US3041215A - Solutions and methods for forming protective coatings on titanium - Google Patents
Solutions and methods for forming protective coatings on titanium Download PDFInfo
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- US3041215A US3041215A US563865A US56386556A US3041215A US 3041215 A US3041215 A US 3041215A US 563865 A US563865 A US 563865A US 56386556 A US56386556 A US 56386556A US 3041215 A US3041215 A US 3041215A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 16
- 239000010936 titanium Substances 0.000 title claims description 16
- 229910052719 titanium Inorganic materials 0.000 title claims description 16
- 238000000034 method Methods 0.000 title description 3
- 239000011253 protective coating Substances 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 2
- 150000007513 acids Chemical class 0.000 description 17
- 239000007787 solid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008247 solid mixture Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000001464 adherent effect Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- -1 hydrochloric Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- VXVXGDWCEVGOET-UHFFFAOYSA-N acetic acid;benzoic acid Chemical compound CC(O)=O.CC(O)=O.OC(=O)C1=CC=CC=C1 VXVXGDWCEVGOET-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Images
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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Definitions
- This invention relates to the formation of adherent protective coatings on titanium and more particularly to chemically formed fluoride coatings on titanium and titaninmbasealloys.
- Forrnaonofthecoating occursfrom asurfaeeofthemetalwithanaqueousacidic solntioncontainingtbellnorideionandionsofoneor moreofthealkalimetals.
- the coatings of the invention are formed by contacting the surface of titanium and the like with an aqueous solution containing one or more of the adds of the above group, viz., hydrouonc acid. and hydrochloric acid, nitric acid or sulphur-ic acid and an organic acid having a primary dissociation constant less than 3 X 10-2 but greater than lxlO" at a pH between 2 and 6; the solution also containing at least 0.5% iluoride ions and at least 0.5% sodium or potassium ions or both.
- the concentration of the above group of acids is maintained so that the pH of the solution is vnthin the optimum range of 2.5 to 5.
- the anion radical of these acids which disociates imm the hydrogen radical appears to be the most important factor accounting for the similarity in elect on coating of the acids when present in the solution, and consequently while including other acids may be present in minor amounts, it is imperative that the greater part, and preferably all of the acidity of the solution is derived from one or more of the acids of the above group.
- Thc Solution preferably should be y free from calcium andotherionsknown toformnondesthat are insoluble in aqueous solutions' as othervme' theuorideionoccursby allowingtlrerntoheprecxpr-v tated as simple insoluble uorides.
- :om canbetoleratedintheamonntsusual'lyfmmdmtap water, and comequently this water may be med for preparing the solutions.
- a tluotitanate compound such as an alkali lluotitanate, as for example, potassium uotitanate can also be included in the coating solution initially and it can be mixed with the solid compositions pre viously mentioned for making up the solutions.
- the solutions can be prepared by dissolving three in gredients in water, viz., one of the above group of acids, atuon'deandanalkalimetalcompoundandinthecase of hydrotuoric acid, two ingredients, viz., the acid and an alkali metal compound.
- two ingredients can also be used, viz., theacidandanalkalimetaluoride.
- a solid composition can be made by mixing a solid binonde and a solid compound o( an alkali metal which when dissolv'ednwates-,ormanaqieoussolntiomwillprovidea woing solution. If the cation of the solid biuoride is analkalimetahanglesoiidcompotmdcanbemedfor dzissolurionwhichmaktheprocessextremelysimple andconvenient. Forcxample,a 15% solution made frumwlidpotassinmbiuorideanda 12% solutionmade from solid sodium biuoride each produced a strongiy adhauzt brown-gray coating on titanium.
- the solution can be prepared from three ingredients, viz., one of these acids, a fluoride and an alkali metal. Alternatively, one of these acids and an alkali metal uoride only need be used to supply the solution.
- a solid composition can be used as the source of these acids and this feature will be illustrated with respect to sulphuric acid.
- a bisulphate or sulphamic acid can be used as the source of sulphuric acid in the solution.
- these are solids their use has advantages and an example of such a composition comprises a.
- solid mixture of a solid bisulphate or sulphamic acid, a solid uoride and a solid alkali metal compound.
- This will provide a work;A ing solution when dissolved in water or an aqueous solution.
- An even simpler solid mixture comprises two compounds, e.g., a bisulphate and an alkali metal uoride.
- Good results were obtained from a solution prepared from a mixture which comprises 5 parts by weight of solid sodium bisulphate and 4 parts by weight of solid sodium fluoride which is dissolved in water in the quantity of 9 parts by weight of the mixture to make parts by weight of solution.
- the solutions tobebroughtntoeontaetwiththemetalsnrfacecanbe prepared by dissolving in water three ingredients, namely, the organic acid, a compound yielding fluoride ions and an alkali metal compound. If desired, two ingredents can be used, namely, the acid and an alkali metal tluoride. Ether a solution ready for use or a concentrate whichisdilutediustpriortousecanbeprepared.
- the organic acids e.g., citric and tartar-ic acids, are solids their use in such form provides the advantages previously set forth for the solid materials.
- a solid composition according to this feature of the invention comprises a mixture of a solid organic acid having a primary dissociation constant between 1x10-4 and 3x10-z with a solidofone ormore ofthe compounds providing the fluoride ion and the alkali metal ion when dissolved.
- Even greater simplification of the processarisesfromtheuseofasolidmixture whichconsists of only two compounds, as for example, citric acid and sodium or potassium uoride.
- Example I Coatings were produced on titanium by the various hydrotluoric acid or hydmiluoric acid-pr0ducing solutions set forth below by pickling titanium panels for 30 seconds in a solution of nitric acid and hydrouoric acid, rinsingthemandthenimmcrsingthaninthevarrms solutionsatroomtemperanneuntilgassingstopped.
- the solutionsandthecoatingweightsohtained were:
- An laqueous add solution for actuating base alloyshavnga onsurfaoesofttaniumandtitanium pHbetwem2and6andofabout0396to896 mxxidematleastabout0596ioofatleastoneof bengsuch that thepnepartoftheacidityofthesolutonisdevedfmm acid.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
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Description
United States Patent Office 3,041,215 Patented June 26, 1962 ign No Drawing. I'led Feb. 7, 1956, Ser. No. 563,865
priority, application Great Britain Feb. 7, 1955 1 Ch'lns. (CL 14S-6.14)
This invention relates to the formation of adherent protective coatings on titanium and more particularly to chemically formed fluoride coatings on titanium and titaninmbasealloys.
It is an important object of the invention to provide improved solutions and methods for chemically forming strongly adherent coatings on surfaces of titanium and titaniuxnbasealloys.
Otherimportant objects oftheinventionaretoprovide arclesoftitaniumandoftitaninmalloyswhichhave iormedthexeoncharacteristiccorrosionresistantcoatings andtoprovidesaidarticlesinsuchcoatcdformwhereby dieymaybedeformedandooldworkodwithoutiniuryto tbesubsuate.
'lheaboveandotberobectsoftheinventionwillbecome apparent during the course of the following description.
Inacoordancewiththenventimtitanirnnandtitanium basealloyscanbemnvidedwithauniformadherem uoridecoating which facilitates drawingandoold work ingofmemetalandwhichimpartsdaeretosuperiorcorrosionresstance. Forrnaonofthecoatingoccursfrom asurfaeeofthemetalwithanaqueousacidic solntioncontainingtbellnorideionandionsofoneor moreofthealkalimetals. Forpurposesofthepresent inventiomammonumisinclndedinthetermalkalimetals. ItisessentialthmapHbetweenaboutZandbemaintainedforthesolutionandpreferablythepliismaintaincdbetweenabout25and5.
Ithasnowheenfonndthatacertaingroupofcomponndshaventhennusualelectofreactingwith ttanirnnandtitaninmbealloysinthepresenceofthe andtheiomofthealkalimetalstoforman ysnperorandfromwhatappeaatypeof oftheooatingremainsunknowmbutitisknownfromits propertiesandeectstoheyadherentandproteotiveandtobeofsolntions havingthe mentionedandoneoftheofthis eertaingroup. Thedistimadvamagesof-theinvention arerealzedarlyunderthe i thatthe partandpreferablyallotftheaa'dityofthesohrtionis thrived fran one of this certain group ofoompounds.
Ammtheinvtiomth'certaingmupof arealladdsandallexhibttoamarkeddegme IethedescribedbeneficialpropertywhcnllstdilllhYPe theprinpalsouroeofaddity. 'Diegmpofaddssofomtoexhibtthispropertycomprisesformhydrotluocacidwhchhasitsowndistinct winappeanandarsohydxhkacacd.
andsimilarlytheirehassepamteadvantages. Discoveredtobeequivalanoftheinm'- gancaddsintheireectonhmalsohavingseparaareorganicaa'dswhichhaveaprimary umstantls than 3x10" butgreater than 1x10- Bygmaryconstantismeantthe s at approximately mom "wmlhmthereare oneatnms. Ofthelattermore adds,i.e.,theorganicacidsewhichareuserlfnrforming coatings of the present invention, the following are preferred: succinic acid; rnaleic acid; salicylic acid; tartaric acid; phthalic acid; acetic acid; benzoic acid; and citric acid.
Acording to a feature of the invention, advantages are realized when solid materials are used as the source of one or more of the above group of acids and/or the other ingredients of the solutions. The solid compositions are much less corrosive than the solutions so that packaging and handling are facilitated, and economies in storage and transportation are effected.
The coatings of the invention are formed by contacting the surface of titanium and the like with an aqueous solution containing one or more of the adds of the above group, viz., hydrouonc acid. and hydrochloric acid, nitric acid or sulphur-ic acid and an organic acid having a primary dissociation constant less than 3 X 10-2 but greater than lxlO" at a pH between 2 and 6; the solution also containing at least 0.5% iluoride ions and at least 0.5% sodium or potassium ions or both. Preferably the concentration of the above group of acids is maintained so that the pH of the solution is vnthin the optimum range of 2.5 to 5. The anion radical of these acids which disociates imm the hydrogen radical appears to be the most important factor accounting for the similarity in elect on coating of the acids when present in the solution, and consequently while including other acids may be present in minor amounts, it is imperative that the greater part, and preferably all of the acidity of the solution is derived from one or more of the acids of the above group.
It has been found that the coatings obtained with solutions containing sodium are formed more rapidly than those obtained with solutions containing potassium. If ammonium or lithium ions or both are used in place of sodium or potassium, their concentration must be substantiallyincreased. and,intbe caseofammonium,thecon centraton ofthe ammonium ion should be at least 2%. InthecaseoflithiumitispreferabletonseatleastZi but it is possible to use less. Unless otherwise' indicated. percentagesasgiventhroughouttheareby weight percent. Mixtures of the above alkali may beusedandinthissetheminimnmconcentratlonwil'llre somewhere between the minimum given above for the iom separately dependrng on the relative proportions of each in the mixture. Excellent coatings have been formed from concentrations of 8% alkali metal `non.
Thc Solution preferably should be y free from calcium andotherionsknown toformnondesthat are insoluble in aqueous solutions' as othervme' theuorideionoccursby allowingtlrerntoheprecxpr-v tated as simple insoluble uorides. However, :om canbetoleratedintheamonntsusual'lyfmmdmtap water, and comequently this water may be med for preparing the solutions. Using the solutiom with the above groupofacidspresentinthestrengthsthe concenu'ationofthelluorideionmustbeatleast0.9% andcanbeedinquantitiesbelowandabovesaturationwhichisappmximatelyoftheorderofl0% thoride ion. 'Iheprefcrredrangeofoonoentraonoitheuoride ionhasbeenfoundtobebetweenaboutOi to8%.
Articlesrnaybetreatedeitherbysprayingorbyimmersion and in handling of the solutions rubber or polythc-lined containers are as the solunom are corrosive.
Entirely satisfactory coatings can be formed without any activation or chemical of the surfaoett However, it is oftentimes tirs! to pickle the :nume with a solution hydro- A 5% hydmduorieacidsolntitm hasbeenfoundtobeamefulpickle. Insomecasesthe nature of the pickle solution may be a factor in obtaining the most successful coating and in such cases its nature must be determined by the particular titanium alloy to be processed. Any grease that may be present on the surface as received for coating will generally be removed by this picltling, but if necessary, a preliminary degreasing treatment may also be applied. lf the titanium has been annealed it may carry a heavy scale, and this, of course, should be removed also.
From the evidence that is available, the coating action of these solutions appears to be the result of the forma tion of a thin layer of solution saturated with titanium at the surface thereof under treatment. Accordingly, when a fresh solution is brought into contact with the metal surface there is a time lag before coating starts while the titanium metal is being dissolved from the surface. It is therefore preferred to add titanium to the solution. It has been found that this can be accomplished conveniently by adding to the solution just prior to immersion of the metal enough uotitanate compound to saturate the solution and simple tests under operating conditions can be made to determine the amount required in a particular operation. A tluotitanate compound such as an alkali lluotitanate, as for example, potassium uotitanate can also be included in the coating solution initially and it can be mixed with the solid compositions pre viously mentioned for making up the solutions.
The solutions can be prepared by dissolving three in gredients in water, viz., one of the above group of acids, atuon'deandanalkalimetalcompoundandinthecase of hydrotuoric acid, two ingredients, viz., the acid and an alkali metal compound. Alternatively, in the case of the other acids, two ingredients can also be used, viz., theacidandanalkalimetaluoride.
With respect to the above group of acids, while they an: substantially equivalent in their e'ect on the type of coatingformedeachorcertainoftheacidsofthegroup have specific advantages when used in the solution alone andthispropertyofcertainoftheacidsmakesnatural subgroupiugs from the above group of acids. The use of hydrouon'c acid without the others oi the group intbesolutionasthepredominantorsolesourceofthe acidity thereof has the additional advantage that the complex uoride coating formed does not contain any other acidorsaltthereofenuainedorotherwisecarried over from the solution. The main advantage (in addition, of course,tothosedescbedfortixegroupasawhole) in using alone the other mineral acids, namely, hydrochloric, niu'icandsulphmicacid,isthattheyarecheapand readilyavailable. 'Iheadvantageoftheuseoftheorganicaddshavingadiociationconstantassetforth above without the others as the sole source of the acidityofthesolntionisthattheeonn'olrequiredtomaintainthepHwithintherequiredrangeissmpler.
Hereinafter,thenvntionwillbedescn`bed withrespccttoeachoftheabovembgroupsoftheacidsofthe generalgroup. ln tbecaseofhydrotuorkacd, the solutionnbeprtparedbydidvinginwatertheaddand an alkali metal compound. Altcmativdy, a Solution of an alkali metal bnoride can be used to provide the es sentia! constituents of this solution. In accordance with the feature of the invention wherein solid materials are employed to facilitate storage and transportation, a solid composition can be made by mixing a solid binonde and a solid compound o( an alkali metal which when dissolv'ednwates-,ormanaqieoussolntiomwillprovidea woing solution. If the cation of the solid biuoride is analkalimetahanglesoiidcompotmdcanbemedfor dzissolurionwhichmaktheprocessextremelysimple andconvenient. Forcxample,a 15% solution made frumwlidpotassinmbiuorideanda 12% solutionmade from solid sodium biuoride each produced a strongiy adhauzt brown-gray coating on titanium.
lnthemeoftheotherminaaladdshydrochloric,
nitric and sulphuric acid, the solution can be prepared from three ingredients, viz., one of these acids, a fluoride and an alkali metal. Alternatively, one of these acids and an alkali metal uoride only need be used to supply the solution. Advantageously, a solid composition can be used as the source of these acids and this feature will be illustrated with respect to sulphuric acid. In the case of sulphuric acid, a bisulphate or sulphamic acid can be used as the source of sulphuric acid in the solution. As these are solids, their use has advantages and an example of such a composition comprises a. solid mixture of a solid bisulphate or sulphamic acid, a solid uoride and a solid alkali metal compound. This will provide a work;A ing solution when dissolved in water or an aqueous solution. An even simpler solid mixture comprises two compounds, e.g., a bisulphate and an alkali metal uoride. Good results were obtained from a solution prepared from a mixture which comprises 5 parts by weight of solid sodium bisulphate and 4 parts by weight of solid sodium fluoride which is dissolved in water in the quantity of 9 parts by weight of the mixture to make parts by weight of solution.
In the case of the organic acids which have a dissociation constant between lXl0- and 3Xl03, the solutions tobebroughtntoeontaetwiththemetalsnrfacecanbe prepared by dissolving in water three ingredients, namely, the organic acid, a compound yielding fluoride ions and an alkali metal compound. If desired, two ingredents can be used, namely, the acid and an alkali metal tluoride. Ether a solution ready for use or a concentrate whichisdilutediustpriortousecanbeprepared. As some of the organic acids, e.g., citric and tartar-ic acids, are solids their use in such form provides the advantages previously set forth for the solid materials. A solid composition according to this feature of the invention comprises a mixture of a solid organic acid having a primary dissociation constant between 1x10-4 and 3x10-z with a solidofone ormore ofthe compounds providing the fluoride ion and the alkali metal ion when dissolved. Even greater simplification of the processarisesfromtheuseofasolidmixturewhichconsists of only two compounds, as for example, citric acid and sodium or potassium uoride.
The following examples illustrate the improved acid fluoride coating solutions of the present invention and method of applying these solutiom to surfaces of titanium1 andaregivenwithrespecttoeachoftheabovesub` groups of acids, namely, hydroiluoric acid, and the ruineral acids, hydrochloric, nitric and sulphuric acid, and the organic acids.
Example I Coatings were produced on titanium by the various hydrotluoric acid or hydmiluoric acid-pr0ducing solutions set forth below by pickling titanium panels for 30 seconds in a solution of nitric acid and hydrouoric acid, rinsingthemandthenimmcrsingthaninthevarrms solutionsatroomtemperanneuntilgassingstopped. The solutionsandthecoatingweightsohtainedwere:
5 Example 2 The solution consisted of:
Percent H2904 1.5 'KF 5 NaNO, 0.25 XiTiP. 0.1
Water t make 100%.
Ahavinggoodadhesionanddarkgmyinap- 'pearanoewaspmdudinmimnesatZOC Example 3 The sohxtion eom'sted of:
Percent KHSO. 7 KF NaNO, 0.25 KJEF. 0.1
Watcrto make 100%.
Thesamepmducxwaansedindnahouampte .andtheaamensuhsweobinei Example4 The solutionof:
Watertomake im.
'lbsurfaofthewirerennnedmgoodoonditonrhlrtlgthedmwmg mmelnmusetfonhnhove.
Exampk Theaolunnof:
Daxkadhexmwueornndontitaninmin Erample7 Theaolutiond:
DarkafllereatwerefmedoninS ninnesltZOC.
Water to make Darkmyooatingsofgoodadhionwereformedon titaniuxninSminutesatZD C.
ltwllthusbeseenthatthcrehasbeenprovided by invention, an article, a composition and axmethod in which the various objects hereinabove set forth, together with many thoroughly practical advantages are successfullyachieved.
Sincatainchangesmaybemadeintheaboveinvention and different embodiments of the invention may be madewithoutdepartingfromthescopehcreotisintendedthatallmattercontainedintheabove-describeddisclosureshallbeintexpretedasilbtrativeandnotina Whatisdaimedis:
l. Anaqueoacidicsolution for pmducingaooating onsurfacoftitaniumandlitaniumbaaealloyshavinga pHbetweenZandandgofatleastabontO oftheuoridion,atlstabont0.5%ofthei0nsof atleastoneoftheaikalimetalgandanacidselected''om the group of hydrouoxic acid, hydrodoxic acid,ntcacid,amisulphuxicacid,thcoonoenn-ationof saidacidhnthesolutionbdngsuchthatthe panoftheacidityofthevsolutionisderivedtmmsaidadd.
LAnaqueousacidicsolutonforproducingawating onsurfasoftitaniumandtitaniumbasealloyshavinga pHbetween2and6andofatleastabout0.5% ofthelwrdematkastaboutoftheonsofat leastoneofthealkalimetals,andanacidselectedfmm the group of hydmuorie acid, hydrochloric adinitcadiandsulphncaciilcncmtrationof saidaeidhtthesolutionbcingsurhthattbe. partoftheacidityofthesolmionisdctivedfmmsaid acid.
3. An for-producing aooatng onsurfasoftitaniumandbmealloyshavinga pHbdWCellZvand 63nd HHC'HH; d3b0l0.9% @8% nodeiomat-leastabomlionsofatlestoneof ofsaidadinthewhlonbdngsnchthattheprt panzoitheacidtyofdtesohxtion'deved'ommid acid.
4. An laqueous add: solution for actuating base alloyshavnga onsurfaoesofttaniumandtitanium pHbetwem2and6andofabout0396to896 mxxidematleastabout0596ioofatleastoneof bengsuch that thepnepartoftheacidityofthesolutonisdevedfmm acid.
amd
$.Anaqueousacidicsolutionforpmducingaooating onsnrfasofttanimnandtitanimnmealloyshavlga p}{betwen2and6andofabout0.9%to8% uorideiomatletaboutojkvofatleastoneofthe ofsaid addinthesohltionbeingsuchthatthepan ofdxeacidityofthesdutionsderivedfmmsaidadd.
6 Anaqneousaddicsolutionforaoting onsmiasoftitaninmandtitanumbasealloyshzvmga pHbetwoen2and6andofabout0.9%to8% horideiomatleastabontij'iionsofatleastoneof partoftheacittyofthesoluonisdexivedfmmsaid and.
7.Asolidoompostionsolublemwamsoastoform asolutioncapableofanadhemon surfasoftitanimnandhaseaoya oflanxuneofabinordganalkalimaal andainanamomnsutcanto saturate said solution, the proportions of said biuoride, alkali metal compound and uotitanate being such as to produce an aqueous acidic solution having a pH between 2 and 6 and containing at least 0.5% of the uoride ion andatleast0.5`% of theaikalimetalion.
8. A solid composition soluble in water so as to form a solution capable of producing an adherent coating on surfaces of titanium and titanium base alloys consisting ofamixtureofatleastoneoompoundofthegoupsulphamicacidandabisulphatgaooridqandanalkali metal the proportions of said acid, fluoride, andalkalimetalcompoundbeingsuchastoproducean acidicsolutionhavingapHbetween2and6and containngatleast0.5% oftheiluorideionandatleast 0.5%ofthealkalimetalion.
9. Asolidcompositiousolubleinwatersoastoform a solution capable of producing an adherent coating on snrfacesoftitaniumandtitaniumbasealloysoonsisting meutiallyofamxtureofatleastoneoompoundofthe groupsnlpharnicacidandabisulphate,auoride,analkali metal compound, and auo'tanatein anamountsn cienttoaatnratesaidsolutiomthepxoportonsofsaid acid,ilnu|ide, andalkalimetaloompoundbeingmchas toproduanaqoeousacdicsolutonhavngaplibetwem2md6andcontaixngatleast0.$% oftheuoride ionandatleast05%ofxealkalimetalion.
10. Amethodfprodncinganadherentcoatingontbe surfacesoftitaniumandtitaniumbasealloyscomprisng saidsmfastotheaclionofanaqueomacidic solutionhavingapHbaween2and6andconsistingof atleastaboot0596oftheuoridciomatleastabont059 oftheionsofatleastoneofdiealkalimetalgandan ad selected from thegxonpofhydrouoric tlnofsaidacidinthesolutionbeingsnch thatthepartoftheacidityofthesolutionis lLAmethodormadha'entcoatii-igon leslxfasofandhnimnbealloyscompris'ngaaidmfaotntheaetionofanaqueo apHbetween 2 and 6 and ofabout09%t08% oftheun'ideioma: leastaboutooftheionsofatleastoneofthealkali metals, andlrydrohocmthe ofsaid acidineadutionbdngsuchthatthepart oftbeadyoftlnisdiwdomsaidadd.
8 consistingoiabout0.9%to8% oftheuorideiomat oftheacidityofthesolutionisdervedomsaidadd. 13. Amethod for producnganadherent coatingon the surfaces of titaniumandtitaniumbasealloys comousacidncsolutxonhavmgaplbetween2and6and cormstingofabout0.9%to8%ofthenondeion,at leastabout0.5% oftheiomofatletoneofthealkah metalgandnitricadmtheconntrationofsaidacidm metakandanacidselectedfromthe group hydrcmicadihydrochloricmnitcaciand md' :.lri tionbeingsndnthatthepartoftheacidity Mecnsinthclcofthispatent UNITEDSTAIESPATEN'IS Panepinto Nov. 22, 1949 Amnndsen May l, 1951 Beach lune 2l, 1955 Miller et al. Doc. 16, 1958 O'I'HHIREFERBCES nalReportGlmSurfzTreatmemofTnaniuninWatawwnAnmalbyBattelleMemmiallmti mOctoherSO, 1953,30pages.
*lwonsacidics'dutinnhmingaplbetwemzandand 50 Amlunell,l95l,p.l52.
Claims (1)
1. AN AQUEOUS ACIDIC SOLUTION FOR PRODUCING A COATING ON SURFACES OF TITANIUM AND TITANIUM BASE ALLOYS HAVING A PH BETWEEN 2 AND 6 AND CONSISTING OF AT LEAST ABOUT 0.5% OF THE FLUORIDE ION, AT LEAST ABOUT 0.5% OF THE IONS OF AT LEAST ONE OF THE ALKALI METALS, AND AN ACID SELECTED FROM THE GROUP CONSISTING OF HYDROFLUORIC ACID, HYDROCHLORIC ACID, NITRIC ACID, AND SULPHURIC ACID, THE CONCENTRATION OF SAID ACID IN THE SOLUTION BEING SUCH THAT THE PREDOMINANT PART OF THE ACIDITY OF THE SOLUTION IS DERIVED FROM SAID ACID.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3041215X | 1955-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3041215A true US3041215A (en) | 1962-06-26 |
Family
ID=10920331
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US563865A Expired - Lifetime US3041215A (en) | 1955-02-07 | 1956-02-07 | Solutions and methods for forming protective coatings on titanium |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928112A (en) * | 1974-01-04 | 1975-12-23 | Us Army | Process for producing stabilized anatase titanium dioxide surfaces for durable adhesive bonding |
| US4075040A (en) * | 1976-03-15 | 1978-02-21 | Societe Nationale Industrielle Aerospatiale | Titanium and titanium alloy surface preparation method for subsequent bonding |
| EP0040461A1 (en) * | 1980-04-16 | 1981-11-25 | Rolls-Royce Plc | Electroplating of titanium and titanium alloy |
| US4728373A (en) * | 1985-09-19 | 1988-03-01 | Nihon Parkerizing Co., Ltd. | Solution and process for cold forming titanium |
| FR2609725A1 (en) * | 1987-01-21 | 1988-07-22 | Nihon Parkerizing | Aqueous solution for the treatment of chemical conversion of titanium or of its alloys |
| EP0291891A1 (en) * | 1987-05-16 | 1988-11-23 | Nihon Parkerizing Co., Ltd. | Process for applying conversion coatings on titanium |
| EP0723602A1 (en) * | 1993-10-15 | 1996-07-31 | Circle-Prosco, Inc. | Hydrophilic coatings for aluminum |
| US20050113603A1 (en) * | 2001-10-05 | 2005-05-26 | Belmonte Frank G. | Method of removing iron oxide deposits from the surface of titanium components |
| US20080280046A1 (en) * | 2007-02-12 | 2008-11-13 | Bryden Todd R | Process for treating metal surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489152A (en) * | 1949-11-22 | Sodium bifltjoride composition | ||
| US2550660A (en) * | 1948-09-04 | 1951-05-01 | Parker Rust Proof Co | Process for producing adherent coatings on stainless steel to facilitate drawing operations |
| US2711364A (en) * | 1953-12-31 | 1955-06-21 | John G Beach | Polishing metals and composition therefor |
| US2864732A (en) * | 1953-10-05 | 1958-12-16 | Battelle Development Corp | Method of coating titanium articles and product thereof |
-
1956
- 1956-02-07 US US563865A patent/US3041215A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489152A (en) * | 1949-11-22 | Sodium bifltjoride composition | ||
| US2550660A (en) * | 1948-09-04 | 1951-05-01 | Parker Rust Proof Co | Process for producing adherent coatings on stainless steel to facilitate drawing operations |
| US2864732A (en) * | 1953-10-05 | 1958-12-16 | Battelle Development Corp | Method of coating titanium articles and product thereof |
| US2711364A (en) * | 1953-12-31 | 1955-06-21 | John G Beach | Polishing metals and composition therefor |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928112A (en) * | 1974-01-04 | 1975-12-23 | Us Army | Process for producing stabilized anatase titanium dioxide surfaces for durable adhesive bonding |
| US4075040A (en) * | 1976-03-15 | 1978-02-21 | Societe Nationale Industrielle Aerospatiale | Titanium and titanium alloy surface preparation method for subsequent bonding |
| EP0040461A1 (en) * | 1980-04-16 | 1981-11-25 | Rolls-Royce Plc | Electroplating of titanium and titanium alloy |
| US4728373A (en) * | 1985-09-19 | 1988-03-01 | Nihon Parkerizing Co., Ltd. | Solution and process for cold forming titanium |
| FR2609725A1 (en) * | 1987-01-21 | 1988-07-22 | Nihon Parkerizing | Aqueous solution for the treatment of chemical conversion of titanium or of its alloys |
| EP0291891A1 (en) * | 1987-05-16 | 1988-11-23 | Nihon Parkerizing Co., Ltd. | Process for applying conversion coatings on titanium |
| EP0723602A1 (en) * | 1993-10-15 | 1996-07-31 | Circle-Prosco, Inc. | Hydrophilic coatings for aluminum |
| EP0723602A4 (en) * | 1993-10-15 | 1996-08-21 | ||
| US20050113603A1 (en) * | 2001-10-05 | 2005-05-26 | Belmonte Frank G. | Method of removing iron oxide deposits from the surface of titanium components |
| US7005011B2 (en) * | 2001-10-05 | 2006-02-28 | Bp Corporation North America Inc. | Method of removing iron oxide deposits from the surface of titanium components |
| US20080280046A1 (en) * | 2007-02-12 | 2008-11-13 | Bryden Todd R | Process for treating metal surfaces |
| EP2094880A1 (en) * | 2007-02-12 | 2009-09-02 | Henkel AG & Co. KGaA | Process for treating metal surfaces |
| EP2094880A4 (en) * | 2007-02-12 | 2011-08-17 | Henkel Ag & Co Kgaa | Process for treating metal surfaces |
| US9234283B2 (en) | 2007-02-12 | 2016-01-12 | Henkel Ag & Co. Kgaa | Process for treating metal surfaces |
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