|Publication number||US2711364 A|
|Publication date||Jun 21, 1955|
|Filing date||Dec 31, 1953|
|Priority date||Dec 31, 1953|
|Publication number||US 2711364 A, US 2711364A, US-A-2711364, US2711364 A, US2711364A|
|Inventors||Beach John G|
|Original Assignee||Beach John G|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (40), Classifications (15)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Uni cdwstatc -Pousnns N GMETALS ANn.. coMrosrm John 6. Beach to Untted States of Anierica as represenfed by the United States Atomic Energy Commission No Drawing. Application December 31, 1953, Serial No. 401,742
4 Claims. (Cl. 4l42) satisfactory because the reaction was too violent and too difficult to control. A mixture of hydrofluoric acid andammonium fluoride has also been employed and this mixture has given very satisfactory results. This method using hydrofluoric acid and ammonium fluoride forms the subject matter of copending application, Serial No. 355,858, filed by John G. Beach et al. on May lS,f 1953. However, in some instances, for instance when zirconium contains occlusions of zirconium carbide, a smooth surface cannot be obtained with a solution of ammonium bifluoride or a mixture of ammonium fluoride and hydrofluoric acid; the surface then shows a relief pattern formed by zirconium carbide granules. 1
A mixture of hydrofluoride acid, ammonium fluoride and nitric acid was also examined for polishing Group VI- metals. A mixture containing 60 grams of ammonium bifluoride per liter in a 50% (byvolume) nitric acid (70%) was used for polishing zirconium containing some tonly .en ploy dglt -isz finally also antob ecttoisthisdnvention toprovide '0 a. method: and E asolntion for polishing; Group -'IV-.me'tals may .be. satisfaef wherebyiternperature as. lawns; 602B are"accomplishedhylimmersing the article to be polished in anaqueous solution containing a water-soluble fluoride, nitric acid and fluosilicic acid. The optional operating temperature is'about .60 F.; how-.
ever, it may vary-.widely. 7
While no treatment is necessary. prior to immersion into the polishing'solution, it has been found advantageous to remove any scale adheringto thesurface by sandor vapor-blasting. I
' I The concentrations of the various components of the polishing solution may vary widely. However, ranges of from 350 to 600 cc.of nitric acid (70%,), 175 to' 400 cc.of fluosilicic acid and at least grams of:
a water-soluble fluoride, such as hydrogen fluoride, am-
monium bifluoride or ammonium fluoride, all per 1 liter I i of solution have been found preferable. Th'efcontent of ammonium fluoride or bifluoride may reach saturation; The best results were obtained with-a solutioncontainin'g 400 cc. of nitric acid, 200 cc. of 30% fluosilicic f acid andSO to l00grams of ammoniumfluorideper liter of solution.
In the following example one embodimentof the in-- it vention is. given in detail.
' 1 Example w g I p Zirconium metal was'immersed .in a solution containing '100 grams of ammonium bifluoride, 400 cc. of a 70% nitric acid and 200 cc. of a 30% fluosilicic acid pe'rll liter zirconium carbide; it was found that both the zirconium exothermic and the temperature is liable togo above 130 F. and the mixture is very unstable at temperatures above 140 F. and starts to decompose. lIt is very difof solution. Immersion 'was carried out at variousf-tem-,
peratures and the thicltnesses of zirconium removed thereby in each instance from each surface per minute were measured. The results are summarized below.
v I removed/mim/surface' 70 to F 0.0006" so" was F 0.000s" to 'F.... 0.001s" to F 0.002s" 110 to F 0.o,o4"
' All surfaces of the zirconium after the treatments at the various temperatures weres'mooth, bright and-uniform.:
Similar results were obtained byftreating titanium, tin and lead witha solution identically composed.
Satisfactory results were obtained with Group IV-' metalsusing solutions containing 480 cc. of 70% nitric i acid, 320cc. of a 30% fluosilicic acid and l9SJcc. of a"- 50% hydrofluoric acid, on solution containing 600 cc.
of a 70% nitric acid, 400cciof a 30% fluosilicic acid and saturated in ammonium fluoride or ammonium bifluoride,
ficult to control the operating temperature within a range as narrow as that from to F. Another disadvantage frequently encountered with the bifluoridemitric acid mixture is the formation of noxious fumes at these high temperatures.
It is an object of this invention to provide a method and a solution for polishing Group IV-metals by which the above-described disadvantages are overcome. I It is another object of this invention to provide a method and a solution for polishing Group IV-metals' whereby the metals are made suitable for plating, and in particular for electroplating, so that the coating obtained thereby is bonded firmly to the polished article. 7 It is another object of this invention-to provide a method and a solution for polishing Group IV-metals whereby the reaction can be controlled easily.
It is still another object of this invention to provide a method and a solution for polishing Group IV-metals whereby no noxious fumes are developed.
metal containing zirconium. carbide occlusions compris-' zirconium prior to or a solution containing 356 ccof a 70% nitricacid, 178 cc. of a 30% fluosilicic acid and 109 cc. of a 50% hydrdfluoricacid. 1
The invention'is applicablefor .all' purposes where a smooth surface is desired, and in particular for electroplatingQas has been mentioned before. For instance, the.
invention is suitable par excellence as a p'retreatment'of electroplating witha metal, e. g. with nickel. V v V It will be understood that this invention is not to be limited tothe details givenherein but that it may be" modified within the scope of the appended claims. What is claimed is: 1. A process of polishing the surface of zirconium ing immersing said surface into' anv aqueous solution of about 60.to 85 F. consisting, per one liter of solution, I.
of water, at least 50 grams of a water-soluble fluoride,
350 to 600 cc. of concentrated nitric acid and from i to 400 cc. of a 30% fluosilicic acid.
2. The process'ofclaim 1 in which the solution cum from 50 to 100 grams of ammonium bifluoride, 400 cc. tains from 50 to-l00 grams of ammonium bifiuoride, of a-70% nitric acid,-and 200 cc. of 21-30% fluosilicic 400 cc. of a 70% nitric acid, and 200 cc. of a 30% fiuoacid. silicic acid per one literof solution.
'3. An aqueous solution for chemically polishing the 5 References 111 file of ihls P surfaces of zirconiumcontaining zirconium carbide occlu- UNITED STA ES P S sio ns consisting; per one'liter of solution, of 175. to 400 1: z r I cc. of a 30% fiuosilicic acid, 350 to 600 cc.-of a 70% $323235??? g1 nitric acid, and at least 50 grams of water-soluble fluorldc. 7, 2,678,811 5 spopngrH H May 18, 71.954
4. The solution of claim 3 in which the contents are 10
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2413365 *||Apr 13, 1944||Dec 31, 1946||Wyandotte Chemicals Corp||Cleaning composition for aluminum and aluminum alloys|
|US2614913 *||Oct 20, 1950||Oct 21, 1952||Gen Motors Corp||Brightening bath|
|US2678875 *||Jun 29, 1950||May 18, 1954||Aluminium Lab Ltd||Chemical brightening of aluminum|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2829091 *||Jun 4, 1956||Apr 1, 1958||Menasco Mfg Company||Method for electroplating titanium|
|US2856275 *||Nov 20, 1956||Oct 14, 1958||Amchem Prod||Chemical treatment of refractory metal surfaces|
|US2864732 *||Oct 5, 1953||Dec 16, 1958||Battelle Development Corp||Method of coating titanium articles and product thereof|
|US2876144 *||Feb 24, 1956||Mar 3, 1959||Crucible Steel Co America||Metal pickling solutions and methods|
|US2879186 *||Jun 7, 1957||Mar 24, 1959||Fur Unternehmungen Der Eisen U||Process for blanching zirconium|
|US2881106 *||Mar 7, 1957||Apr 7, 1959||Lord Mfg Co||Surface bonded titanium product, composite structure thereof and method of bonding atitanium surface|
|US2900715 *||May 28, 1956||Aug 25, 1959||Steel Improvement & Forge Co||Protection of titanium|
|US2921836 *||Apr 24, 1956||Jan 19, 1960||Carborundum Co||Process of treating metals|
|US2921888 *||Oct 26, 1956||Jan 19, 1960||Vertol Aircraft Corp||Electroplating titanium ano titanium alloys|
|US2942954 *||Oct 20, 1955||Jun 28, 1960||Gen Motors Corp||Non-hazardous etching solutions|
|US2955061 *||Aug 2, 1957||Oct 4, 1960||Parker Rust Proof Co||Fluoride coating on zirconium|
|US2974021 *||Feb 8, 1957||Mar 7, 1961||Albert Borowik||Process and composition for chemically treating titanium and its alloys|
|US2981609 *||Nov 20, 1956||Apr 25, 1961||United Aircraft Corp||Etching bath for titanium and its alloys and process of etching|
|US3007830 *||May 29, 1957||Nov 7, 1961||Raytheon Co||Surface treatments of semiconductive bodies|
|US3010854 *||Dec 31, 1954||Nov 28, 1961||Armco Steel Corp||Pickling solution and method|
|US3019194 *||Feb 18, 1957||Jan 30, 1962||Alan D Brite||Cleaning composition and method|
|US3025189 *||Dec 10, 1958||Mar 13, 1962||Purex Corp Ltd||Composition and process for removing heat scale from metal parts|
|US3030286 *||Nov 21, 1958||Apr 17, 1962||Titanium Metals Corp||Descaling titanium and titanium base alloy articles|
|US3033795 *||Jun 10, 1957||May 8, 1962||Purex Corp Ltd||Compositions and process for removal of radioactive contaminants|
|US3041215 *||Feb 7, 1956||Jun 26, 1962||Parker Rust Proof Co||Solutions and methods for forming protective coatings on titanium|
|US3087874 *||Feb 13, 1961||Apr 30, 1963||Edward Thompson Robert||Electropolishing of titanium base alloys|
|US3106499 *||May 11, 1959||Oct 8, 1963||Rohr Corp||Process and composition for cleaning and polishing aluminum and its alloys|
|US3457103 *||Apr 4, 1967||Jul 22, 1969||Hoechst Ag||Process for protecting titanium and titanium alloys against corrosion by oxidizing acid media|
|US3514407 *||Sep 28, 1966||May 26, 1970||Lockheed Aircraft Corp||Chemical polishing of titanium and titanium alloys|
|US3622391 *||Apr 4, 1969||Nov 23, 1971||Alloy Surfaces Co Inc||Process of stripping aluminide coating from cobalt and nickel base alloys|
|US3850712 *||Jun 12, 1972||Nov 26, 1974||Rolls Royce||Method of etching a titanium or titanium alloy part|
|US3986970 *||Apr 26, 1974||Oct 19, 1976||The Furukawa Electric Co., Ltd.||Solution for chemical dissolution treatment of tin or alloys thereof|
|US4017368 *||Nov 11, 1974||Apr 12, 1977||General Electric Company||Process for electroplating zirconium alloys|
|US4277289 *||Jul 6, 1979||Jul 7, 1981||Aluminum Pechiney||Process for removing titaniferous and silico-aluminous incrustations from surfaces|
|US5100500 *||Feb 8, 1991||Mar 31, 1992||Aluminum Company Of America||Milling solution and method|
|US5102033 *||Apr 16, 1991||Apr 7, 1992||Kaiser Aluminum & Chemical Corporation||Method for improving the fillet-forming capability of aluminum vacuum brazing sheet products|
|US5114532 *||Mar 21, 1991||May 19, 1992||Seagate Technology, Inc.||Process of etching iron-silicon-aluminum trialloys and etchant solutions used therefor|
|US5993559 *||Apr 16, 1998||Nov 30, 1999||Siemens Aktiengesellschaft||Method for removing tin|
|US7501073||Feb 2, 2004||Mar 10, 2009||Depuy Products, Inc.||Methods for producing metallic implants having roughened surfaces|
|US7901462 *||Jun 23, 2005||Mar 8, 2011||Depuy Products, Inc.||Implants with textured surface and methods for producing the same|
|US8696759||Apr 15, 2009||Apr 15, 2014||DePuy Synthes Products, LLC||Methods and devices for implants with calcium phosphate|
|US20040167632 *||Feb 24, 2003||Aug 26, 2004||Depuy Products, Inc.||Metallic implants having roughened surfaces and methods for producing the same|
|US20040167633 *||Feb 2, 2004||Aug 26, 2004||Depuy Products, Inc.||Metallic implants having roughened surfaces and methods for producing the same|
|DE1101899B *||Sep 19, 1957||Mar 9, 1961||American Chem Paint Co||Saure, waessrige Loesung zum Entzundern und Glaenzen von Gegenstaenden aus Titan, Zirkon und deren Legierungen|
|EP0034733A1 *||Feb 3, 1981||Sep 2, 1981||Ab Asea-Atom||Method for treating a tube of a zirconium-based alloy when applying a protective layer|
|U.S. Classification||216/109, 510/269, 134/3, 205/212, 216/108, 510/257, 252/79.3|
|International Classification||C25D5/34, C23F3/00, C25D5/38, C23F3/06|
|Cooperative Classification||C25D5/38, C23F3/06|
|European Classification||C25D5/38, C23F3/06|