2) United States Patent Izawa et al ay METHOD FOR MANUFACTURING SURFACE, ‘TREATED STEEL MATERIAL USING A CHEMICAL CONVERSION TREATMENT QUID Go, Inventors: Masaru awa, Kobe (JP): Ku Kobe (P) Assignee: Sumitomo Metal Industries, Ltd, Osaka (IP) Notice: Subject to any disclaimer, the term ofthis pateat is extended or adjusted under 38 USCC. 1540) by 733 days. 107771,204 (21) Appl. No. (22) Filed: Feb. 5.2004 6s) Prior Publication Data US 200410154700 A1 Aug. 12,2004 Related US. Application Data Division of application No, 10/277,964, filed on Oct 23, 2002, now Pat. No 6,756,092 @) G0) Foreign Application Priority Data Feb. 26, Dee. 3 2001 2001 2001-050740 2001-36876 or) cr) Gh me. C2ic 2208 ‘00 (2006.01) (2006.01) 148/262; 148/253; 106/14.05 106014.11; 106114.12; 106/14.14 Field of Classification Search 1480253, 148262; 106/14.05, 14.11, 14.12, 14.14 See application file for complet search history. S.C 'US007918945B2 (10) Patent No.: US 7,918,945 B2 (45) Date of Patent: Apr. 5, 2011 66) References Cited US. PATENT DOCUMENTS AAMKESL A$ 1O198 Yanda 255320 ake 81 A + 121981 Donoho 148 262 Ss00as1 A+ 'F1SKS Outalek al [e881 77090 A | 11988 Hakama el A197 A #1 I9KD Calera ro6140s Goran a” S00 Matoshins el A R199 Capocea A+ M1998 Boulos a 8, Soman A” 1999. Napahina cl G23i688 BL $2001 het al aondiori2st Al* 12002 Gokeea FOREIGN PATENT DOCUMENTS ca 0395902101990 (Continved) (OTHER PUBLICATIONS “Metals Handbook: Desk Editon 1998, pp. 1157-1158." 2nd el, ASM International, Primary Examiner — Roy King Lois Zheng (74) Attornes, Agent, or Firm — Clark & Brody Assistant Examiner on ABSTRACT A method of mantfacturing a surface treated ol wel pipe ‘comprising performing chemical conversion ieatment onan ‘il well pine having a steel composition containing 0.5-139% Cr sing a chemical conversion treatment liquid containing inc and phosphoric acid or manganese and phosphor acid ‘and further containing potassium tetraborateto form chemi: «al conversion film ofa zinc-phosphate type or a manganese shosphate type, wherein the chemical conversion treatment is ‘arred out in the absence of faerie tons. 6 Claims, 1 Deavsing SheetUS 7,918,945 B2 Page? FOREIGN PATENT DOCUMENTS z gest ye 2 acts al tar * Biase wise ot Ip lose a» 2001--335956* 12/2001 ® fits | 103 = ® ‘100020 A 11980 i) CN ® cee 8 ee ® woe + cited by examinerU.S. Patent Apr. 5, 2011 US 7,918,945 B2US 7,918,945 B2 1 METHOD FOR MANUFACTURING SURFACE, ‘TREATED STEEL MATERIAL USING 4 (CHEMICAL CONVERSION TREATMENT. LIQUID ‘This application is divisional of application Ser. No 10/277,964, filed on Oct. 23, 2002, now US. Pat. No. 6,756, 092 ‘TECHNICAL FIELD This invention relates to chemical conversion treatment liguid for forming a chemical conversion film on te surface ‘ofa steel material sich as a Crcontaining steel and to 3 surface treatment method employing the liquid. ‘The present invention also relates to a surlace treated stl material which is manufactured using such a surface tret- ‘ment method and partieularly oa surface treated steel mate- Fial having excellent seizing resistance BACKGROUND ART Chemical conversion treatment is a type of treatment in hich the surface ofa stel material anda corosive solution ‘are chemically reaeted with each other to form a film of 3 ‘corrosion product having good adhesion tothe surface ofthe ‘eel material. Chemical conversion teatment i frequently refered to as phosphate treatment, chromate treatment, ‘oxalate treatment, ete, depending upon the type of eorosive solution which is employed, However, a chemical conversion film cannot be formes by such conventional chemical conversion treatment of ses] svel asa high-Cr sted. ‘As disclosed in Japanese Published Unexamined Patent Application $7-82478, for example, a method is known in ‘which chemical conversion treatment is performed on the surface ofa steel material using a chemical conversion treat- ‘ent guid hased on an alkali metal phosphate and contain- ing a titanium compound and a chlorate salt, alter whieh funer chemical conversion treatment is performed using & ‘chemical conversion treatment quid containing azine phose phate. However this method las the disadvantage that treat ‘ment must be perfommed two times. Moreover, this method ‘cannot form a sound chemical conversion film ofa phosphate ‘on. high-Ce stool such as 13% Cr sto Tapanese Published Unexamined Patent Application 5.40034 discloses a method of surface treatment using. & ‘chemical conversion treatment liquid containing manganese and phosphoric seid to whieh fluoride ions are added. How= ‘ever, even with this method, itis not possible to fom a ‘chemical conversion film on & Cr-contaiing ste! (il well steel pipes are connected to each other through ‘couplings. Fortis purpose, mae threads formed on the ends ‘of ol wel steel pipes are mated with female threads formed. ‘onthe inner surface of couplings, andthe threads are tight ‘ened to forma gas- and lquid-ight joint connecting the pipes. At the time of tightening, a lage torque is applied to the threads, soit becomes easy for detects suchas galling o occur ‘on the thread surface, which reduces the number of times, which the oil well ste! pipes can be repeatedly connected 10 ‘each other, In addition, if corrosion oscurs on the thread surface, it becomes dificult to guarantee an adequate gas fightness and liquid tightness. ‘Accordingly. in the past the thread surface ofa threaded jin foroil well steel pipes made of aCr-containing steel was plated witha soft metal sue as Cu in order to prevent galling. 0 o 2 However, due to the man hours required for plating, the plat- ‘ng method is not satisfietory, aad there is room fr improve. sens, DISCLOSURE OF INVENTION “Ths, there has been a demand fora technique which can stably form a sound chemical conversion film such asa zine phosphate film ora manganese phosphate flm on the surface ‘of Creontaining stl ‘An object ofthis invention ist provide a chemical con- version treatment liguid which can stably form a chemical ‘conversion film ofa phosphate even on the surface of a Cr containing steel such as one containing 05-13% Cr Another objet of ths invention isto provide a method of | ‘manufacturing a surface teated steel material in which the surface treatments performed in such a manner that ache «al conversion film ofa phosphate ean be stably formed even ‘on the surface of the above-described Cr-contining steel ‘Yet another object ofthis invention is to provide surface treated stl material having such a chemical conversion fila ‘ofa phosphate formed thereon, ‘The present inventors found thatthe ation of a potas sium compound to a phosphate-type chemical conversion ‘eeatment liquid result in a significant improvement in the ‘ilmcfoming ability and makes it possible to stably form a phosphate ype chemical conversion film even on a Cr-con- faining tee, on which it has been dificult to form. chemical conversion fil, Based on these findings the present inventors continued esearch and development and further found that such effet ‘of a potassium compound and particularly of potassium tet raborate is generally seen in chemieal conversion fin formed by chromate treatment, oxalate treatment, and the like, and completed the present invention. Tn broad sense, the present invention isa surface teat steel material comprising @ stee! material and a chemical conversion fil formed on at last a portion ofthe surface of the sce! materia, the chemical conversion film containing potassium in an amount of O.1-1000 mg? and having a {jekness of 5-50 micrometers anl preferably 5-35 mierome- Ina preferred embodiment of the invention, the chemical conversion film is a phosphate-ype chemical conversion film, such asa zine phosphate-ype chemieal conversion film, ‘ora manganese phosphate-type chemical conversion fm. ia the case ol well see! pipes, itis prefered thata manganese phosphate type chemical conversion flm is formed ona joint portion of couplings and a zine phosphate-type chemical conversion fil is formed on a jot portion of oil well steel Pipes. ‘According 10 another aspect, the present invention is a method of manufacturing a surfce treated ste! material ‘wherein chemical conversion treatment is earied out on the surface ofa stee! material sing a chemical conversion i sent liquid containing zine and phosphoric acid oe mang ‘ese and phosphoric acid, and farther containing potassium. The chemical conversion treatment liquid preferably has ‘molar concentration of potassium-containing ions of at least 6x10-*% and at most 710%, "The chemical conversion treatment may’ be carried ot by immersing the stel material in the chemical conversion reat- iment liquid for at least five minutes at @ temperature of 60-100°C. and preferaly of 70-100° C ‘Altematively. the chemical conversion treatment may be carried out by supplying the chemieal conversion treatmentUS 7,918,945 B2 3 Tiguid tothe steel material fora least ive minutes a a perature of 60-100” C. al preferably 70-100° C, According to yet another aspect, the present invention isa ‘chemical conversion treatment liquid forastecl material con- ‘ain zine and phosphor acid or manganese and phospho- ric acid and further containing potassium, Ina prefered embodiment, the molar concentration of potassium-contaning ions inthe chemical conversion treat- tment liquid ie prefembly at least Gx10™% and at most el0-%, ‘When the chemical conversion tratment liguid of this ‘invention contains manganese and phosphor ack and fre ther contains potassium, the total eid number is preferably at Jeast 30nd fess than 35, and the ratio of the total eid numbee to the fre acid number is preferably 315, BRIEF DESCRIPTION OF DRAWINGS FIG. 158 a schematic view of a setup for a dripping test, sthod use in an example ofthe present invention. BEST MODE FOR CARRYING OUT THE INVENTION ‘The present invention will now be described in more detail, In this spevitieat ss otherwise specified, “96” means According to the present invention, after the surface ofa steel material tobe treated has been degreased and rinsed with ‘water, chemical conversion treatment such as phosphate- type, chromate-type, or oxalate-type treatment is performed ‘onthe stel material, Chemical conversion treatment using 2 ‘chemical conversion treatment liquid conlsining zine and phosphoric acid or manganese and plosploric acid is partieu- iy preferred, Such chemical conversion treatment liquid Js refered o as. zine phosphor acid type ora manganese- Phosphoric acid type chemical conversion treatment liquid. ‘The chemical conversion treatment method itself is known, ‘Therefore, description of the chemical conversion treatment method ise wil be onsite, “There are no particular restrictions on the chemical com= position of ste] material used in the present invention, but the present invention is particularly advantageous when car- ried out on a Cr-contsning steel containing 0.5-13 mass % (indicated below simply by %)ofCr,on which itis difficult 10 perform chemical conversion treatment by conventional ethos. “There are also no limitations onthe form of the stel mate= Fal. For example itean be seamless pipe sed as anol well steel pipe or & coupling therefor and particularly’ a threaded jin portion ofthe pipe or coupling. Altematively.itean bein the form of another type of pipe rod, plate or sheet, or the like. The present invention is particularly advantageous Irom the standpoint of economy when appli toa threaded joint ora seamless ste! pipe such as anil well tel pipe made of a Creontsining sel “The sure roughness Rmax of the portion ofthe surface ‘of the stool material which is to be treated is preferably adjusted 10 be 0.1-60 micrometers, ‘The term “chemical conversion film’ used herein refers to film whieh i formed when product of a chemical reaetion between. solution and the surface of steel material adheres to the steel surface in the form ofa film, Among the various ‘ypesof chemical conversion film ae phosphate types, chro- mate types, oxalate types, et., depending upon the type of solution nse to fom the film. In the presen invention, there ‘re no particule restrictions on the type of the chemical 0 o 4 conversion fl a5 lang as it contains potassium, However, ‘whe the preset invention i applied to joint for seamless steel pipe such a anol well tet pipe, ce film is preferably ‘1 phosphate-type chemical conversion film, This i because phosphate types and particulary phosphoric acid-manganese fypes or phosphoric acid-rine types of chemical conversion film have excellent adhesion toa steet surface and aso have excellent ust preventing properties and resistance to galling, ‘More preferably the chemical conversion film is phosphoric acid-manganese type chemical conversion film. ‘A “chemical conversion eatment gui” refers to a twat ment liquid used to form such a chemical comversion film. Chemical conversion treatment Tiguids also include phos- phate types, chromate types, oxalate types et, In the present inveation, a chemical eonversion treatment liquid contains » potassiuo compound for promoting the {formation ofa chemical onersion film, increasing the uni- {ormity ofthe chemical conversion film, and preventing lack of hiding (exposure of the metalic substrate beneath the film). However, iF ions and Al ions are present together in the chemical conversion treatment liquid, dv tothe action of Fe ions and Zn ions which are present atthe same time, @ sldge of K,Al(Pe.Zn)P, may form and precipitate, and the addition ofa potassium compound othe chemical conversion {reatment liquid cannot produce the desired effects. Accord ingly, chemical conversion treatment is preferably carried out inthe absence of fluoride ions. Examples of potassium compounds which ean be used in the present invention include borates (such as potassium tet- rahorate), hydroxides (such as potasium hydroxide), fivo- Fides (such aspotasias Borde) niteats (sachs passim nitrate) chlorides (sueh as potassium chloride), sulfates (such as potassium sulfate), and the like. A single one of these potassium compounds may be used, or two oF more may be ‘used in combination. Preferably the potassium compound isa borate, and more preferably it s potassium tetraborate. The potassium compound is used by adding toa chemical con- version treatment liguid containing zine oF manganese ‘The mechanism af the effect which potassium has om the formation ofa chemical conversion film is thought to be as follows in the case of «pospaate-type chemical comversion treatment liquid, The ation ofa potassium compound toa chemical con version treatment liguid destroys the equilibrium condition of inc or manganese with phosphoric wei i the liguid, soluble potassium phosphates formed, and it cssolves inthe liquid ‘At the same time, the excess zinc or manganese Forms & foating insoluble gel having feather-ike projections. It is ‘thought that this Rating material s rapidly adsorbed by the surface ofthe steel material and acts as nuclei for promoting the formation ofa filmof a phospatcon the stel surface, and that it forms a sound phospate flm having a minimized ‘amouat of lack of hiding (exposure of the metalic substrate). ‘Although thecause is not clear, withachemica eanversion| treatment” Tiguid to which’ a sodium — compound (Na,B.0,-10H,0) is aldo instead ofa potassium compound, ‘chemical conversion film witha thickness of 10 mierome- ters can be obtained, but thee isa large amount of lack of hiding, snd the film canaot be said to be prictical, Accord ingly, the above-described excellent effect is thought to be specific with potassium compounds. "A potassium compound ean be added toa chemical con- version treatment liquid inthe form ofa powder or inthe form ‘of an aqueous solution. Itean be added when initially prepar- ing the chemical conversion treatment Fighid, or i ean be added immediately before chemical conversion treatment oF ‘during chemical conversion treataent,US 7,918,945 B2 5 In a prefered embodiment of the present invention, the ‘chemical conversion treatment liquid is manganese phos phate-type chemical conversion eatment liquid eontining & Potassium compound, in which the liquid is adjusted 1 have ‘total acid ntber of at least 30 and less than 5S and to have ‘ratio of total acid number to free acid number of 315. The “total acid number” of a chemical conversion teat- mnt igi isthe titration value al) when a 10 ml sample of the liquids subjected to neutralization tiation witha soxiom hydroxide solution having a concentration of 0.1 mil using phenolphalein as an indicator. The “five acid number” of a ‘chemical coaversion treatment iguid is the tiation value (inl) when neutralization station is performed on a 10 ml sample ofthe liquid using bromophenol as an indicator. The “rato of total seid number to fee acid number” isthe total ‘acid number divided by the free acid number and is also referred to a$ the acid ratio. the total acid aumber of «chemical conversion treatment Jiguid containing potassium is fess than 30, the manganese phosphateype film which is formed on the steel material being treated is not suficently uniform, and lack of hiding (exposure ofthe metallie substrate) may beeur. Furthermore ‘even if a uniform chemical conversion film is formed, the treatment time required fr film formation is extremely long. 0 chemical conversion treatment becomes uneconomical I the (otal acid number is 5S or preater, the manganese phos- phate crystals formed on the surface of the steel material being treated become extremely coarse, so lek of hiding may also occur, and the adhesion of the chemical conversion fim to the steel material being treated deteriorates, leading to a deterioration in the resistance ofthe stel material to galling, Preferably, the ftal acid number is 35-53, “The ratio of the total acid number tothe fre cid numbers 3-15 and preferably 6-11 for the same reasons that the total dumber is limited tothe above-described range “The concentration of potassium compound in the chem ‘al conversion treatment liquid in mass" is preferably 0.01- 10%, IF the concentration of potassium compounds i Tes than 0.01%, the film thickness is insufficient. On the other han, ifthe eoncentration of potassium compounds exceeds 10%, the effet of the potassim componinds on film forms tion ssturates. From the standpoint of obtaining unifom film thickness, the concentration ofthe potassium compound Js more preferably 01-10% and tll more preferably 0.1-1%. “This concentration corresponds to a molar concentration of potassium-containing ions of atleast 61096 and at most 7e10-%6, A stil more potassium-containing ions is at least 610-*% and at most 710%. A still more preferred range 5s at least 6e10-°% and at most 7x107%, ‘When the chemical conversion trestment fguid and the surface ofthe ste] material are acted, wether the liquid is applied by immersion, spraying, or otber method! the tem- perature of the chemical conversion Ireatment liquid is adjusted fo 60-100" C. and preferably to 70-100° C Por example, the temperature of manganese phosphate type chemical conversion treatment liguid is preferably 60-100°-C. The temperature ofa phosphorie acid-rine type ‘chemical conversion treatment liquid is 70-100" C- and pref ‘erably 70-80" C. Ifthe temperature is less than 60°C. or 71 «respectively, the speed of a film-forming reaction may ‘extremely deercase, The temperature of manganese phos Phate-fype chemical conversion treatment liquid is desirably atleast 85° C, and preferably 95.98° C, This s because ifthe ‘chemical conversion treatment liquid boils, the evaporation ‘ofwaterhecomes violent, and the concentration ofthe chemi ‘cal conversion treatment liquid ends up being too high. Par- ticularly in the ease ofa zine phosphate-type chemical con 0 o 6 ‘version teatime ligid ifthe temperature exceeds 50° C., etching of the substrate iron surface becomes severe during te inital reaction stage, a lage amount of hydrogen gs is formed, and gas can accumulate inthe bottom of see pipe such a joint Foran il well st pipe so film formation ean be obstructed, and there isa case thal uniform and sound {lm eannotbe formed. At such temperature the immersion timefte tel material being treated or the length of contact ‘atecen the sto! material and the chemical conversion eat iui inthe ease of spraying is atleast S minutes “Thee are no panicularresrictionson metodo onning chemical coaverson film on a sec srfae using 8 na ‘eat igsidcontsining potassium. After subjected to pretreat reat sich os degreasing and rinsing with water the stel ‘atrial can he immersed inthe chemical conversion teat ‘ment liquid, othe teatment liguid can be supplied tothe sures othe tel material by spraying or other method TIngeoeral, ia manganese phospte-type chemical eomver- sionteeatmet twas tout that after the tel material tobe ‘rated is subjected to preveatment suchas depeasing. Hns- jg with water. pickling. and rinsing with wate, it must be furersubjecte ty surace adjustment weaumeat with an agucoussoltion of a mixtere of manganese phosphate ad Sexium pyrophosphate, bu inthe preset invention, rior performing manganese phorpbatesype chemical conversion ‘reat, such surfaceadjstment treatments not necessary ‘A chemical conversion film which is formed using the chemical conversion treatment guid according tothe present Javention can uniformly covee the steel sures. The pots sum contet of such chemical conversion fiz 61-1000 ‘mpi, and in this case, by making the thickness 5-50 micrometer, preferably $35 micrometers the elect thereoF can be adagustely exhibited. Furthermore, the crystals are fine and dense, x0 they have aa excellent ability to retain a Jubricant suchas prease ora old lubricant between erst, 00d Tobicating properties are exhibited and when its po- Vide in a joint for an oi Wel ste pipe and pariclary 00 threads, it exhibits excelent properties “The uniformity ofthe ehmical conversion film increases ann exposure of the metic subsea is reduced if the mount of passe i the fil st least Ot mn”. There reno farther impeovensentsin the properties ofthe film when the amount of potassium in the film excocds 1000 mg. 30 in light of economy, the amount s preferably at most 1000 mei ‘he thckness ofthe chemical conveeson fils ss than 5 micrometers, the film cannot exhibit quate properties such as corrosion resistance. On the other hand, if the fl thickness excess $0 micrometers, the amountof phosphoric acid and rine or manganese consid in the eerie cone ‘ersion reatment liquid naturally becomes lng ad the i ‘ids rpily sca up. ight of economy, thei thickness is prefeably at mos 35 micrometers The content of potassium compounds inthe chemical con- version treatment igoid and the content of potassium com pounds in the chemical conversion fila are not always the Same sine the Iter varies depending upon the type of tel ‘material and her chemical conversion eater conditions In particular. ia the ease ofa C-conaning sted, with low temperate of 20.30°C. ora chemical conversion time of Jess than 5 minutes, the resting chemical conversion film doesnot contain an equate amount of potassium and it has fn increased lack of baling with an inferoe resistance to saliUS 7,918,945 B2 1 Next, the effects of the present invention will be described more specifically in connection with working examples. EXAMPLES Example 1 example, phosphate chemical conversion treatment od out using three Cr-containing steels (C: 0.25%) witha Cr content of 1%, 3%, oF 13% Each of the Crcontaining steels was melted in a vacusm melting furnace aoe then cast nto 25-ka rectangular ing, Which was hot rolled to a thickness of 8 mm and thea ‘machined to foam test pieces having thickness of S mm, & ‘width of 25 mm, length of 30 mm, anda surface roughness imax of S micrometers Potassium ttrahorate was used as a potassium compound ‘and a commercially available zine phosphate chemical con- version treatment Iguid was used as a chemical conversion treatment lig, 8 A chemical conversion treatment liquid was prepared by’ adding potassium tetrborate tothe zine phosphate liquid to givea concentration of 0-10% and twas placed at a tempera- ture of 75° C. in a $00 ml container, Test pieces which had bee subjected to pretreatment suchas degreasing and rinsing ‘with water were immersed in the liquid for5 minutes and thea pulled out and rinsed with water ad dried. “The thickness ofthe film which was formed onthe surface ‘ofthe rest pieces was measured with an electromagnetic film thickness meter. The uniformity of the film was evaluated ‘with a scanning electron microscope (SEM) and with an image analyzer. The potassium content of the flim was deter ‘mined by immersing the chemically treated test pieces in an ‘aqueous 5% chromie seid solution at 75°C. to dissolve just the film followed by atomie absorption analysis ofthe resul- ing solution to determine the amouat of potassium, “The test results are shown in Table 1 TABLE L ws Males Tete an) Pal! Comte’) Uioiy 5? os ites fe 8S 8 bs fate on 8 8 oe 8 tos Syews 8 tk oo ine © &z 6 8 8 farce 8 ie 8 tos Sant ok oe x OX oie eo 8S 3 Poi $ oS 8 oR 8US 7,918,945 B2 9 Inthe table, the flan thickness was evaluated as fllows: X (unacceptable) indicates # film thickness of less than S imierometersand > (good) indicates film thiekness of at least 5 micrometers. The uniformity ofthe film was evaluated by the test result of ara ratio (%) of unidden surface (exposed metallic surface) observed in the film formed on the test Pieces. 2 (good) indicates an area ratio of at most 5%, & {sual indicates an area ratio of greater than $% and at most 20P%, and X (unacceptable) indicates an area ratio exceeding 20R%, Fore overall evaluation,» (acceptable) indicates that the fet ress wre «fo bth te ln thiekness ad the uniformity of thefil and X (unacceptable) indicates tet ule nore or Torons or bt ofthe Bm icknes andthe fil unin. le 2 “The test materials used in this example were steels having the following stl compositions (1) Carbon stel-C: 0.25%, @) Cr—Mo stecl-C: 0.25%, Cr: 1.0%, Mo: 0.5%, @)Cr steel -C: 0.25%, Ce: 3%, 5%, 13%, oF 29%, 10 Example 1 was repeated except that a commercially avai able manganese phosphate chemical conversion treatment liquid was used as chemical conversion treatment liquid Potassium tetraborate was added tothe manganese phos hate chemical conversion treatment liquid to give a concen: tration of 0-109 andthe resulting chemical conversion te sent guid was placed a a temperature of 85°C, in 9 $00 al container. Test pieces which had been subjected to pret ‘meat such as deyreasing and rinsing were immersed in the chemical ennversion treatment liquid forten minutes and then were pulled out aad rinsed with Water and dried, The resulting chemical conversion film was evaluated the same manner a8 in Example The 22Cesteel wasa comparative example, while the other steels (carbon stl, 1 Cr-0.5 Mo steel. 3 Cr soo, $ Cr stool and. 13 Cr steel) were examples of stels for use in a steel ‘material aecoring tothe present invention The test results are show in Table 2 ad Table 3 TABLE? i Miers Mies Tatham)! Cone ain?) Uiniy_ 08? wiht & & 8 8 farce ce 8 Poise Fe 8 8 OR 8US 7,918,945 B2 u TABLES i unum srtonte Thicke eum Mas _Mole% Tet No, Gin) _Bu"_Comer gia?) ssc ins oa om > on 8 3 ar es 4 ans Bon % i a oo is & Bo ; a Se ie Gun 633% x fun ot 634% s 1 634% x Inthe tables, the film thickness was evaluated as follows: X (unacceptable) indicates a film thickness of less than micrometers and » (good) indicates a thickness of atleast § ‘iieromters. The uniformity ofthe lm was evaluated by the test result of area ratio (%) of unhidden surface (exposed metallic surfce) observed in the film formed on the test pieces. © (good) indicates an area ratio of at most 5%, & {sual indicates an area ratio of greater than 5% and at most 20%, and X (unacceptable) indicates an stea ratio exceeding 20P%. For the overall evaluation, > (acceptable) indicates that the test results were » for both the film thickness and the uniformity of the film, and X (unacceptable) indieates thatthe test resis were A oF X Tor one or both of the film thickness ‘and the film uniformity. Example 3 In this example, an oi well see pipe which i a seamless steel pipe made from s Cr-contaning steel (C: 0.25%) with a Creontent of 1%, 3%, oF 13% Was Used for treaimest ‘A test picce meastring § mim thick, 25 mm wide, and 30 sum long Was eu fom each of the above-described Crcon 12 Unmity 08? xx taining steel pipes, which had been adjusted so that its outer surlace had a surface roughness Rmax of $ micrometers, In this example, a chemical conversion teatment liguid vas prepared by adding potassium tetraborate toa commer- cially available zine phosphate chemical conversion treat ‘meal liquid to give a concentration of O-10% FIG. Lisa sehematie ustraton showing the setup used ia «dipping type test method used employed inthis example, "As shown inthe FIGURE, achemical conversion treatment liquid 1s kept ata temperature of 80°C. ina vessel having a capacity of S00. The chemical conversion treatment ighid 1 was dripped for S minutes from a deipping apparatus 3 onto the outer suriee side of a test piece 2 which had been sub- “6 jected to pretreatment such as degreasing and rinsing with ‘Water, The test piece 2 was then rinsed with water aus die ‘The chemical conversion treatment lguid 1 was heated by 2 ‘hot water for heating S, and it was rcirenated and reused by pump 4 "The resulting chemical conversion film sas evaluated in the same manner a in Pxample 1, The test results are shown in Table 4 0US 7,918,945 B2 13 TABLE i unum srtonte Thicke eum Mas _Mole% Tet No, Gin) _Bu"_Comer gia?) Tose ins a oom om tS 2 ar ‘ w ans 5 % i ° os a » So ; in fa Tose Son x aL Inthe tables, the film thickness was evaluated as follows: X (unacceptable) indicates a film thickness of less than micrometers and » (good) indicates a thickness of atleast § ‘iieromters. The uniformity ofthe lm was evaluated by the test result of area ratio (Y6) of unhidden surface (exposed metal surface) observed in he film formed on the see! pipe test pieces. = (good) indicates an area ratio of at most ¥%,& osu) indicates an area ratio of greater than 5% and at most 20%, and X (unacceptable) indicates an stea ratio exceeding 20P%. For the overall evaluation, > (acceptable) indicates that the test results were » for both the film thickness and the uniformity of the film, and X (unacceptable) indieates thatthe test resis were A oF X Tor one or both of the film thickness ‘and the film uniformity. Example 4 In this example, an oil wel sto! pipe made ftom a Cr ‘containing see (C-0.259%) having a Crcontent of 1%, 3%, oF 13% was prepared, “Test pieces were cut from the above-described ste! pipe hich had been adjusted so that its outer surface hada surface Un 0 o 14 tomy O87 x Xx roughness Rmax of S micrometers. Each test piece was § mm thick, 25 mm wide, and 30 mam long. ‘A chemical conversion treatment liquid was prepared by adding potassium tetraborate to a commercially available ‘manganese phosphate chemical conversion treatment liquid to give a concentration of O.1-1.0% and then adjusting the total acid number to at Teast 30 und les than $$ and the ratio ofthe toial acid number to the free acid number to $.2-90. ‘The chemical conversion treatment liquid was placed at a temperature of 95° C. in 1008 ml container. Test pieces on hich pretreatment such as degreasing and rinsing with water hha been performed were immersed for twenty minutes the chemical conversion treatment liquid and then were washed ‘with water and dried, “The chemical conversion film formed on the surface of the steel ofthe test pieces was evaluated nthe same manner asin Example 1 Tnthe table flim uniformity was evalssted by the area aio of unhidden surface (exposed metallic surface) as follows: © (excellent) indicates an area ratio of at most 1%, « (good) indicates an area ratio of preaterthan 1% and at most SUS 7,918,945 B2 15, the overall evaluation,» (acceptable) indicates that the test results were © of » forthe uniformity ofthe film. The test results ae shown in Table 5, TABLES semiomse Teal re Th rein ‘ tite state Sie fa ‘eu ° 3.8 8 Bs 33 9 162 48 9 126 a8 Bee mo 8 bo % ” INDUSTRIAL APPLICABILITY, According o the present ination, using a chemical con- version treatment liquid containing zine and phosphoric acid ‘or manganese and phosphoric acid to which 0.01-10% of a potassium compound is added, itis possible to easily and ably form a sound phosphate chemical conversion film ‘which i uniform and has excellent adhesion othe surface of asec] containing O.5-13% Cr Furthermore, using the present invention, itis possible (0 easily and stably form a thick ‘chemical conversion lm having adhesion superior to tt of the prior ant on a carbon steal as well “The invention claimed is 1A method of manuficturing o surface treated oil well pine comprising performing chemical conversion treatment ‘on an oil Well pipe having a steel composition containing 16 05-13% Cr using a chemical conversion treatment liguid containing zine and phosphoric acid or manganese and plos- phorie acid and furter containing potassium tetraborate to im Oven 8 8 et {form «chemical conversion film of a zine-phosphte type oF 1 manganese phosphate type, wherein the chemical conver sion treatment is carried out in the absence of fluoride ions and further wherein a total acid number of the chemical conversion treatment liquid is at least 30 and less than $5, a fee acid number is 3.6 to 60, and a ratio of the total acid bet tothe free seid number is 610 1 2..A method of manufacturing a surface vated oil well pipe as claimed in claim 1 wherein the chemical conversion freatment liguid has @ molar concentration of potassium: containing ions of atleast 6 10~*% and at most 710". 3. A method of manufacturing a surface treated oil well pipeasclsimed inclaim I wherein chemicel conversion treat- ‘meat is caried out by immersing the surface of the ol well pipe inthe chemical conversion treatment liquid ata temaper- {re of 60-100° C. for at least five minutesUS 7,918,945 B2 7 18 4.4 method of manufacturing a surface tested oil well _ 6."The method of els 1, wherein the chemical eouversion pipe as laimed in elam I wherein the chemical conversion films formed on the sel surface ofthe oil well pipe whet a trzatmentiscarriedout by supplying the chemical conversion. product of chemical reaction between a solution and the sur ‘treatment to the surface ofthe oil well pipe at temperatureof face of the oil well pipe adheres to the steel surface in the 60-100" C. for atleast five minutes pcan canesin ect 5. The method of claim 1, wherein rinsing treatment with * PEMA! ‘eeatment water and drying treatment is followed alter the chemicalUNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 27,918,945 B2 Page | of 1 APPLICATION NO, : 10/771294 DATED + April 5, 2011 INVENTOR(S) + Heawa etal Its certified that error appears in the above-dentfied patent and that said Letters Patent is hereby corrected as shown below: Title page, item [62] Related U.S. Application Data should read: Division of application No. 10/277,964, filed on Oct. 23, 2002, now Pat. No. 6,756,092, which is a Continuation of PCT/SP02/01521, filed on Feb. 21, 2002, Signed and Sealed this First Day of November, 2011 Dud 3: Capps David 1. Kappos Director of the United States Patent amd Trademark Office