2) United States Patent oy 3) om (60) G0) eb. 26, 2001 Dee. 3, 2001 on) (2) (58) Izawa et al CHEMICAL CONVERSION TREATMENT LIQUID Inventors: Masaru Lawa, Kobe (JP); Kunio Goto, Kobe (P) Assignee: Sumitomo Metal Industries, Led. Osaka (IP) Notice: Subject to any disclaimer, the team ofthis patent is extended or adjusted under 35 USC. 154(b) by 0 days, Appl. No 131039,656 Filed: Mar. 3, 2017 Prior Publication Data S 201100146847 AL Jun, 23,2011 Related U.S. Application Data Division of application No, 10/771,294, filed on Feb 5, 20M, now Pat.No. 7,918,945, which sa division of ‘pplication No. 10/277.964, filed on Oct. 23, 2002, now Pat, No, 6,756,092, whieh is a continuation of ‘pplication No, PCT/IP02I01521, filed on Feb. 21 2002, Foreign Application Priority Data or) (P) 2001-50740 2001-36876 Int.Cl. C23C 228 C2ic 2A2 (2005.01) (2006.01) us.cl. 148/262; 106/14.05; 105/14.11;, 10611412; 148/253; 148/261 Field of Classification Search =... 148/253-263; 106/14 12, 1408, 14.11 ‘ce pplication file for complete search history. US008333847B2 (10) Patent No. 4s) Date of Patent: US 8,333,847 B2 Dec. 18, 2012 66) References Cited US. PATENT DOCUMENTS AU7Ag6SL A 1OIOE Vance 4a8eo41 A 121981 Donato Boose 2 "Frost male at 47098 4 91988 Halaman ota GSRL97S A AVIS) Callers Goomea A 'S1990° Masushima ta S258505 A 81993 Cape etal S728235 A M1908 Boulos eal Soan292 A 81999 Nagas etal 28688 BL $2001 ent a @aeLASD BL* 102002 Risop eta Continved) POREIGN PATENT DOCUMENTS ep 2611597 A 3/1988 ca ose © 101980 (Continved) OTHER PUBLICATIONS “Metals aadbook: Desk iin pp 1is7-1158 of, ASM nterations, 1998 Primary Examiner (74) Attorney Lois Zheng, Agent, or Firm — Clark & Brody on A chemical conversion treatment liquid which can stebly form a phosphate-type chemical conversion film on a stee! smateral fora joint portion of ano well tel pipe containing (05-13% Cris developed, Using a chemical conversion treatment iguid to which @ prescribed amount of potassium is added, a chemical conver on film containing a prescribed amount of potassium com- pounds and having a preseribed thickness can he formed on the threaded surface of a joint portion ofan oil well tee! pipe ABSTRACT 4 Claims, 1 Drawing SheetUS 8,333,847 B2 Page 2 USS. PATENT DOCUMENTS w on2v7sss 101992 20020011281 AL 2002. Gebel. Hy bee | ed w oo2es9se 101997 FOREIGN PATENT DOCUMENTS. a een ra ‘sais AL 711907 Wo ‘9610710 AL 41096 Fe varia! ass Wo wosasss “© 12ige7 ® somes 1982 WO WooasiTt © ‘9199 ie ‘1000260 A 1198 ® ore 91089 * cited by examinerU.S. Patent Dee. 18, 2012 US 8,333,847 B2US 8,333,847 B2 1 (CHEMICAL CONVERSION TREATMENT Liguip ‘TECHNICAL FIELD ‘This invention relates to chemical conversion treatment Tiguid for forming a chemical conversion film on the surface ‘of steel material sch as a Creontaining steel and to 8 surface weatment method employing the liquid ‘The present invention also roltes to a surlace treated stl material which is manulactured using such a surface treat ‘ment method and particularly to a surface treated see mate- rial having excellent seizing resistance Chemical conversion treatment is a type of treatment ia which the surface of stel material ands corosive solution ‘are chemically reacted With each other to form film of 3 ‘corrosion product having good adhesion to the surface ofthe steel material. Chemical conversion treatment is frequenty referred to as phosphate treatment, chromate treatment ‘oxalate treatmea, etc. depending upon the ype of eorosive Solution which is employed, However, chemical conversion film cannot be formes by such conventional chemical conversion eatment on & sos) sueh asa high-Cr see. "As disclosed in Japanese Published Unexamined Patent Application $7-82478, for example, a method is known in ‘which ciemieal conversion treatment is performed on the surface ofa steel malerial using a chemical conversion tret- ‘ment guid based on an alkali metal phosphate and contain- ing a titanium compound and a chlorate salt, alter whieh further chemical conversion treatment is performed using & ‘chemical conversion treatment quid containing a ine phos- Pate. However this method has the disadvantage that reat ‘ent must be perfonmed two times, Moreover this method ‘cannot fom sound chemical conversion film ofa phosphate ‘on a high-Ce ste! such as a 13% Cr ste Japanese Published Unexamined Patent Application 5.40034 discloses a method of surface treatment using. 2 ‘chemical conversion teatment liquid containing manganese and phosphorie acid to which fluoride ions are aed. Hows- ‘ever, even with this method, itis not possible to fomm a ‘chemical conversion film on # Cr-containing steel (il well ste! pipes are connected to each other through ‘couplings. Fortis purpose, male treads formes onthe ends ‘of ol Wel steel pipes are mated with female threads formed. ‘onthe inner surlace of couplings, and the threads are tight ‘ene to form agas- and ligui-tight joint connceting the At the time of to tightening, a lage torgue is applied to the threads, soit becomes easy for delecs sueh as galling o occur ‘on the thread surfice, which reduces the number of times which the ol well ste! pipes can be repeatedly connected t0 ‘each other, In addition, if cortosion occurs on the thread sutlice, it becomes dificult o guarantee an adequate gas tightness and liquid tightness. “Accordingly. in the past the thread surface of a threaded Joint forol well steel pipes made of aCr-contaning steel was plated witha soft metal suc as Cu in order to prevent galling. However, due tothe man hours required for plating, the plat- jing method is not satisfactory, and there is room forimprove- ments DISCLOSURE OF INVENTION “Thus, there has been a demand fora technique which ean stably form a Sound chemical conversion film such asa zine Phosphate film ora manganese phosphate film on the surface of a Crcontaining see 0 o 2 An object ofthis invention i to provide a chemical con- version treatment liquid which ean stably form a chemical conversion flm ofa phosphate even on the surface of Cre ‘cntining steel such as one containing 05-13% Cr Another object of this invention is to provide n method of manufacturing a surface treated steel material in which the surface treatments performed in such a manner that chem «al conversion film ofa phosphate ean be stably formed even ‘on the surface of the above-described Cr-contining ste ‘Yel another object ofthis invention sto provide a surface treated stel material having such a chemical conversion film ofa phosphate formed thereon, ‘The present inventors found thatthe addition of a pot sium compound to a phosphate-iype chemical coaversion treatment liguid results ina significant improvement in the ‘ilmcforming ability and makes it possible to stably form a phosphate-ype chemical conversion film even on a Cr-con- ‘aining ste!, on which thas been dificult to forma chemical conversion il ‘Based on these findings the present inventors continued esearch and development and further found that such effect ‘of a potassium compound and particularly of potassium tet raborate is generally seen in chemical conversion films formed by chromate treatment, oxalate treatment, and the like, and completed the present invent In. broad sense, the present invention isa surface tated steel material comprising a stee! material and a chemical conversion fil formed on at least a portion othe surface oF the sce! materia, the chemical conversion film containing potassium in an amount of O.1-1000 mgs? and having a {hiekness of 5-50 micrometers and preferably 5.35 mierome- a a preferred embodiment of the invention, the chemical conversion film is a phosphate-ype chemical coaversion film, such asa zine phosphate-ype chemical conversion ill, ‘ora manganese phosphate-type chemical conversion im. in the case ol well see! pipes, itis prefered thata manganese hosphate-ype chemical conversion film is formed on a joint portion of couplings and a zine phosphate-type chemical conversion fil is formed on a joint portion of cil well stecl pipes. ‘According to another aspect, the preseat inveation is a method of manufacturing a surfice treated steel material ‘wherein chemical conversion treatment is euried out on the surlace ofa stee! material using a chemical conversion treat- sient liquid containing zine and phosphoric acid oe mang nese and phosphoric aid, and further containing potassium. “The chemical conversion treatment liquid preferably has 3 ‘molar concentration of potassinm-contaning ions of at last 6«10-% and at most 7x10", ‘The chemical conversion treatment may’ be carried out by ‘immersing the stel materia inthe chemical coaversion rea ‘ment liquid for at least five minutes at temperature of 60-100" C. and preferably of 70-100° C ‘Altematively, the chemical conversion treatment may be carried out by supplying the chemieal conversion treatment liquid to the steel material fora least ive mintes ata tem- perature of 60-100" C. and preferably 70-100° C. According to yet another aspect the present invention is 3 chemical conversion treatment lguid fora steel materia eon- taining zine and phosphorre acid or manganese and phospho ric aid and further containing potassium. In a preferred embodiment, the molar concentration of potassium-containing ions in the chemical conversion ta rent liquid i preferably at least Gx10~% and at most Tel,US 8,333,847 B2 3 ‘When the chemical conversion treatment liguid of this ‘vention contains manganese and phosphor aed and fur- ther contains potassium, the total seid number is preferably at Jeast 30 and less than 5S, and the rato of the total acid number to the fre acid number is preferably 3-15, BRIEF DESCRIPTION OF DRAWINGS FIG. 1 isa schematic view ofa setup for a dipping test, method used in an example ofthe present invention BEST MODE FOR CARRYING OUT THE INVENTION ‘The present invention will now be described in more detail, ss otherwise specified, “6” means According to the present invention; after the surface of 3 steel material tobe treated has been degreased and rinsed with Water, chemical conversion twatment such as phosphate- ‘ype, chromate-type, or oxalate-type treatment is porformed ‘onthe steel material, Chemical coaversion treatment using 2 ‘chemical conversion teatmient liquid cont phosphoric acid or manganese and phosphor Jaely prefered. Such a chemical conversion treatment liquid Js refered to. zine-phosphiorie acid type ora manganese- Phosphoric acid type chemical conversion treatment liquid. ‘The chemical conversion treatment method itself is knowa, ‘Therefore, a description of thechemical conversion treatment method ise wil be onsite, “There are no particular restrictions on the chemical com= position ofa sel material used inthe present invention, but the present invention is particularly advantageous when car- ried out on a Cr-contsining steel containing 0.5-13 mass % (indicated below simply by %)ofCr,on which itisdiffcult to perform chemical conversion treatment by conventional ethos. “There are also no limitations onthe form of the stel mate= rial For example itcan bea seamless pipe used asanoil well steel pipe ora coupling therefor and particularly a threaded jin portion ofthe pipe or enupling. Altematively. it ean bein the form of another type of pipe, rod, aplate o sheet, othe like. The present invention is particularly advantageous Irom the standpoint of eeonomy when applied toa threaded joint {ora seanles steel pipe suchas anil well tel pipemade of ‘aCrcontaining sel. “The sure roughness Rmax of the portion ofthe surface ‘ofthe stool material which is to be treated is preferably adjusted 0 be 0.1-60 micrometers. The term “chemical conversion fil” used herein refers to film whichis formed when a product of a chemical reaction between solution and the surface of stel material adheres 0 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 fomm the film. in the present invention, there ‘re no particular restitions on the type of the chemical ‘conversion fil as long a8 it contains potassium. However, when the present invention i applied toa joint fora seamless steel pipe such as anil wel stl pipe the film is preferably ‘a phosphate-type chemical conversion film, This is because phosphate types and parieulary phosphoric acie-manganese |ypes or phosphor acid-zine types of chemical conversion film have excellent adhesion toa stel surface and also have ‘excellent rust preventing properties and resistance to galling, “More prefer the chemical coaversion film isa phosphoric ‘acid-manganese type ebemical conversion film. 0 o 4 A “chemical conversion treatment iguid” refers to teat ‘meat liquid used to form such a chemical conversion film. Chemical conversion treatment liguids also include phos: phate types, chromate types, oxalate types. ee Tn the present invention, a chemical conversion treatment liquid contains 9 potassium compound for promoting the ormation ofa chemical conversion film, increasing the uni- ‘ormity ofthe chemical conversion film, and preventing lack of hiding (exposure of the metallic substrate beneath the lilm). However fF ions and Al ions are present together in the chemical conversion veatment liquid, dueto the ction of Fre ions and Za ions which are present atthe same time, @ sludge of K,Al(Fe-Zn)F, may form and precipitate. and the addition ofa potassium compound othe chemical eoaversion {eeatment liquid cannot produce the desired effects. Acor ingly, chemical conversion treatment is preferably carried inthe absence of fuoride ions Examples of potassium compounds which can be used in the present invention include borates (such as potassium tet- ruborate), hydroxides (Sueh as potassium hydroxide), fvo- Fides (such a polassivas Nuoride) tats (such as poassinza nite), chlorides uel as potassium chloride, sulfates (sueh as potassium sulfate), and the like. A single one of these potassium compounds may be used or two oF more may be sed in combination, Preleraby the potasium compound is borate, and more prefers it s potasiam tetraborate. The potassiim compound is nsed by adding to a chemical cone ‘Version treatment liguid containing zine or manganese “The mechanism of the effect whieh potassium has on the formation ofa chemical conversion film is thought To be as follows in the ease of a phosphate-type chemical conversion treatment liquid. "The addition ofa potassium compound toa chemical con- version treatment guid destroys the equilibrium condition of ine or manganese with phosphoric sci in the liquid, soluble potassium phosphates formed, and it dissolves in the Laud ‘At the sae time, the excess Zinc or manganese Torms & Hoating insoluble gel having featherike projections. It is thought that this Hating material s rapidly aclsorbed by the strlace ofthe steel material and acts as nuclei for promoting the formation ofa flmofa phospaateon thestel surface, and that it forms a sound phosphate film having a minimized ‘amouat of lack of hiding (exposure of the metalic substrate). ‘Although he cause is not lear, with chemical eonversion treatment Figuid 1 which’ a sodium compound (Na,8,0,-10H,0) sade instead ofa potassium compound, a chemical conversion film with 2 thickness of 10 mierome- ters can be oblained, but there isa large amount of lack of hiding, snd the film cannot be said to be practical, Accord- ingly, the above-described excellent effet is thought to be specific with potassium compounds. ‘A potassium compound can be added 10a chemical con- version treatment liquid inthe form ofa powder or inthe form ‘ofan aqueous solution. ean be added when initially prepa ing the chemical conversion treatment liguid, or it ean be ‘added immediately before chemical conversion reatmeat or ‘during chemical conversion treatment, Ina preferred embodiment of the present invention, che ebemical conversion treatment liquid is @ manganese phos- ‘hate-type chemical conversion treatment liquid containing a ‘potassium compound, in whieh the liguid is adjusted to have ‘foal acid numberof at least 30 and less than 35 and to hve rato of total acd number free acid number of 3-15. “The “total acid number” of a chemical conversion teat. ‘ment guid isthe titration value (ml) when a 10 ml sample of theliquidis subjected to neuteaizaton stration witha soinm hydroxide solution having a concentration of 0.1 mill sing phenolphthalein as an indicator. The “Tree acid number” of a Chemical conversion treatment liquid isthe titration value (cal) whea neutralization titration is performed on 10US 8,333,847 B2 5 sample ofthe liquid using bromophenol as indicator: The “ratio of total acid number to free acid number” i the total ‘acid number divided by the fre acid number and is also referred toa the acid ratio, the total seid number ofa chemieal conversion treatment Figuid containing potassium is less than 30, the manganese phosphate-type film which is formed on the steel material being treated is not suficiently uniform, and lack of hiding (exposure ofthe metallic substrate) may beeur.Furthemore, ‘even if uniform chemical conversion film is fonmed, the treatment time required for film formation is extremely long, 0 chemical conversion treatment becomes uneconomical. 1 the total acid number is 5S or greater, the manganese phos- phate crystals formed on the surfiee of the steel material being treated become extremely coarse, s lek of hiding may also occu, and the adhesion o the chemical conversion fl to the stee! material being treated deteriorates, leading to & deterioration in the resistance ofthe stel material o galling, Preferably, the foal acid number is 35-83. “The ratio ofthe total aid numbero the free acid numbers 3-15 and preferab dumber s limited tothe shove-deseribed range ‘The concentration of potassium compounds in the chemi ‘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 insuficient. On the other hand, ifthe concentration of potassium compounds excoeds 10%, te elfet of the potassium compounds on film forma tion saturates. From the standpoint of obtaining a uniform film thickness, the concentration ofthe potsssium compound ‘is more preferably 01-10% and still more preferably 0.1-1%. This concentration corresponds toa molar concentration of polassiuicontaining ions of atleast 610% and at most 7e10°%, A more prefered range forthe molar concentration ‘of potasium-containing ions sat least 6x10""% and at most 710°, A still more preferred range i at east 610" "%and mast 7x107%. ‘When the chemical conversion treatment fguid and the surface ofthe ste! material are reacted, whether the liquid is applied by immersion, spraying, or other method, the fem- perature of the chemical conversion Weatment liquid is adjusted fo 60-100" C. an preferably to 70-100" C For example, the temperature of manganese phosphate type chemical conversion treatment liguid is peeferably 60-100" C. The temperature of « phosphoric aeid-rineIype ‘chemical conversion treatment Tiguid is 70-100" C. and pref ‘erably 70-90" C. Ifthe temperature is less than 60° C. or 7° C, respectively, the speed of a film-forming reaction may ‘extremely deercase, The temperature of manganese phos= phate-type chemical conversion treatment liquid is desirably at least 85°C. and preferably 95-98° C, This is because ifthe ‘chemical conversion treatment liquid boils, the evaporation ‘ofwaterbecomes violent, and the concentration ofthe chem ‘cal conversion treatment liquid ends up being oo high. Par- ticularly in the case ofa zine phosphate-type ehemical con- version treatment lguid, if the temperature exceeds 90° C., ‘etching of the substrate iron surface hevomes severe during the inital reaction ste, a large amount of hydrogen gas is ormied, and gas ca accumulate in the bottom ofa stel pipe suchas a joint foran oil well ste pipe, so film formation ean be obstructed, and there isa ease thats uniform and sound film cannot be formed. At such a temperature, the immersion time ofthe steel material being reated or the Fength of contact between the steel material andthe chemical conversion treat ‘mnt liquid inthe case of spraying i at least $ minutes, “There are no particular restrictions on amicthod of forming ‘chemical conversion fl on steel surface using a teat 0 o 6 liquid containing potassium. After subjected to pretreat ‘meat such a dezreasing and rinsing with water, the steel ‘material ean be immersed inthe chemical conversion te smeat liquid, or the treatment liquid can be supplied to the surface ofthe steel material by spraying or other method. In general in manganese phosphate-ype chemical cover: siontreatment it was thoughtthat after the sec! material tw be treated is subjected to protreatment such as dogreasing, rns- ‘ng with wate, pickling, and rinsing with wate, it mst be further subjected to surface adjustment treatment with an ‘aqueous solution of a mixture of manganese phosphate and sodium pyrophosphate, but in the present invention, rior to performing manganese phosphale-iype chemical couversion ‘reatment,such surface adjustment treatment isnot necessary. "A chemical conversion film which is formed wsing the henical conversion treatment liquid according tothe present invention ean uniformly cover the stel surface. The potas- sium conteat of such a chemical conversion film i 01-1000 ‘mgim®, and in this case, by making the thickness 5-50 mierometers, preferably 5.35 micrometers, the eflect thereof can be adequately exhibited. Furthermore, the erystals are fine and dense, so they have an excellent ability t retin a Ibricant such ae greave oa solid lubricant between crystals, _good lubricating properties are exhibited, snd when i spro- Yided ina joint for an oil wel ste! pipe and particularly om ‘heads, it exhibits excellent properties. ‘The uniformity ofthe chemical conversion film inereases and exposure of the metallic substrate is reduced if the ‘amount of potassium in the film is at least 0.1 man", There ‘reo fueer improvements in the properties ofthe film when ‘the amount of potassium inthe film exeeeds 1000 mgm”, so in light of economy, the amount is preferably at most 1000 gin’ ‘the thickness ofthe chemical conversion film is less than 5 mierometers, the film eannot exhibit aloquate properties ‘such as eartosion resistanee. On the other hand, if he film ‘thickness exceeds 50 micrometers, the amountof phospharic seid and zine or manganese consumes in the ehemieal eon- ‘version reament liquid naturally becomes lange and the lige Lids rapidly used up. In ight of economy, the film thickness is preferably at most 35 micrometers. "The content of potassium compounds inthe chemical con- version treatment liquid and the content of potassium com- pounds in the chemical conversion film are not always the Same since the llter varies depending upon the type of steel vaterial and other chemical conversion teatment conditions In particular, inthe case of a Cr-containing steel, with low temperature of 20:30" C. or a chemical conversion tine of Jess than 5 minutes, the resulting chemical conversion film {does not contain an adequate amount of potassium and it has fan increased lack of hiding with an inferior resistance to salling ‘Next, the effects of the present invention wil be described pore speifially in connection with working examples, EXAMPLES Example 1 Inthis example, phosphate chemical conversion treatment was carried out using three Cr-contaning stels (C: 0.25%) witha Cr eontent of 1%, 3%, oF 13% Fach of the Cecontaining steels was melted in a vacuum smelting farace and then cast into a 25-kg rectangular ingot, ‘was hot rolled to & thickness of 8 mm and theaUS 83 1 ‘machined to form test pieces having a thickness of Sma, 2 ‘width of 25 mm, a length of 30 mm, anda surfce foughness| imax of S micrometers. Passium tetraborate was used as a potsssium compound, and a commercially available zine phosphate chemical con- version treatment liquid was used as a chemical conversion treatment liquid ‘A chemical conversion treatment liquid was prepared by adding potassium tetrabocate to the zine phosphate liquid 10 ive concentration of 0-10% and twas placed ata temper- ture of 75° C. in a 500 ml container. Test pieces which had been subjected 1 pretreatment suchas degreasing andrinsing ‘with water were immerse in the liquid for S minttes and then piled out anal rinsed with water and dried. ‘The thickness ofthe film which was forme onthe surface ‘ofthe test pieves was measured with an electromagnetic fa thickness meter. The uniformity of the film was evaluated ‘with a scanning eloctton microscope (SEM) and with an, mage analyzer. The potassium content ofthe film was deter 33,847 B2 8 athe table, the fl thickness was evaluated as fllows: X (unacceptable) indicates 4 flm thickness of less tau S micrometers and © (good) indicates a film thickness of at least $ micrometers. Te uniformity ofthe film was evaltated by the test result of area ratio (26) of unhidden surface (ex- posed metallic surface) observed inthe film formed on the test pieoes. O (good) indicates an area ratio of st most 5%. & (usual indicates an area ratio of greater than $% and at most 20%, and X (unacceptable) indicates an area ratio exceeding 20%. For theoveral evaluation, O (acceptable) indicates that the test results were O for both the film thickness and the uniformity of the film, andX (unacceptable) indicates thatthe test results were A oF X for one or beth of the film thickness Example 2 The test materials use inthis example were stels having the following steel compositions: The potassium : 20 “UpCathon test -C:025%, mined mening he chemialy rated st pcesinan oS on, Mo 08% ‘aqueous 5% chronic sed soluion a 75°C. to disolejust eran. “Cr bashe Geese He, Le on ae them allowed by atomic sbaorptionanaysiofthe rel Lyne Iwas repeal ncop tat acer ing solution to detemine te amount of potassium able manganese pvphate chemical comesiontstment “Te test resus are shown in Table 1 Tiquid wos used aa cemicol conversion eatin Tig TABLE Tose Teed tian owen aun se es ex Thtsen "Comet Ms Mole Naum) pn?) _Untomiy O87 No, gam) Baran?) fon canoe 2 $8 fm 8 toe ous go8 te ak 8 ‘oe a foto oo 3 ths ; oe oR 8 8 8 8 2s 10 as Q wm ° oO n Q 1 Mier Mile Unley O82 No. am) Fa!” (agin!) Unity OR? Sos Sane rr x a eatsaes oo 8 Safle 6 Bb 8 a 8 imUS 8,333,847 B2 9 Potassium tetraborate was added to the manganese phos- phate chemical conversion treatment liquid to give concen- tation of 010%, and the resulting chemical conversion treat- ‘met iid was placed at a temperature of 85°C. in. 500 al ‘container. Test picees which had heen subjected to pretreat ment such as degreasing and rinsing were immersed in ‘chemical conversion trestment guid forten minutesand then, ‘ere pled out and rinsed with water and dried Manet Mlo% No. en) aos $3720 on esos os 37a as Lana Manet Malo% Xo, in) film was evaluated she same manner ain Example The 22Crsteel wasa comparative example, while the other steels (Carbon stel, 1 C105 Mo steel, 3 Cr steel, $ Cr steel and 13 Cr steel) were examples of stels for use in a steel ‘material aocording to the present invention ‘The test results are shown in Table 2 and Table 3 TABLE? fal! (etn?) Unity OF? No (am) Eall_ (ni?) er 45Mo se ein nity O87 Na gm) Boll agin) _Uniomiy OE? Roe o os AX $ 8 2 s 7 8 5 Rm » 9 8 Bee 3% 8 8 TABLE Sal! (ain?) Unity O18? Na (omy) _Euall_ (nin)US 8,333,847 B2 i TABLE Sonn = ae «Om : scone ln Takka Moe Net Uno OE No er ts tere FOF Bo age sab ue _ tar ot Se st oe no Inthe tables. the fn thickness was evaluated as flows: X (unacceptable) iniates af thickness of fess than injerometersand © (god) indicates thickness o eas, inerometers: Theunformity ofthe in was cvainted byte text result of area rato) of onion sine (exposed ticle sortie) obser in the fl formed om the tet pisses © (good) indicates sm area aio of at mot 9%, 3 {onal inietes an area rato o preter than 9% and at most 2h, aad X unsecetabe ndcstes an re ati enceding 20%, For the overall evaluation, O (acceptable) indicates that the text ests were © for bik the film thickness and the snformity ofthe nn. and (nace inet hat te tet ress were or X for on or both of the fm hikes tthe fil wifi “ Fxample3 In this example, an ol well stool pipe which i a seamless steel pipe made from a Cr-containing steel (C: 0.25%) witha 45 Crcontent of 1%, 3%, oF 13% was used for treatment ‘A test piece measuring S mm thick, 25 mm wide, and 30 sum long was eu fom each of the above-described Crcon- Comat Fn alt agin’) _Unioenty OF? x x. x Xe x me ex x xx x xe x xx x xox ‘aining stool pipes, which had heen adjusted so that its outer surface had a surface roughness Rmax of $ micrometers In this example, a chemical conversion treatment Figuid ‘vas prepared by adding potassium fetaborate toa commer cially available ine phosphate chemical conversion trea ‘meat liquid to give a concentration of 0-10%. FIG. Lisa schematic illustration showing the setup used in dripping type test method used employed inthis example. Asshown in the FIGURE, chemical conversion treatment liquid 1 iskept ata temperature of 80° C. ina vessel having a capacity of S00 mi. The chemical conversion treatment ign 1 Was dripped for S minutes from a dripping apparatus 3 onto the outer surface side af a test picce 2 which had been suh- jected to pretreatment such as depreasing and rinsing with ‘Water The test picce 2 was then rinsed with water and dried ‘The chemical conversion treatment lghid 1 was heated by 8 hot water for heating §, and it was recirculated and reused by a punp 4 "The resulting chemical conversion film sas evahusted in the same manner as in Example I. The test results are shown in Table 4. TABLE Eat ne mice Crim rea These ‘Mao Mews Nn _im)_Eht ng?) Uli OE? Nom) cmp’) or ites $B § 8h b 8 3 Yi 3 8 h 8 omUS 8,333,847 B2 13 14 TABLE 4-contined + age sa een) oe ase Poesia 31 See Poe tenbonte i Test ‘Thskness Content ils Masts Moles —_Unfomity O87 No eal! (on?) _Unitnity O18? 7 7 sere xx hon eset XX eb xx im 63410 eine el 1 5 fins $3910 et | 5 8 te 6Sbn0 om ‘ 6 0S Stee ea lor 5 68h 02 CR RB Oo we 6 8 6st 30 0% % 0 86 0 Inthe ables, the film thickness was evaluated as follows: X (unacceptable) indicates film thickness of Tess than '$ imcrometers and © (good) indicates a thickness of atleast 5 micrometers. The uniformity of the film was evaluated by the yy test result of area rao (Y) of unhidden surlace (exposed ‘metallic surface) observed in the film formed on the sce pipe test pieces. O (good) indicates an area ratio of at most 5, (sual indicates an area ratio of greater than $% and at most 20R%, snd X (unacceptable) indicates an ateaeatio exceeding 20R%,Fortheoverall evaluation, O (acceptable) indicates that the test results were © for both the film thickness and the ‘uniformity of thefilm,and X (unacceptable) indiates thatthe test reslls were A oF X Tor one or both of he film thickness ‘andthe film uniformity. Example 4 In this example, an oil wel steel pipe made from. a Cr. ‘containing see! (C:0.25%%) having a Creonten of 1%, 3%, oF 13% was prepared, "Test pieces were cut from the above-described stel pipe hich had been adjusted so that its outer surface hada surface roughness Rmax ofS micrometers. Fach test pice was § mm thick, 25 mm wide, and 30 mm 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 0.1-1.0% and then adjusting the total acid number to atleast 30 and les tha $5 and the tio ofthe total acid number tothe fre acid number to 82-90, Te chemical conversion treatment liguid was placed at a temperature of 95° C, in 1008 ml container. Test pieees on retreatment suchas degreasingand rinsing with water dna been performed were immersed for wenty minutes inthe chemical conversion treatment liquid and then were washed swith water and dried, "The chemical conversion film formed on the surface of the steel ofthe test pieces was evaated inthe same manner asin Example 1 Inthe table film unifomity was evaluated by the area ratio ‘of unhiden surface (exposed metallic surface) as follows: © (excellent) indicates an area ratio of at most 1%, O (good) indicates an area ratio of ureater than 1% and at most 5%. For the overall evaluation, O (acceptable indicates thatthe test results were 9 of O forthe uniformity of the il. The test results are shown in Table 5, TABLES Mart MORN Niner Nir ao) ng?) nioiy_ atin ORM 5 3 8 Bs 3US 8,333,847 B2 15 ‘TABLE S-continued wes 33 ¢ 23 8 1 6543107 8 INDUSTRIAL APPLICABILITY According tothe present invention, using a chemical con= version treatment liquid containing zinc and phosphoric acid ‘or manganese and phosphor avid to whieh 0.01-10% of Potassium compoutd is added. it is possible to easily and stably form a sound phosphate chemical conversion film Which is uniform and his excellent adhesion to the surface of ‘a stee containing 0.5-132% Cr. Furthermore, using the present jnvention, itis possible to easily and stably form a thick ‘chemical conversion film having adhesion superior to that of the prior at on a carbon steel as well “The invention claimed is: 1. chemical eonversion treatment liquid for threaded steel joint for stel pipes containing zinc and phosphoric acid 16 log) sstionity_eaton ‘3 oO » 3 38 G8 8 126 8 > & 3 38 5 8 8 b 8 * or manganese and phosphoric acid and further containing potassium tetaborate, wherein the chemical conversion lig- ‘uid has a total acid number of 35-53 and a ratio of total acid number to free acid number of 3-1 2. Achemieal conversion treatment liquid fora steel mate- sal as claimed in claim 1 which has a molar oncenteation of | potassium-containing ions of at east 610% and at most x10", 3. A chemical conversion treatment liquid for a threaded steel joint for steel pipes as claimed in claim 1, wherein it contains manganese and phosphoric acid, 4. chemical conversion treatment liguid for threaded steel joint for steel pipes as claimed in claim 2, wherein it ‘contains manganese and phosphoric acid,