.
A wide variety of commercially available and other known materials are suitable for component (D) of anionic surfactants. Examples include sulfonic acids, partial esters of sulfuric and phosphoric acids, and the like, and salts of all of these acids, in each CA 02248~68 l998-09-09 instance selected from molecules that contain a hydrophobic moiety cont~ining from 8 to 22, more preferably from 10 to 20, or still more preferabiy from 12 to 18, carbon atoms and not more than, with increasing preference in the order given, 5, 3, 2, 1, or 0 atoms other than carbon, hydrogen, and halogen atoms. Largely for reasons of economy, sulfonic acids, partial esters of sulfuric acid, and salts of both these types of are preferred.
Linear alkylbenzene sulfonic acids and their corresponding sulfonates are most preferred for component (D). The amount of component (D) in a working composition according to the invention preferably is at least, with increasing preference in the order given, 2, 4, 6, 8, 10? 1 1.0, 12.0, 13.0, 14.0, 15.0, or 15.8 g/kg and independently preferably is not 10 more than, with increasing preference in the order given, 75, 60, 50, 40, 35, 30, 25, 23, 21, 19, 18.0, 17.0, 16.5 or 16.2 g/kg.
As with component (D), a wide variety of commercially available and other known surfactants are suitable for component (E) of non-ionic surfactant. Preferred molecules for component (E) conform to the general chemical formula (I):
RlO(CH7CH2O)y(CH2CHCH3O)zH (I) where R' is a moiety selected from the group consisting of saturated-and-unsaturated straight-and-branched-chain-aliphatic-monovalent-hydrocarbon-moiety-substituent -bearing phenyl moieties in which the aromatic ring of the phenyl moiety is directly bond-ed to the oxygen atom appearing immediately after the R' symbol in formula (II); y is a positive integer; and z is zero, one, or two. More preferably, independently for each preference stated, z is 1 or 0, most preferably zero; the aliphatic monovalent hydrocarbon moiety substituent in R' has at least, with increasing preference in the order given, 5, 6, 7, 8, or 9 carbon atoms and independently preferably has not more than, with increasing preference in the order given, 12, 11, 10, or 9 carbon atoms; the aliphatic monovalent hydrocarbon moiety substituent in R' is straight chain rather than branched; and the average value of y is at least, with increasing preference in the order given, 3, 4, 5, 6, 7, or 8 and independently preferably is not more than, with increasing preference in the order given, 16,15,14,13, 12,1 1,10, or 9.
Independently of its specific chemical composition, the amount of component (E) in a composition according to the invention preferably is such that it has a ratio to the amount of component (D), measured in the same units, in the same composition that is at least, with increasing preference in the order given, 0.015:1.0, 0.030:1.0, 0.045:1.0, CA 02248~68 l998-09-09 W O 98/30652 PCT~US97/00006 0.060:1.0, 0.075:1.0, 0.090:1.0, 0.100:1.0, 0.110:1.0, 0.115:1.0, 0.120:1.0, or 0.123:1.0 and independently preferably is not more than, with increasing preference in the order given, 2.0:1.0, 1.5:1.0, 1.0:1.0, 0.50:1.0, 0.40:1.0, 0.30:1.0, 0.25:1.0, 0.20:1.0, 0.1~:1.0, 0.16:1.0, 0.150:1.0, 0.140:1.0, or 0.130:1Ø
The presence of optional hydrotroping agent component (F) is generally preferredin concentrates according to the invention. Conventional hydrotroping agents such as the salts of alkyl benzene sulfonic acids, particularly of cumene sulfonic acid, are suitable for compositions according to this invention and are generally preferred for reasons of economy. However, if very low tolerances for residual sulfur on the deoxidized surface are prescribed, at least one of two other types of hydrotropes are then preferred: (i) organic phosphate esters and (ii) alkyl and alkenyl substituted cyclic acid anhydrides, particularly the anhydrides of C4 6 terminal dicarboxylic acids substituted with alkyl or alkenyl groups having 6 to 20 carbon atoms. Particularly preferred examples of this type of hydrotrope are octenyl and nonenyl succinic anhydrides.
The amount of hyd~ vping agent, when it is used at all, is preferably such as tohave a ratio to the amount of component (E), measured in the sarne units, that is at least, with increasing preference in the order given, 2:1.0, 4:1.0, 6:1.0, or 8:1.0 and independ-ently, primarily for reasons of economy, preferably is not more than, with increasing preference in the order given, 25:1.0, 20:1.0, 15:1.0, 13:1.0, 1 1:1.0, or 9:1.0, with the higher ratios within this range generally preferred for very highly concentratedcompositions according to this invention and lower ratios, including omission of any hy-drotroping agent at all, often satisfactory for working compositions.
Optional colorant component (G) is often preferred in a composition according to this invention, to serve as a visual indicator of the thickness of the coating applied to a substrate surface with a complicated shape and thereby make it easier to achieve the usual goal of an approximately equally thick coating over the entire surface to be deoxi-dized/etched. Numerous conventional dyes and/or pigments, as known to those skilled in the art, may be used for component (G).
Optional biocidal component (H) is not normally needed, but may be preferably present in a liquid composition according to the invention in an amount effective to re-press the biodegradation of any of the components of the composition, when the compo-sition is used in an environment in which acid-tolerant microorg~ni~m~ are prevalent.
CA 02248~68 1998-09-09 WO 98/306~2 - PCT/US97/00006 Optional oxidizing agent component (J) is not normally needed, but may be useful to accelerate the etching process on some substrates. Hydrogen peroxide is preferred when this component is used; it also has some biocidal activity and may be used for that purpose as part of component (H).
sIn preparing the compositions according to this invention, it is preferable to add the viscosity increasing agent to water before adding any of the other ingredients. If this is not done, long term viscosity instability may be experienced.
Preferably a substrate to be deoxidized and/or etched in a process according to this invention should be cleaned to remove most gross soils before being exposed to a 10composition according to this invention as described above.
A process according to the invention is normally performed at ambient tempera-ture, if for no other reason than that m~int~ining a different temperature would be a con-siderable practical difficulty in view of the large size of the substrates usually treated.
A contact time from 1 to 20 minutes, or more preferably from 8 to 12 minutes, is5normally preferred in a process according to this invention.
The invention may be further appreciated by consideration of the following ex-amples and comparison examples.
Materials Used BRIJTM 35 surfactant was obtained commercially from ICI Americas, Inc. and is 20reported by its supplier to consist of ethoxylates of lauryl alcohol with an average of 23 moles of ethylene oxide per mole of lauryl alcohol.
CAB-O-SILTM M5 dispersion of finely divided silica in water was obtained com-mercially from Cabot Corp. and is recommended as a viscosity increasing agent CALSOFTTM LAS 99 surfactant was supplied by Van Waters and Rogers, 25Icirklzlnfl~ Washington and is reported by its supplier to be linear alkyl benzene sulfonate.
KELZANTM AR xanthan gum powder was commercially obtained from the Kelco division of Merck & Co., Inc. and is reported by its supplier to contain 86 - 92 % solids of xanthan gum (which is constituted of polymers of ~-l ,4-linked D-glucose units) that has been modified to give lower viscosity at low shear rates than unmodified natural xan-30than gum. For example, a solution of 0.3 % of each of potassium chloride and KEL-ZANTM AR in water has a viscosity of about 800 centipoises (hereinafter usually abbreviated as "cps") at a shear rate of 0. l reciprocal seconds (hereinafter usually abbre-CA 02248~68 l998-09-09 WO 98/306s2 PCT/US97/00006 viated as "sec~"'), whereas an otherwise identical solution of natural xanthan gum has a viscosity of almost l 0,000 cps. At a shear rate of l 0 sec-', the viscosities of these solu-tions are about l 00 and 500 cps respectively.
NAXONATETM SC hydrotroping agent was obtained commercially from Ruet-gers-Nease Chemical Co., Inc., Ross, Ohio and was reported by its supplier to be 93 %
sodium cumene sulfonate.
TRITONTM N-l01 surfactant was commercially supplied by Van Waters and Rogers, Kirkland, Washington and was reported by its supplier to be a nonionic surfactant consisting of ethoxylated nonylphenol molecules with residues from an10 average of 9.5 molecules of ethylene oxide per molecule of surfactant;
UNISPERSETM Blue colorant was obtained commercially from Ciba-Geigy as a paste. It is reported by its supplier to contain about 50 % of copper phthalocyanine blue pigment in dispersion.
VEEGUMTM T was obtained commercially from R. T. Vanderbilt Co., Norwalk, Connecticut and is reported by its supplier to be hydrated magnesium aluminosilicate smectite clay. It is recommended as a viscosity increasing agent.
Working Coating Compositions and Processes Therewith Example and comparison example working compositions are set forth in Table l below. Blank cells in the table indicate that none of the material was added to the com-position, or that the property value that would properly appear in the cell was notmeasured. The viscosities reported in Table l were measured with a Brookfieldviscosimeter using spindle # 4. The balance of each composition not shown in Table l was water.
In the lower part of Table l, etch rates and times of exposure that achieved satisfactory deoxidizing/etching with some of the working compositions are also shown.
W 0 98/30652 PCTrUS97/00006 INGREDIENT PERCENT BY WEIGHT OF INGREDIENT IN COMPOSITION NUMBE~:
Ammonium 1.4 1.4 2.8 2.8 2.8 2.8 4.2 4.2 Bifluoride H2SO4,96.5 % 2.0 2.0 4.0 4.0 4.0 4.0 6.0 6.0 CAB-O-SILTM M5 4.0 4.0 KELZANTM AR 2.0 2.5 3.0 2.5 3.0 VEEGUMTM T
CALSOFTTM LAS 99 0.80 0.80 1.60 1.60 1.60 1.60 2.40 2.40 BRIJTM 35 1.0 1.0 TRITONTM N-101 0.10 0.10 0.20 0.20 0.20 0.20 0.30 0.30 NAXONATETM SC 0.40 0.40 0.80 0.80 0.80 0.80 1.20 1.20 30 % H202 in water UNISPERSET''' BIUC 0.0050.005 0.005 0.005 0 005 VISCOSITY IN POISES
NIIMBER:
At 20 RPM 14 6.7 22.6 85.2 At 10 RPM 145 131 166 At 5.0 RPM 246 At 2.5 RPM 410 480 At 1.0 RPM 652 At 0.5 RPM 920 PROCESS CIIARACTER_ ISTICS
Minutes of Contact 20 20 20 20 Etch Rate, ~lm/hr 0.38 2.67 2.84 3.5 Abbreviation in Table 1: "RPM" means "Revolutions per Minute"
... Ihis table is continued on the next page....
TABLE I continued INGREDIENT PERCENT BY WEIGHT OF INGREDIENT IN COMPOSITION NUMBER:
Ammonium 5.6 5.6 5.6 6.7 6.9 2.8 5.6 6.7 Bifluoride H2SO4,96.5 % 8.0 8.0 8.0 9.6 9.8 4.0 8.0 9.6 CAB-O-SILTM M5 4.0 KELZANTM AR 2.0 2.5 3.0 2.0 2.0 VEEGUMTM T 4.0 4 0 CALSOFl'rM LAS 3.2 3.2 3.2 3.8 3.92 ].6 3.2 3.8 TRITONTM N-101 0.40 0.40 0.40 0.48 0.49 0.20 0.40 0.48 NAXONATETM SC 1.60 1.60 1.60 1.92 1.96 0.80 1.60 1.92 30 % H2O2 in water 2.0 4.0 4.8 UNISPERSETM 0.005 0.005 0 005 0.0050.005 0 005 0 005 Blue POISES OF
COMPOSITION
NIJMBER:
At20RPM 11.5 < 1 91 14 11.5 < 1 At 10 RPM 13] 194 At 5.0 RPM
At 2.5 RPM
At 1.0 RPM
At 0.5 RPM
PROCESS
CHARACTERISTICS
Minutesof 20 20 20 20 20 Contact Etch Rate, ~m/hr 4.7 4.3 4.9 1.1 18.5 CA 02248~68 l998-09-09 W O 98/30652 PCT~US97/00006 The coatings were formed for these examples simply by immersing the test panels in the composition and then withdrawing them after a few seconds, with no deliberate aid or hindrance to drainage of the composition from the panel surface. The coated panel was then held with its highest area surfaces vertical for the contact time indicated in the Table. The viscous liquid coating over the panel surfaces was then rinsed away with water. Panels had been weighed before applying the working composition and were weighed again after this rinsing and subsequent drying to determine the mass loss which was converted to an etch rate by the usual mathematical calculations (i.e., dividing the total mass loss for the panel by the area of the panel to determine loss per unit area, then 1C dividing the loss per unit area by the density of the panel to determine the thickness of metal corresponding to the mass loss.) Some of the panels treated, instead of being dried to determine etch rates, weretreated after rinsing with a commercially available composition (ALOD~NE~) 1000 Chromate Conversion Coating Liguid, available from the Parker Amchem Division ofHenkel Corp., Madison Heights, Michigan) to produce a conventional chromate conver-sion coating on the panel surfaces. The coatings produced are fully as good in properties as those produced by using the same treatment on otherwise identical panels that had been deoxidized/etched by a conventional high quality, low viscosity liquid composition for use by immersion of the substrates being treated.
FOR VERTICAL ALUMINUM SURFACES
Field of the Invention This invention relates to an improved composition and process for etching and/ordeoxidizing aluminum and aluminum alloy surfaces that may be at any angle to the local gravitational force of the earth and are not immersed in the composition. (Hereinafter, unless the context requires otherwise, the simple term "aluminum" is to be understood as including alloys cont~ining at least 50 % by weight of aluminum.) As a result, the compositions must have sufficient viscosity at low shear rates to resist flowing off the surfaces to which they are applied under the influence of the gravitational force of the earth.
10 Discussion of Related Art Common chemical and mechanicaJ treatments of aluminum often leave the surface with an oxide coating that must be removed before subsequent surface finishing steps can be satisfactorily completed. This process is generally known in the art as "deoxidizing" or, if the oxide coating is dark colored, alternatively as "desmutting". In order to assure full removal of the undesired oxide coating, the surface is often etched, i.e., some fraction, preferably a small one, of the metal of the surface itself is removed, along with the oxide layer on it.
For aluminum objects of sufficiently small size, a deoxidizing/etching process is normally accomplished by immersing the objects in a relatively low viscosity aqueous liquid, traditionally an aqueous acid solution including hexavalent chromium. This method is generally effective, but it can not be practically applied to large aircraft, rail cars, and the like which are too large to immerse in any available container. For such substrates a composition that will cling for a sufficient time to the entire surface to be deoxidized/etched, even if all or part of the surface is vertical to the local gravitational force of the earth, is needed.
DESCRIPTION OF THE INVENTION
Objects of the Invention A major object of the invention is to provide a new type of flow resistant deoxi-CA 02248~68 l998-09-09 dizing/etching eomposition that is improved with respeet to available prior art eounter-parts in at least one of the following desiderata: (1 ) an etching rate of 2.5 + 0.5 micromet-res per hour of exposure (hereinafter usually abbreviated as "~lm/hr") on all parts of an aluminum surfaee to whieh it is applied; (2) minim:~l etch of titanium or ferriferous sur-faces, whieh are often adjacent to alurninum surfaees desired to be deoxidized and diffi-cult to protect completely against some exposure to the eomposition applied to deoxidize neighboring aluminum parts of a eomposite structure; (3) easy visual detection of the presenee of the composition on a large aluminum strueture being treated with it; (4) fac-ile removal of the composition when its desired aetion is complete by an at least predom-10 inantly aqueous rinsing liquid; (5) effective removal of any moderate amounts of organiecont;~min~nts that may be on the aluminum surface to be deoxidized; (6) facile wetting of and/or spreading over ahlminum surfaees to be treated with the eomposition; (7) uni-formity of visual appearance of the substrate surfaee after treatment with the composition; and (8) minim~l pollution from the compositions. Other objeets will be ap-parent from the deseription below.General Principles of Deseription Exeept in the elaims and the speeific examples, or where otherwise expressly in-dieated~ all numerieal quantities in this deseription indieating amounts of material or eon-ditions of reaetion and/or use are to be understood as modified by the word "about" in describing the broadest seope of the invention. Praetiee within the numerieal limits stat-ed is generally preferred, however. Also, unless expressly stated or necessarily implied h! the context to the contrary: percent, "parts of", and ratio values are by weight; the term "polymer" includes "oligomer", "copolymer", "terpolymer", and the like; the first definition or description of the meaning of a word, phrase, aeronym, abbreviation or the like applies to all subsequent uses of the same word, phrase, acronym, abbreviation or the like and applies, mutatis mutandis, to normal grammatical variations thereof; the deseription of a group or class of materials as suitable or preferred for a given purpose in eonnection with the invention implies that mixtures of any two or more of the mem-bers of the group or class are equally suitable or preferred; specifications in chemical terms of materials in compositions refer to the materials at the time of addition to any composition so specified, and do not necessarily exelude the possibility of reaction between sueh materials and other materials already present in the eomposition at the time CA 02248~68 l998-09-09 of addition of the specified materials; specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole; and any counterions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; oth-erwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects of the invention.
Summary of the Invention It has been discovered that the above stated object of the invention can be achieved with a viscous liquid composition that comprises, preferably consists essentially of, or more preferably consists of, water and:
(A) an amount of a source of dissolved fluoride ions;
(B) an amount of a source of an acid with a larger ionization constant than hydro-fluoric acid;
(C) an amount of a viscosity increasing agent that is not part of any of the previously recited components;
(D) an amount of anionic surfactant that is not part of any of the previously recited components;
(E) an amount of nonionic surfactant that is not part of any of the previously recited components; and, optionally, one or more of the following:
20 (F) a hydrotroping agent that is not part of any of the previously recited components;
(G) a coloring agent that is not part of any of the previously recited components;
(H) a biocidal agent that is not part of any of the previously recited components; and (J) an oxidizing agent that is not part of any of the previously recited components.
Another embodiment of the invention is a process comprising, preferably consist ing essentially of, or more preferably consisting of, at least steps of:
(I) forming on an aluminum substrate surface to be deoxidized/etched a coating of a viscous liquid composition according to the invention as described above;
(II) m~int~ining in place the coating formed in step (I) for a time sufficient to deoxi-dize/etch the aluminum substrate surface; and 30 (III) subsequently removing the coating of viscous liquid composition formed in step (I) from further contact with the aluminum substrate surface.
Other steps, including those conventional per se, may be included in a process according CA 02248568 l998-09-09 WO 981306~2 PCT/USg7/00006 to the invention along with these necessary steps.
Other embodiments of the invention include substrates prepared by a process ac-cording to the invention as described above, the use of such substrates in any application to which aluminum articles are adapted? and the like.
Detailed Description of the Invention~ Including Preferred Embodiments For various reasons, it is often preferred that compositions according to the inven-tion be substantially free from various constituents that can cause practical difficulties when present. More particularly, with increasing preference in the order given and with independent pl~relellce for each noted component, compositions according to the inven-10 tion preferably contain no more than 4.0, 2.2, 0.90, 0.50, 0.20, 0.12, 0.070, 0.030, 0.010,0.0050, 0.0020, 0.0010, 0.00050, 0.00020, or 0.00010 grams of constituent per kilogram of total composition (hereinafter usually abbreviated as "g/kg") of any of the following:
metal cations with a valence of 2 or higher; chloride, bromide, or iodide ions (which can cause pitting corrosive attack on aluminum); any anions containing a metallic element in a valence state of +3 or more; organic peroxides; halate or perhalate anions; and any organic molecules containing at least two but not more than twelve moieties selected from the group consisting of hydroxyl, amino, phosphino, carboxyl, and carboxylate moieties, wherein any two of said at least two but not more than twelve moieties are separated from each other by exactly 2 or 3 other atoms within the organic molecule, so that a chelate complex can readily be forrned between the organic molecules and metal ions.
Fluoride ions component (A) is preferably supplied by one or more substances selected from hydrofluoric acid and all of its water soluble salts, including fully and partially neutralized salts, and the stoichiometric equivalent as fluoride of all of these dissolved materials present in the composition is to be considered as part of component (A), irrespective of the actual extent of ionization existing in the composition. Inasmuch as "free fluoride" is needed to achieve the levels of etching speed desired, complex fluoride anions such as fluoborate, fluotitanate, fluosilicate, and fluozirconate are not considered part of component (A) if present in a composition according to the invention and preferably, at least for reasons of economy, are not present at all. Ammonium and alkali metal fluorides and/or bifluorides are preferred and arnmonium fluoride and/or bifluoride is most preferred.
CA 02248~68 l998-09-09 Irrespective of the source, the amount of fluoride ions present in a working com-position according to the invention preferably is at least, with increasing preference in the order given, 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, 14.0, 16.0, 17.0, or 18.0 grams per kilogram of total composition (hereinafter usually abbreviated as "g/kg") and independently pref-erably is not more than, with increasing prer~lence in the order given, 60, 50, 40, 35, 30,28, 26, 24, 22, 20.07 or 19.0 g/kg.
Component (B) of strong acid is, primarily for reasons of economy, preferably selected from inexpensive strong mineral acids such as sulfuric7 hydrochloric, and nitric acids, with sulfuric most preferred. Irrespective of the source, the amount of acid from 10 component (B) in a working composition according to the invention preferably is such as to provide at least, with increasing preference in the order given, 0.080, 0.15, 0.30, 0.40, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.78 moles of ionized hydrogen atoms per kilogram of total composition (hereinafter usually abbreviated as "mH/kg") and independently preferably to provide not more than, with increasing preference in the order given, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.2, 1.0, or 0.80 mH/kg. In calculating these amounts of hydrogen ions for known chemical compositions, all of the hydrogen atoms of any acid present that ionize with a larger ionization constant than hydrofluoric acid are assumed to be completely ionized. Thus, for example, both hydrogen atoms of eachdissolved H2SO4 molecule are assumed to be ionized, because the second ionization constant of sulfuric acid is 0.012 while that for HF is only 0.00072. For H3PO4, however, only its first ionization constant is greater than that for HF, so that only one hydrogen would be assumed to ionize from this molecule.
Independently of their separate amounts, the amount of ionized hydrogen ions in mH/kg preferably has a ratio to the amount of fluoride in g/kg that is at least, with in-creasing preference in the order given, 0.0040:1.0, 0.0060:1.0, 0.0080:1.0, 0.0100:1.0,0.015:1.0, 0.020:1.0, 0.025:1.0, 0.030:1.0, 0.035:1.0, 0.038:1.0, 0.040:1.0, or 0.042:1.0 and independently preferably is not more than 0.40:1.0, 0.30:1.0, 0.20:1.0, 0.15:1.0, 0.10:1.0, 0.090:1.0, 0.080:1.0, 0.070:1.0, 0.060:1.0, 0.055:1.0, 0.050:1.0, or 0.045:1Ø
A working liquid substrate coating composition according to this invention pref-erably is highly thixotropic, i.e., it preferably has a relatively high viscosity when begin-ning to be disturbed from a motionless state, but becomes relatively low in viscosity when subjected to stronger forces, so that it may readily be applied by convenient meth-CA 02248~68 l998-09-09 Wo 98/30652 PCT/US97/00006 ods such as spraying, dipping, brushing, and the like to a substrate to be protected, to form a coating that will remain in place against the influence of natural gravity without becoming thinned to an undesirable degree. The thixotropy may convenient}y be mea-sured by means of a well known type of instrument, a Brookfield viscometer, using spindle # 4. The viscosity at 25 ~C of a viscous liquid working composition according to the invention measured in this way, when measured at 0.5 revolution per minute (hereinafter usually abbreviated as "rpm") preferably is at least, with increasing preference in the order given, l O0, 200,300, 400, 500, 600, 650, 700, 750, 800, 850, 870, 890, or 910 poises (hereinafter usually abbreviated as "ps"); independently preferably is, 10 when measured at 2.5 rpm~ at least, with increasing preference in the order given, 25, 50, 75, 100, 150, 200, 250, 300, 350~ 370, 390~ or 400 ps; and also independently preferably is, when measured at 20 rpm~ not more than, with increasing preference in the order given~ 400, 350, 300, 250, 210, 170, 130, 105, lO0, 95, 90, or 86 ps.
A wide variety of natural and synthetic materials, such as natural gums and other 15 polysaccharides, various synthetic polymers, and finely divided inorganic solids such as certain clays and silica sols, are known in the art for achieving thixotropy and may be used in a composition according to the invention. The most preferred material for com-ponent (C) is xanthan gum, preferably a type of this gum which has been modified from its natural state to result in smoother flow properties at low shear rates, as described in 20 more detail in connection with the working examples according to the invention below.
For any viscosity modifying component, the amount preferably should be selected to achieve preferable values of viscosities at various measuring speeds as already specified above. For the preferred modified xanthan gum as noted above, along with other pre-ferred types and amounts of components (A) and (B), the concentration of the modified 25 xanthan gum in a viscous liquid working composition according to the invention prefer-ably is at least, with increasing preference in the order given? 2.0, 4.0, 6.0, 8.0, 10.0,12.0, 14.0, 15.0, 16.0, 17.0, 18.0, l9.0, 20.0, 21.0, or 22.0 g/kg and independently preferably is not more than, with increasing preference in the order given, 150, 125, 100, 80, 60, 50, 40, 30, 25.0, or 22.5 g/kg.
A wide variety of commercially available and other known materials are suitable for component (D) of anionic surfactants. Examples include sulfonic acids, partial esters of sulfuric and phosphoric acids, and the like, and salts of all of these acids, in each CA 02248~68 l998-09-09 instance selected from molecules that contain a hydrophobic moiety cont~ining from 8 to 22, more preferably from 10 to 20, or still more preferabiy from 12 to 18, carbon atoms and not more than, with increasing preference in the order given, 5, 3, 2, 1, or 0 atoms other than carbon, hydrogen, and halogen atoms. Largely for reasons of economy, sulfonic acids, partial esters of sulfuric acid, and salts of both these types of are preferred.
Linear alkylbenzene sulfonic acids and their corresponding sulfonates are most preferred for component (D). The amount of component (D) in a working composition according to the invention preferably is at least, with increasing preference in the order given, 2, 4, 6, 8, 10? 1 1.0, 12.0, 13.0, 14.0, 15.0, or 15.8 g/kg and independently preferably is not 10 more than, with increasing preference in the order given, 75, 60, 50, 40, 35, 30, 25, 23, 21, 19, 18.0, 17.0, 16.5 or 16.2 g/kg.
As with component (D), a wide variety of commercially available and other known surfactants are suitable for component (E) of non-ionic surfactant. Preferred molecules for component (E) conform to the general chemical formula (I):
RlO(CH7CH2O)y(CH2CHCH3O)zH (I) where R' is a moiety selected from the group consisting of saturated-and-unsaturated straight-and-branched-chain-aliphatic-monovalent-hydrocarbon-moiety-substituent -bearing phenyl moieties in which the aromatic ring of the phenyl moiety is directly bond-ed to the oxygen atom appearing immediately after the R' symbol in formula (II); y is a positive integer; and z is zero, one, or two. More preferably, independently for each preference stated, z is 1 or 0, most preferably zero; the aliphatic monovalent hydrocarbon moiety substituent in R' has at least, with increasing preference in the order given, 5, 6, 7, 8, or 9 carbon atoms and independently preferably has not more than, with increasing preference in the order given, 12, 11, 10, or 9 carbon atoms; the aliphatic monovalent hydrocarbon moiety substituent in R' is straight chain rather than branched; and the average value of y is at least, with increasing preference in the order given, 3, 4, 5, 6, 7, or 8 and independently preferably is not more than, with increasing preference in the order given, 16,15,14,13, 12,1 1,10, or 9.
Independently of its specific chemical composition, the amount of component (E) in a composition according to the invention preferably is such that it has a ratio to the amount of component (D), measured in the same units, in the same composition that is at least, with increasing preference in the order given, 0.015:1.0, 0.030:1.0, 0.045:1.0, CA 02248~68 l998-09-09 W O 98/30652 PCT~US97/00006 0.060:1.0, 0.075:1.0, 0.090:1.0, 0.100:1.0, 0.110:1.0, 0.115:1.0, 0.120:1.0, or 0.123:1.0 and independently preferably is not more than, with increasing preference in the order given, 2.0:1.0, 1.5:1.0, 1.0:1.0, 0.50:1.0, 0.40:1.0, 0.30:1.0, 0.25:1.0, 0.20:1.0, 0.1~:1.0, 0.16:1.0, 0.150:1.0, 0.140:1.0, or 0.130:1Ø
The presence of optional hydrotroping agent component (F) is generally preferredin concentrates according to the invention. Conventional hydrotroping agents such as the salts of alkyl benzene sulfonic acids, particularly of cumene sulfonic acid, are suitable for compositions according to this invention and are generally preferred for reasons of economy. However, if very low tolerances for residual sulfur on the deoxidized surface are prescribed, at least one of two other types of hydrotropes are then preferred: (i) organic phosphate esters and (ii) alkyl and alkenyl substituted cyclic acid anhydrides, particularly the anhydrides of C4 6 terminal dicarboxylic acids substituted with alkyl or alkenyl groups having 6 to 20 carbon atoms. Particularly preferred examples of this type of hydrotrope are octenyl and nonenyl succinic anhydrides.
The amount of hyd~ vping agent, when it is used at all, is preferably such as tohave a ratio to the amount of component (E), measured in the sarne units, that is at least, with increasing preference in the order given, 2:1.0, 4:1.0, 6:1.0, or 8:1.0 and independ-ently, primarily for reasons of economy, preferably is not more than, with increasing preference in the order given, 25:1.0, 20:1.0, 15:1.0, 13:1.0, 1 1:1.0, or 9:1.0, with the higher ratios within this range generally preferred for very highly concentratedcompositions according to this invention and lower ratios, including omission of any hy-drotroping agent at all, often satisfactory for working compositions.
Optional colorant component (G) is often preferred in a composition according to this invention, to serve as a visual indicator of the thickness of the coating applied to a substrate surface with a complicated shape and thereby make it easier to achieve the usual goal of an approximately equally thick coating over the entire surface to be deoxi-dized/etched. Numerous conventional dyes and/or pigments, as known to those skilled in the art, may be used for component (G).
Optional biocidal component (H) is not normally needed, but may be preferably present in a liquid composition according to the invention in an amount effective to re-press the biodegradation of any of the components of the composition, when the compo-sition is used in an environment in which acid-tolerant microorg~ni~m~ are prevalent.
CA 02248~68 1998-09-09 WO 98/306~2 - PCT/US97/00006 Optional oxidizing agent component (J) is not normally needed, but may be useful to accelerate the etching process on some substrates. Hydrogen peroxide is preferred when this component is used; it also has some biocidal activity and may be used for that purpose as part of component (H).
sIn preparing the compositions according to this invention, it is preferable to add the viscosity increasing agent to water before adding any of the other ingredients. If this is not done, long term viscosity instability may be experienced.
Preferably a substrate to be deoxidized and/or etched in a process according to this invention should be cleaned to remove most gross soils before being exposed to a 10composition according to this invention as described above.
A process according to the invention is normally performed at ambient tempera-ture, if for no other reason than that m~int~ining a different temperature would be a con-siderable practical difficulty in view of the large size of the substrates usually treated.
A contact time from 1 to 20 minutes, or more preferably from 8 to 12 minutes, is5normally preferred in a process according to this invention.
The invention may be further appreciated by consideration of the following ex-amples and comparison examples.
Materials Used BRIJTM 35 surfactant was obtained commercially from ICI Americas, Inc. and is 20reported by its supplier to consist of ethoxylates of lauryl alcohol with an average of 23 moles of ethylene oxide per mole of lauryl alcohol.
CAB-O-SILTM M5 dispersion of finely divided silica in water was obtained com-mercially from Cabot Corp. and is recommended as a viscosity increasing agent CALSOFTTM LAS 99 surfactant was supplied by Van Waters and Rogers, 25Icirklzlnfl~ Washington and is reported by its supplier to be linear alkyl benzene sulfonate.
KELZANTM AR xanthan gum powder was commercially obtained from the Kelco division of Merck & Co., Inc. and is reported by its supplier to contain 86 - 92 % solids of xanthan gum (which is constituted of polymers of ~-l ,4-linked D-glucose units) that has been modified to give lower viscosity at low shear rates than unmodified natural xan-30than gum. For example, a solution of 0.3 % of each of potassium chloride and KEL-ZANTM AR in water has a viscosity of about 800 centipoises (hereinafter usually abbreviated as "cps") at a shear rate of 0. l reciprocal seconds (hereinafter usually abbre-CA 02248~68 l998-09-09 WO 98/306s2 PCT/US97/00006 viated as "sec~"'), whereas an otherwise identical solution of natural xanthan gum has a viscosity of almost l 0,000 cps. At a shear rate of l 0 sec-', the viscosities of these solu-tions are about l 00 and 500 cps respectively.
NAXONATETM SC hydrotroping agent was obtained commercially from Ruet-gers-Nease Chemical Co., Inc., Ross, Ohio and was reported by its supplier to be 93 %
sodium cumene sulfonate.
TRITONTM N-l01 surfactant was commercially supplied by Van Waters and Rogers, Kirkland, Washington and was reported by its supplier to be a nonionic surfactant consisting of ethoxylated nonylphenol molecules with residues from an10 average of 9.5 molecules of ethylene oxide per molecule of surfactant;
UNISPERSETM Blue colorant was obtained commercially from Ciba-Geigy as a paste. It is reported by its supplier to contain about 50 % of copper phthalocyanine blue pigment in dispersion.
VEEGUMTM T was obtained commercially from R. T. Vanderbilt Co., Norwalk, Connecticut and is reported by its supplier to be hydrated magnesium aluminosilicate smectite clay. It is recommended as a viscosity increasing agent.
Working Coating Compositions and Processes Therewith Example and comparison example working compositions are set forth in Table l below. Blank cells in the table indicate that none of the material was added to the com-position, or that the property value that would properly appear in the cell was notmeasured. The viscosities reported in Table l were measured with a Brookfieldviscosimeter using spindle # 4. The balance of each composition not shown in Table l was water.
In the lower part of Table l, etch rates and times of exposure that achieved satisfactory deoxidizing/etching with some of the working compositions are also shown.
W 0 98/30652 PCTrUS97/00006 INGREDIENT PERCENT BY WEIGHT OF INGREDIENT IN COMPOSITION NUMBE~:
Ammonium 1.4 1.4 2.8 2.8 2.8 2.8 4.2 4.2 Bifluoride H2SO4,96.5 % 2.0 2.0 4.0 4.0 4.0 4.0 6.0 6.0 CAB-O-SILTM M5 4.0 4.0 KELZANTM AR 2.0 2.5 3.0 2.5 3.0 VEEGUMTM T
CALSOFTTM LAS 99 0.80 0.80 1.60 1.60 1.60 1.60 2.40 2.40 BRIJTM 35 1.0 1.0 TRITONTM N-101 0.10 0.10 0.20 0.20 0.20 0.20 0.30 0.30 NAXONATETM SC 0.40 0.40 0.80 0.80 0.80 0.80 1.20 1.20 30 % H202 in water UNISPERSET''' BIUC 0.0050.005 0.005 0.005 0 005 VISCOSITY IN POISES
NIIMBER:
At 20 RPM 14 6.7 22.6 85.2 At 10 RPM 145 131 166 At 5.0 RPM 246 At 2.5 RPM 410 480 At 1.0 RPM 652 At 0.5 RPM 920 PROCESS CIIARACTER_ ISTICS
Minutes of Contact 20 20 20 20 Etch Rate, ~lm/hr 0.38 2.67 2.84 3.5 Abbreviation in Table 1: "RPM" means "Revolutions per Minute"
... Ihis table is continued on the next page....
TABLE I continued INGREDIENT PERCENT BY WEIGHT OF INGREDIENT IN COMPOSITION NUMBER:
Ammonium 5.6 5.6 5.6 6.7 6.9 2.8 5.6 6.7 Bifluoride H2SO4,96.5 % 8.0 8.0 8.0 9.6 9.8 4.0 8.0 9.6 CAB-O-SILTM M5 4.0 KELZANTM AR 2.0 2.5 3.0 2.0 2.0 VEEGUMTM T 4.0 4 0 CALSOFl'rM LAS 3.2 3.2 3.2 3.8 3.92 ].6 3.2 3.8 TRITONTM N-101 0.40 0.40 0.40 0.48 0.49 0.20 0.40 0.48 NAXONATETM SC 1.60 1.60 1.60 1.92 1.96 0.80 1.60 1.92 30 % H2O2 in water 2.0 4.0 4.8 UNISPERSETM 0.005 0.005 0 005 0.0050.005 0 005 0 005 Blue POISES OF
COMPOSITION
NIJMBER:
At20RPM 11.5 < 1 91 14 11.5 < 1 At 10 RPM 13] 194 At 5.0 RPM
At 2.5 RPM
At 1.0 RPM
At 0.5 RPM
PROCESS
CHARACTERISTICS
Minutesof 20 20 20 20 20 Contact Etch Rate, ~m/hr 4.7 4.3 4.9 1.1 18.5 CA 02248~68 l998-09-09 W O 98/30652 PCT~US97/00006 The coatings were formed for these examples simply by immersing the test panels in the composition and then withdrawing them after a few seconds, with no deliberate aid or hindrance to drainage of the composition from the panel surface. The coated panel was then held with its highest area surfaces vertical for the contact time indicated in the Table. The viscous liquid coating over the panel surfaces was then rinsed away with water. Panels had been weighed before applying the working composition and were weighed again after this rinsing and subsequent drying to determine the mass loss which was converted to an etch rate by the usual mathematical calculations (i.e., dividing the total mass loss for the panel by the area of the panel to determine loss per unit area, then 1C dividing the loss per unit area by the density of the panel to determine the thickness of metal corresponding to the mass loss.) Some of the panels treated, instead of being dried to determine etch rates, weretreated after rinsing with a commercially available composition (ALOD~NE~) 1000 Chromate Conversion Coating Liguid, available from the Parker Amchem Division ofHenkel Corp., Madison Heights, Michigan) to produce a conventional chromate conver-sion coating on the panel surfaces. The coatings produced are fully as good in properties as those produced by using the same treatment on otherwise identical panels that had been deoxidized/etched by a conventional high quality, low viscosity liquid composition for use by immersion of the substrates being treated.
Claims (12)
1. A liquid composition of matter suitable either as such or after dilution withadditional water to form a viscous liquid layer, over at least a portion of a surface of an aluminum substrate to be deoxidized and etched in a location within one mile of Earth, said viscous liquid layer having the property that it will not, in response to Earth's gravitational force, fall away from contact with any initially covered portion of said aluminum substrate during a period of time sufficient to deoxidize and etch said initially covered portion of said aluminum substrate, irrespective of whatever angle may exist between any part of said initially covered portion of said aluminum substrate and any part of Earth's surface, said liquid composition comprising water and:
(A) an amount of a source of dissolved fluoride ions;
(B) an amount of a source of an acid with a larger ionization constant than hydrofluoric acid;
(C) an amount of a viscosity increasing agent that is not part of any of the previously recited components;
(D) an amount of anionic surfactant that is not part of any of the previously recited components; and (E) an amount of nonionic surfactant that is not part of any of the previously recited components.
(A) an amount of a source of dissolved fluoride ions;
(B) an amount of a source of an acid with a larger ionization constant than hydrofluoric acid;
(C) an amount of a viscosity increasing agent that is not part of any of the previously recited components;
(D) an amount of anionic surfactant that is not part of any of the previously recited components; and (E) an amount of nonionic surfactant that is not part of any of the previously recited components.
2. A composition according to claim 1, wherein: the amount of fluoride ions is from about 2.0 to about 60 g/kg; the amount of ionized hydrogen atoms is from about 0.080 to about 6.0 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from ahout 0.0040:1.0 to about 0.40:1.0; the viscosity of the composition, measured at 25 °C
with a Brookfield viscosimeter using spindle # 4, is at least about 100 poises at 0.5 rpm and is not more than about 400 poises at 20 rpm; the amount of anionic surfactant is from about 2 to about 75 g/kg; and the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.015:1.0 to about 2.0:1Ø
with a Brookfield viscosimeter using spindle # 4, is at least about 100 poises at 0.5 rpm and is not more than about 400 poises at 20 rpm; the amount of anionic surfactant is from about 2 to about 75 g/kg; and the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.015:1.0 to about 2.0:1Ø
3. A composition according to claim 2, wherein: the amount of fluoride ions is from about 4.0 to about 50 g/kg; the amount of ionized hydrogen atoms is from about 0.15 to about 5.0 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from about 0.0060:1.0 to about 0.30:1.0; the viscosity of the composition, measured at 25 °C with a Brookfield viscosimeter using spindle # 4, is at least about 200 poises at 0.5 rpm and is not more than about 350 poises at 20 rpm; the amount of anionic surfactant is from about 4 to about 60 g/kg; and the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.030: 1.0 to about 1.0: 1Ø
4. A composition according to claim 3, wherein: the amount of fluoride ions is from about 6.0 to about 40 g/kg; the amount of ionized hydrogen atoms is from about 0.30 to about 4.0 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from about 0.0100:1.0 to about 0.20:1.0; the viscosity of the composition, measured at 25 °C with a Brookfield viscosimeter using spindle # 4, is at least about 300 poises at 0.5 rpm and is not more than about 300 poises at 20 rpm; the amount of anionic surfactant is from about 6 to about 40 g/kg; and the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.045:1.0 to about 0.50:1Ø
5. A composition according to claim 4, wherein: component (A) is selected from the group consisting of ammonium and alkali metal fluorides and acid fluorides; component (D) is selected from the group consisting of sulfonic acids, partial esters of sulfuric acid, and salts of both of these types of acids; and component (E) is selected from the group of molecules conforming to general chemical formula (I):
R1O(CH2CH2O)y(CH2CHCH3O)zH (I), where R1 is a moiety selected from the group consisting of saturated-and-unsaturated straight-and-branched-chain-aliphatic-monovalent-hydrocarbon-moiety-substituent -bearing phenyl moieties in which the aromatic ring of the phenyl moiety is directly bonded to the oxygen atom appearing immediately after the R1 symbol in formula (I); y is a positive integer; and z is zero, one, or two.
R1O(CH2CH2O)y(CH2CHCH3O)zH (I), where R1 is a moiety selected from the group consisting of saturated-and-unsaturated straight-and-branched-chain-aliphatic-monovalent-hydrocarbon-moiety-substituent -bearing phenyl moieties in which the aromatic ring of the phenyl moiety is directly bonded to the oxygen atom appearing immediately after the R1 symbol in formula (I); y is a positive integer; and z is zero, one, or two.
6. A composition according to claim 5, wherein: the amount of fluoride ions is from about 8.0 to about 35 g/kg; the amount of ionized hydrogen atoms is from about 0.40 to about 2.5 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from about 0.020:1.0 to about 0.10:1.0; the viscosity of the composition, measured at 25 °C with a Brookfield viscosimeter using spindle # 4, is at least about 400 poises at 0.5 rpm and is not more than about 250 poises at 20 rpm; the amount of anionic surfactant is from about 8 to about 30 g/kg; and the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.060:1.0 to about 0.40:1Ø
7. A composition according to claim 6, wherein: the amount of fluoride ions is from about 12.0 to about 28 g/kg; the amount of ionized hydrogen atoms is from about 0.55 to about 2.0 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from about 0.030:1.0 to about 0.080:1.0; the viscosity of the composition, measured at 25 °C
with a Brookfield viscosimeter using spindle # 4, is at least about 600 poises at 0.5 rpm and is not more than about 170 poises at 20 rpm; the amount of anionic surfactant is from about 11.0 to about 25 g/kg; the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.100:1.0 to about 0.20:1.0, and component (E) is selected from molecules that conform to general chemical formula (I) when R1 has from 5 to 12 carbon atoms, the average value of y is from 5 to 14, and z is 1 or 0.
with a Brookfield viscosimeter using spindle # 4, is at least about 600 poises at 0.5 rpm and is not more than about 170 poises at 20 rpm; the amount of anionic surfactant is from about 11.0 to about 25 g/kg; the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.100:1.0 to about 0.20:1.0, and component (E) is selected from molecules that conform to general chemical formula (I) when R1 has from 5 to 12 carbon atoms, the average value of y is from 5 to 14, and z is 1 or 0.
8. A composition according to claim 7, wherein: component (B) is selected form the group consisting of sulfuric, nitric, and hydrochloric acids; component (C) is selected from natural and modified xanthan gums; component (D) is selected from linear alkyl benzene sulfonic acids in which the alkyl moiety has from 4 to 14 carbon atoms and salts of said linear alkyl benzene sulfonic acids; and component (E) is selected from molecules that conform to general chemical formula (I) when R1 has from 7 to 12 carbon atoms, the average value of y is from 7 to 12, and z is 0.
9. A composition according to claim 8, wherein: the amount of fluoride ions is from about 16.0 to about 22 g/kg; the amount of ionized hydrogen atoms is from about 0.70 to about 1.2 mH/kg and has a ratio to the amount of fluoride ions in g/kg that is from about 0.038:1.0 to about 0.050:1.0; the viscosity of the composition, measured at 25 °C
with a Brookfield viscosimeter using spindle # 4, is at least about 800 poises at 0.5 rpm and is not more than about 105 poises at 20 rpm; the amount of anionic surfactant is from about 14.0 to about 18.0 g/kg; the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.115:1.0 to about 0.140:1.0; and component (E) is selected from molecules that conform to general chemical formula (I) when R1 has from 8 to 10 carbon atoms and the average value of y is from 8 to 10.
with a Brookfield viscosimeter using spindle # 4, is at least about 800 poises at 0.5 rpm and is not more than about 105 poises at 20 rpm; the amount of anionic surfactant is from about 14.0 to about 18.0 g/kg; the amount of nonionic surfactant has a ratio to the amount of anionic surfactant that is from about 0.115:1.0 to about 0.140:1.0; and component (E) is selected from molecules that conform to general chemical formula (I) when R1 has from 8 to 10 carbon atoms and the average value of y is from 8 to 10.
10. A composition according to claim 9, wherein: component (A) is ammonium bifluoride; component (B) is sulfuric acid; component (C) is modified xanthan gum having the property that a solution of 0.3 % of each of potassium chloride and the modified xanthan gum in water has a viscosity of about 800 centipoises at a shear rate of 0.1 sec-1 and a viscosity of about 100 centipoises at a shear rate of 10 sec-1; component (D) is selected from linear alkyl benzene sulfonic acids in which the alkyl moiety has from 6 to 12 carbon atoms and salts of said linear alkyl benzene sulfonic acids; component (E) is selected from nonylphenol ethoxylates; the composition also contains sodium salt of cumene sulfonic acid in an amount that has a ratio to the amount of nonylphenol ethoxylates that is from about 6:1.0 to 9:1.0; and the composition contains a colorant in an amount sufficient to facilitate visual judgment of the uniformity of thickness of a coating formed with the composition.
11. A process for deoxidizing and etching at least a portion of a surface of an aluminum substrate, said process comprising steps of:
(I) forming on said portion of said surface of an aluminum substrate to be deoxidized and etched a coating of a viscous liquid composition according to any one of claims 1 through 10;
(II) maintaining in place the coating formed in step (I) for a time sufficient to deoxidize and etch the portion of the surface covered by the coating formed in step (I);
and (III) subsequently removing the coating of viscous liquid composition formed in step (I) from further contact with the aluminum substrate surface.
(I) forming on said portion of said surface of an aluminum substrate to be deoxidized and etched a coating of a viscous liquid composition according to any one of claims 1 through 10;
(II) maintaining in place the coating formed in step (I) for a time sufficient to deoxidize and etch the portion of the surface covered by the coating formed in step (I);
and (III) subsequently removing the coating of viscous liquid composition formed in step (I) from further contact with the aluminum substrate surface.
12. A process according to claim 11, wherein during step (II) the portion of thesurface covered by the coating formed in step (I) is etched at a rate of about 2.5 ~ 0.5 µm/hr.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1997/000006 WO1998030652A1 (en) | 1997-01-09 | 1997-01-09 | Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces |
| CA002248568A CA2248568A1 (en) | 1997-01-09 | 1997-01-09 | Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1997/000006 WO1998030652A1 (en) | 1997-01-09 | 1997-01-09 | Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces |
| CA002248568A CA2248568A1 (en) | 1997-01-09 | 1997-01-09 | Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2248568A1 true CA2248568A1 (en) | 1998-07-16 |
Family
ID=25680519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002248568A Abandoned CA2248568A1 (en) | 1997-01-09 | 1997-01-09 | Acid deoxidizing/etching composition and process suitable for vertical aluminum surfaces |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2248568A1 (en) |
| WO (1) | WO1998030652A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343189C (en) * | 2000-04-28 | 2007-10-17 | 默克专利有限公司 | Etching pastes for inorganic surfaces |
| DE10150040A1 (en) | 2001-10-10 | 2003-04-17 | Merck Patent Gmbh | Etching passivating and antireflection layers made from silicon nitride on solar cells comprises applying a phosphoric acid and/or etching medium containing a salt of phosphoric acid the surface regions to be etched |
| US20040043143A1 (en) * | 2002-08-30 | 2004-03-04 | Rochester Thomas H. | Mechanical deposition process |
| CN103980905B (en) * | 2014-05-07 | 2017-04-05 | 佛山市中山大学研究院 | A kind of etching solution and its engraving method and application for oxide material system |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE25953E (en) * | 1966-02-22 | Process and composition for brightening aluminum | ||
| US2687346A (en) * | 1953-04-24 | 1954-08-24 | Kelite Products Inc | Process and composition for brightening the skin of aircraft |
| US2942956A (en) * | 1958-10-13 | 1960-06-28 | Wyandotte Chemicals Corp | Aluminum brightener compositions |
| US3448055A (en) * | 1965-03-31 | 1969-06-03 | Diversey Corp | Aluminum alloy deoxidizing-desmutting composition and method |
| US3379645A (en) * | 1965-11-15 | 1968-04-23 | Rohr Corp | Process and composition for removing protective paint films |
| US3578499A (en) * | 1968-08-02 | 1971-05-11 | Grace W R & Co | Gelling composition for general purpose cleaning and sanitizing |
| DE3119538A1 (en) * | 1981-05-16 | 1982-12-02 | Henkel KGaA, 4000 Düsseldorf | CLEANING OF SURFACES FROM ANODIZED ALUMINUM AND ITS ALLOYS |
| JPS59123772A (en) * | 1982-12-27 | 1984-07-17 | Toppan Printing Co Ltd | Etching solution for aluminum-base metal |
| US4614607A (en) * | 1984-09-26 | 1986-09-30 | The Boeing Company | Non-chromated deoxidizer |
| US4959105A (en) * | 1988-09-30 | 1990-09-25 | Fred Neidiffer | Aluminium cleaning composition and process |
| US4921626A (en) * | 1989-08-23 | 1990-05-01 | Automark Corporation | Glass etching composition and method of making |
| US5393447A (en) * | 1993-07-09 | 1995-02-28 | Henkel Corporation | Composition and process for desmutting and deoxidizing without smutting |
-
1997
- 1997-01-09 CA CA002248568A patent/CA2248568A1/en not_active Abandoned
- 1997-01-09 WO PCT/US1997/000006 patent/WO1998030652A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998030652A1 (en) | 1998-07-16 |
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