CA1257527A

CA1257527A - Cold deformation process employing improved lubrication coating

Info

Publication number: CA1257527A
Application number: CA000496351A
Authority: CA
Inventors: Thomas W. Tull
Original assignee: Parker Chemical Co
Current assignee: Henkel Corp
Priority date: 1984-12-20
Filing date: 1985-11-27
Publication date: 1989-07-18
Also published as: AU577424B2; ZA859171B; DE3582873D1; EP0186823A2; GB2169620B; GB8531408D0; JPH0465151B2; EP0186823B1; EP0186823A3; ES550112A0; ES8703943A1; AU5052285A; DE3543733A1; ATE63575T1; GB2169620A; JPS61157684A

Abstract

ABSTRACT OF THE DISCLOSURE

In the practice of the instant invention, a lubricating phosphate coating is applied to the surface of a ferrous-base metal article by contacting the surface with an aqueous acidic phosphate coating solution which contains an amount of hydroxylamine which is effective in increasing the rate at which the phos-phate coating deposits from the solution. The resulting coated article is then subjected to cold deformation.

In a preferred embodiment, the metal article is additionally contacted with a second lubricating compound after the phosphate coating is applied. In addition to phosphate, the coating solutions employed preferably contain one or more of the following ions:
zinc, manganese, nitrate, nickel, ferrous, ferric, copper, fluoride, or mixtures thereof.

Description

.~ ~ U, U J~ ~2~5~7 ~ LUBRIC~CN C~G

of pho~ ric acid and o~r ch~nicals ~ich are applied to the su~faoe of ~#tal; ~ su~aoe o~ ~al . reacts w~th the 5 so.l.uti~ ms an in~al layer (on ~ surface of th~ netal) o~ substantially i~soluble crys~alline phosE~e. q~his layer i~
aE~lied prima~ily ~ n ~m corrosicn, or as a base ~.or the applicati~ of a s~c~d aoating (eOgO~ pa~t~ or as a vehicle bo retain a li~uid lubricaalt ~ th~ ed s~aceO
lû ~al p~osphate ooa~ings are well hx~ as b~ing usefuL
in th~ ~orI;i~g of metalsO qhe me~al p~o~a~e coating, wh~
ap~lied to ~ s~rface of an art:icle about to be s~bjected to formation, reduces the f~ created by drawing or cold forming opera~i~s; 'ehe coating re&ceY the grl3at acrount of friction 15 ba~ the metal ~rface and the die. me carmersian of the m~tal sarfaoe to a p~sp~ate coati~sg re~ces this ~riction pr~ily ~ in :reasinq th g al~ y of the mEtal to reta~ a rm fi~m of lubr~t over the e~tire dace; this ability to retain a lub~icant is cril:ical ~ it is thi seccrld lubrica~

2 û ~ich actu;~lly F~ts ~ældi~ and scra~hin~ ~n draw~ng ~atian~, ar~ re~ce~ al to m~al oantact irl cold fo~g by cold ~or~ which w~uld o~wise }~ ~3 E~ossible or prac~.G~:~le.

~1$

'7S27 The present invention relates to a cold deformation process which employs phosphate coating solutions particularly suited to applying a lubricating (or lubricant-retaining) phosphate coating. The ~nique character of this coating stems from its application or deposition from a coating solution employing hydroxylamine.
The use of hydroxylamine in coating solutions is known in the art.
U.S. Patent No. 2,298,280, issued October 13, 1942, discloses the use of hydroxylamine in phospha e coating solutions as an accelerator to assist in depositing corrosion-resisting paint base phosphate coatings. However, the absence of nitrate, in combination with relatively lcw levels of zinc and phosphate, render the exemplified solutions capable of providing lubricating coatings which are only marginally effective for undemanding cold forming processes (e.g., wire and tube pulling); such solutions would be wholly unacceptable for providing lubricating phosphate coating for metal surfaces about to undergo demanding cold deformation operations (e.g., the extrusion of large parts).
U.S. Patent No. 2,702,768, issued February 22, 1955, describes the use of hydroxylamine in "noncoating phosphate"
solutions, such as those which contain sodium, potassium and ammonium phosphates.
U.S. Patent No. 2,743,204, issued April 24, 1956, discloses the use of EDTA as an essential component to increase coating weights in conjunction with accelerators including hydroxylamine. Cold deformation is generally suggested but not demonstrated for the hydroxylamine system.
U.S. Patent 2,928,762, issued March 15, 1960, discloses the use of hydroxylamine phosphate as a reducing agent ~ZS'75~'~

~n an o~sphoric: aci~ p~eli~3ry ~ solllticn in a p ~ ~ a~e a~ating pro~ess.
U.~. PatQ~t ~. 4~003,761, i~s~ed Jar~ary 18, 1977, disclos~ a p~ f~ aE~?l~ a p~spha~e ~ati~g to a ferric acid sol~i~n }~Tir~ a pEI o~ 4.3 tl~ 6.5 and ~ich ~tains loO gram per lil:~r o~ a C2-C4 al~lol~ns, a~d a w~ti~ age~t.
1~ . 4,149,909, is~d Apri1 17, 1979, iani ~o pr~de a }~ds~l~mine plus chlorate/bramate U.S. Pates~t ND. 4,220,486, i~ d Septe~ 2, 1980, c~rs~an c~ating so1utions having a p~I o~ 5.5 to 6.5 which optianally e~p~y 0.2 to 5.0 gr2ms per Lit~ of ~azole, h~0~1ami~ cx h~azine 3~d~. q~se c0F~unds are ad~ed to stabi.~ize 'che use s~1utions.

d~3iti~ ~1i~æ d~sigr~d to s2rve a3 a p~int base, or as a partic~ y well suit~ to a~ as 1ul~ating (or ... . _ .. . .

~S~7~2~ -lubricant-retaining) coatings on ferrous-base metal surfaces which are about to undergo oold deformation even in the absence of EDTA.
It has also been surprisingly discovered that phosphate coatings particularly suited for prelubrication of articles about to undergo cold deformation can be deposited even in the presence of ferrous, or ferrous and ferric, ions, when hydroxylamine is employed.

3~
The present invention relates to a process for the cold deformation of metal articles. The benefits and advantages of the present invention are achieved by providing an integral phospha~e coating upon the surface of the metal article from a phosphate coating solution which contains hydroxylamine.
In the practice of the instant invention, a lubricating phosphate coating is applied to the surface of a ferrous-base metal article by contacting the surface with an aqueous acidic phosphate coating solution which contains an amount of hydroxylamine which is effective in increasing the rate at which the phosphate coating deposits from the solutionO The resulting coated article is then subjected to cold deformation.
In a preferred embodiment, the metal article is additionally contacted with a second lubricating compound after the phosphate coating is applied. In addition to phosphate, the coating solutions employed preferably contain one or more of the following ions: zinc, manganese, nitrate, nickel, ferrous, ferric, copper, fluoride, or mixtures thereof.

75~

p ~ps s~h as n~alizing, ri~s~, dr~i~g or ~ like ~ to ool~ ~@fo~i~; a~ti~g may al~ folla~ by a s~d ~b~e of px~vidi~ lubE:ici~y tl~s ~sin~ ~ ei~Gie~y o ~a~ ld defa~ p~eS8S~, ~ped~c ~canples p~v~ded.

1~ DE;CRIPLICN ~ T~h ~CN
~._ l.d fo~ p~c~3e o~ the prese~t i~tian employ a high~li~ lubricating p~sphate surfaoe coati~g.

~es of th~ pres~ ~ti~ are deposi~ed ~ the surfaoe . 20 of a f~ous~ ~tal ar~cle ~i~ dergo cold du~ cold ~@~O~B~ p3:e~5S~ d/or (2) t~r abili~ ~o 52~7 retai~i a se~d ltab3~ica~ o~ lub~cating agent d~uri~ such ~5ses.

nE~ a~ fc~ ~ati~s w~e ~s~ a:rti~le (e.g., blanlc, slug -or pr~or~n) abo~ to ~go de~ornati~n e~ the deformQtia~
pr~ess at a temperat~e ~ppx~i~bly be~w ~ re~ystallizatio~
~ture, and pre:~ly w~thin 100& of roc~ te~era~ure; ar~d ~u~ r~ m ~pe2~a~3 is p~i.l.y ~ue ~o 1~
ii:iction and/or heat i~ran w~r3c har~ing cau~ ~ng defo~ra~i~.
a~i~ a~ Ls ~:m a~e co:Ld ~BlC~ cold ,h~, a~ w~:e ar~d 1:t~be pull~~ig deforna~ic~ op~ati~ns.
~ uali~e coating~ are provided by a p}~spha~e coati~g tion. $~e phosphate coating solutions useful ~n the processes of the present ~tian are c~ti~2al ~n many respecl:s o~h~r t}~ the critical ~i~t that they ~ntain an effective am~unt of t}~e accelerating agent h~roxylanine. ~e presence of ~ylanine i~parts a ~qlle character to the resuLting phos-phatiny ~a~i~g, a charact~ that nE~ th~n ex~ly useful in cold ~ ~ooe ~ the practioe o~ the preserl~ inventian, a ferrous-base metal article, su~ a~ a blank, slug or preform, is provided with a ~que su~ace c~a1~ y ctacting it with an a~us acidic phosphate ~a~ing ~ol~ ~:taining ar~ effectiv~ a~unt of .. .... . .. . . ... .. _ .. .. .. .. .. .. . .. .

2~75~

r~lamine. q~e cQated article i~ th~ subjected to cold d~rma~c~.

articles are s~e~l ar~icles ~ith a ca~ a:~t le~;5 1.0 p~ nt, ana Ex~bly ab~t: 0.05 to a~ 0.6 a shel~ rdr~rlamine salt or a:npl~; many of t}~ese are ite~ of cc~nE~rce a~d ~tly exisl: in a }~ated ~orm. ~re 20 F~:ef~ably, ~ h~r~lamine salrce is a ~oating solutian sta~le alt oi~ ~lamir~e. ~S i~ also r~ferred to as ~ ~ tNEI;2~2-~ )4 0~ ~3aEI)2-S~4-A~ e~ ousrt of ~lani~

3~2S~S2t7 "effec~ive ar~", as used he:rein, Lg ~ sufficierst ~dr~l-a~ne (regaxdless of the sc~e) to accelerate the c:oati~ process.
q~at is, w~n t~ sabstarltially ide~tical ph~sphate coati~g solu tiarls (di~g arll~ in t}~t one ~ a~unt of ~7droxyl h~lam~ ~ (1) ~s t}~e coa~:ing weig}~t deposited aver a given period of ti~ 3 or (2) deOEeases t:he time it takes the ~olution to d~posit a g~ven coa~ir~ we~gh~.

the pro~s8es of the E~ st i~rrt~n cor~ a aon~ of h~l~nine of f~m abou~ 0.01 pexcent ~ about 10 p~ by we~gh~; similar ca~ce~trati~s expressed as percE3lt weight of hydr~71~nine per volume of use soluti~ y be ~erchangeab1y l~d as ~ use solut~ons are pr~Qrily a~ us having a specific gravity d about 1. M~e preferably, the hydr~lanine i~ pr~t in the phosphate coating sol~t~cns o the present pmcess at a le~?al of about 0 . 01 perc~t to abou~ 3 . 0 percen~, and still mDre preferably at a level of about 0.05 peme~t to about 1.0 percerlt ~y ~ght.
~le n~t being bour~d ~ theory, it is thought tha~
preær~e of }~wqTl~mir~ in the coating soluti~s ~ loyed in the prccesses o the present i~ntis~ a~ribu~e to the q~ality of lu~ g or lub~icant-~taini~ phl~sphate a~at-~es~t in t}~ resulting coating. ~Ihis i~s~ the lubri-cating ~ti~s of the p~osphate crystals t}~nselves. More ~L;257527 i~rt~ly, h~, ~ ~creas~d level of z~ ~n the a~ating ~ntain a f~ acid sr fa~y acid soap. E~r example, wh~ a p~~;pl2ate coating cc~taisling zinc i# cun1~ ed w~th a sec~d w~h steara~e ~ties. The resoltiDg z~c ~ stearate is an ~tac~d with a ~di~n OE pO~U3Sil~l 5teara~ (soap) C~l~ailling lubrica~t. ~his ~D~se ~n zin~ ~d~ s~ra~e sig~i~icarltly ill~:e~!l~eS 1 he abilit~ of the s~ Eace ~ r~ain ~e sea~nd lub~icant -- ~ a i tional z~nc hydr~ st~rate also si~ icantly ~es overall lub~icit~.

EXmCeS~ie5 of the EXreserlt i~:v~:ei~ CO~llta~ Z~, ma~l~eSe, or mixh:i~s th~eo~. ~f tbese, æin~ he 50DcaLled high-z~c preferably a~rtain a 1~1 of abaxt 0. 25 perc~t to about 7 . 5 p~nt by ~l~t, and ~re preferab1y ab~ut 0O75 perc~ to a~aut 5.,5 p~ z~ by weig~rtO Highly prei~rred are l~ls of z~nc oi~ t loO pl~t to al~ t 3~0 E~ce~1 }~ w~ig~t~
~e~ c~ating solu~ians fQr us~ he praci:ioe of ~ ~es~ i:~3~ =~ain ~hate a~ a level o~ a~ O . 5 . .

~575~7 ~r~nt ~o about ~.0 pe~t, m~ efera~ly about 1.0 percerlt ts a~ 7.0 p~rrt~ e Exreferably a~ 2.0 perce~
ab~ 4.0 pe~@n~ by w~g}~t. ~i3 ca~ be ~pressed as w~ight of ?O4] ~ w~g~ solut:i~., ~he E~d pt70spha~ coa~ing soluti~ for use in the ~ ir~an al~o ac}~tai~ nit:eate at a l~ of abaut 0 0 5 p a~t 1.0 p~E to a~ 7.5 peroe~ weight. Ir~ a hi~ly l?r~fe~d ~i~, a p~pha~e co~n~ solu~ian ha~ a al~at~ level o~ 3~0 percerrt t~ about 7.,0 pera~k by we~
i~ e~loy~d ~ ~ cold d~oYma~ E~ooe~s o ~ E~ t .inv~i~., ~ ~h ~a~e and p~ospha~3 are prese~rst in the p}~osp~ate coa~ing ~ s en~layed in the E~ce~ses of the preænt ~a~, ~e quotien~ of the c~trati~ of nitrate [NO~ C~VOE ~e G4nc~c~ of the phosphate [PO~], or [Nt)3]/~PO4~1 is about 0.3 to a~ 6.0, a~d m~re pre~ably abaut 0.5 to a~ut 5uO; this quotient is about 0.9 to about 4.5 irl a highly pr~ sed ~t.
~e o~ ~i~ featu~g~ of ~e phosEihate :oa~i~

abilit~y of t:~2ese ~lu~ic~ ~o d@po~it ~oati~gs poss~ssing a high o zinc, ev~ ~n tha pres~noe of f~ and ~;~S7S2~7 be p¢es~t a~ a level of 0.05 peroent to a~ 0.6 percent by ~ghtO It ~11 be app~eciated that i~ erric ir~ i~ pr2serrt, alt~ i~, f~c and f~ i~ l~ls ~a ~olu~i~ ~s~ be de~ni~d a~lied 'co the su~rfa;~ of t~ fer~Ose ~al a~icle to b~

10 1~ of ~ art~l~ d ~ facto~s whi~:h can be easily fas:~ a ~ a se~ l~rica~ wLll be applied, and if so, applied are in tt~ r~ of a~ 250 to a~t 6000 milli~rans of 15 ~ating per sq~:e faot o metal ~ ace. Coatir~ ~ghts of a~out 350 ~o ab~t 4500 IrdLLigra~s per square fuot are ~re p~ef~d, w~ ating we~g~ of ~ut 500 to aba~ 3500 20 a~a~2g S~9~ e~p~d i~ C~llt:~ N~L ~he nick~!l is p~!i~era~ly pre~lt at a o~ t 0.005 pe~ t:o about 0.~ æIlt b~ t~@!ight, ~
mc~ pr~ably prese~ at a level o ab~ 0.01 peroe~t to ab~ 0.05 pe~:c~. .
~ a hi~l~ b~3re, ~ the ~tal ~nployed irl ~he cold deformati~ prooesses of the present ~ti~, t~e solu~ions are nR~ntained at a ~ature of abou~ 130F to a~ 205C'F, and re E~ erably a~ a ~a ture of al~ut~ 160F to about l90~F; the solutiDns a~e prefer-abl~ ma~'cair~ a~ a pEI of a~out 1.8 ~o ako~t 2.5 while in this ~a~ range.

m~ds; t~ are ~ erably appli~ 7 flaodi~}~ or imn~sion, an~ mDst pq:e:ferably ~;ian. ~ time of exposure or aontact 10 tile~ ar ~ic~ c:an be ~an a~out 0.5 mi~utes to abou~ 30 m~te~;, a~d i~ pre~ out 5 m~m~es bo about 15.
suefac:e of ~e fermu~-base m~tal ar~ide preferably sl~bjected to a dil~te, alkaline n~u~aliz~ng rinse.
.5 Foll~g r~g, tE~e coated article which will even~ually ~ ld d~ormation is preferably contacted with a seco~d, m~ ld fo~ lu~ricant. ~s can ~e dc)ne im~diately after coating (or r~ns~ng), at press side ~ately befare fo~t~on, or dDr:Lng pæt or a~l of the c~ld defor~ation 20 prooe~s ~conjointly~.
IS~ 5~0~ lu~ ant c~ be a soap, oil, dra~i~g c~, o~ an er~ion of an oil and fa~:y acid, ~atty acid salt, or soap. q~ sec~ lu~ric~t Exreferably contairls a C8-C18 fatty acid ~ fat~ acid salt o~ soa~? a~ a 13vsl of a~out- 3 ~2st752~7 p~ent to ab~u~ roent ~ we~ht; nDre preferably, the second lu~æ~cant c~n~ai~ a soa~ selected ~n sodium s~earate, Ex*as5ium stearate, or mixh~s ~eof. AS sug~ested b~fore, ~ese soa}?s z~ le~Jels f~d ~1 the p~;osp}~te c~a~g.e e~pl.oy~d ~D. 'che p8e~t ~:i~l. 1~3 resul~ Zi~lG h~ sl:eæab~ p~des a highly p~e~ed lubricant for cold ~fo~maticn processes.
~ryin~ ~ prccess~g or b@~ aE7erations may b0 eX~ec~ed by ~ti~al techniques su~ or~ed a~r or flash 1~ drying.
II1 a~i~orl ~ ~3 criti~al s~eps arld preferred ~i~ents e2~essly recited abave, a metal article subjected to the cold de~or ~i~ pr~s o the pres~t ~N~ti~ may be a~ition~y subjected to n~ny c~i~l or ~erci~l pr~cesses such articles o~dinarily u~.
Eor e~le, t}~ m.etal article: llay un~ precoating clearLir;~ and rinsin~ step~ as needed to r~nave dekr~s and to.
pr~are the n~tal surface ~or the phospha~e ooating; the articles may also ba pic3cled E~or to coating.
q~ tal a~les sabjected to the pn:cesses of the pres~t ~ti~n may also ur~ ~ entio~al pos~oa~g pL~SSeS, eith~ b~fure the cp~ional app~ of a sec~
lu~ric:ar~t, or be:Eore the cold de~ormatiDrl step, a~ bo~. For eæ~le, in a plrPferred em~ l~lt th~ ph~:)sphat~ab3d metal 2~ article is r:~nsed s}rtl~ af~ coating w~th a dilute~ alXalirle, chr~mi~i~ree n~ub:aliz~ng rinse. Such a rin~e can e~loy weak ~lis a~ baæs SlX:Il ?S bomx Ilitrite, triethanolamine, or mix~s th~.

~L3 ~Lzs~s~

a~d pbospa~e cvaki~ soluti~ OEnta~ an effe~iv~ a~t of dil~, ~ lly al}~aline soluti~; (6) ac~ac~ xoess o~

rably a co~ al pickli~g step is ad~ed.. I~e i o~3ia~ely ae ~o beiflg ~0 until needed for th~
~o~:ma~ s~ ~

af~van~:age~ o ths ~resent ~ti~, l:he follawing speci~ic 15 li~liting of th~ sc~ oi~ the ~nvenl:icn as herein disclosed a~d as set fclrth in the cl;~;~.

~EE 1 me foll~i~g exalipl~ d~ates ~ preparatio~ and use ~ a p~phate coa~ solul:i~ fc~ uæa ~ the ~xractioe of the 20 p~ses~
A i~re~ pho~phating soluti~ c~nta~ 4. 05 percerst , 5.00 pen~t ph~ate (P~), 5.5~ per~st n~trate (N0~), 0.01 pOE~ r~i~al and a t~tal acid of 60 }~o~ts (5.0 ml ~2mple poi~ bei~ equal tc m~llilit~r ~ 0.1 N ~ us~d to er~nt) 5~7 was heated to 180~. ance at 180F, 5.0 gm/l (0.5 peroen~) h~r~lamine sul~ate (E~.A.S. ~ was ~dd~ ter all~g 5 mi~s for e~rium to }:e reached, 0.007 pe3:oent sodi~n ~xab 3 ~;~) w~a~ ad~d. A~t:OE as~ 5 ~es, 4" x 6" x 14 c:oated Qr ~ s (5) mi~ate im:~rsio~s ev~ t~n (10) minu~s (QLc~ate ~oad~g rate of 3. 8 f~2 sur~aoe/hr. gal) . Z~c E~sE~ha~e Qoa~ing ~g~ arlaly~is r~led ~hat ~ ly was t~r~
a tw~old inGreas~ isl coa~ w~i~t, bu~ also that t~ ~a'ciny 10 weig~ ~o not d~ease as r~pi ly as seeD usin~ th~ sa~ ba~ and re~ined ~ ~ ~ us~ II.A.S., with P~ratio~ [ratio of p ~s~l~y) ~ ~eing ab~ut 0. 105 var~us 0. 165 fo~ e process Wl~: H.A~S. qhis indi.cates an ac~able 1~3vel of z~ isl the p ~, was 1~WOE when H.A.S. was incor~orated ~n~o the p aE~i~Dately 30 d~ys af~ c~ating].

t}~n 1: e subjec~ed to ~:ti3ul ~akly a~line r~nsing. A

aE~?liQti~n of 1:he se~o~d l~carl~, ~e a~ic is s~je~d ;'75~7 p~oess such as e~rus~ w~th ~ s. S~lch arciclpc SOl~G~S.

E~E 2 A p~ soluti~ cance~at~ is p¢epared for u~e ~ the p~s of the Exr~ im~tic~ a~ ~11~8:
Ca~c#n~a:at~ A
:~r P~ ~ ~aEr~
Wa~r 360.S
ZiI1G R~ci~ (80.3~6 Zn) 159.0 Cid (42 Be' 67% ~3) 255.5 PhO~iC Acid (75% H~PO4) 216~,7 ~lz~ Eate 6. 0 Nickel Nitrate (13.9% Ni;29.37.NO3) 2.3 1000.O
q~is cona~ntrate is ~ diluted to pa:epa~:e a use soluticn; this diluti~ i~ E~3fexably dane by u~g a ratio o~ 175 p~ of c~c~xat~ ffr~y 100 gaL~ O 5~ ) o~ fir~al u~a 20 ~ tian, ~ 210 gr~ p~r liter of use solutian.

~L;25752'~ -~noent~at~ B

302. 2 Z2~s:: Q~.. de (~30~3% Z.n) 13203 ~i~ic ~id (42 Be' 67~ ~O33 143~1 ~s~c ~d (7S% El3PO4) d~Oû.8 N~chæ:L Nitra~e (13.9% ~;li; 29.3% NO3) 1.6 ~la~e Su~ate 20.0 1~0~, 0 acid:i~e add ill th~a use sol~ti~ ~ ab~2 ~@ de~ired l~el;

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for facilitating the cold deformation of a ferrous-base metal article by applying a lubricating phosphate coating upon the surface of said ferrous-base metal article comprising the steps of:
(a) contacting the surface of a ferrous-base metal article with an aqueous acidic phosphate coating solution to provide a lubricating phosphate coating; said coating solution containing an amount of hydroxylamine effective to increase the rate at which the lubricating phosphate coating deposits an said surface; and (b) thereafter subjecting the phosphate-coated article

2. A process according to Claim 1 which comprises the further step of applying a second lubricant to the metal after the phosphate coating step (a) and prior to, or conjointly with, the cold deformation step (b).

3. A process according to Claim 2 wherein the second lubricant contains about 3 percent to about 15 percent of a C8 to C18 fatty acid, fatty acid salt, fatty acid soap, or mixtures thereof.

4. A process according to Claim 3 wherein the fatty acid soap is selected from the group consisting of sodium stearate, potassium stearate, or mixtures thereof.

5. A process according to Claim 1 wherein the phosphate coating solution is a zinc phosphate coating solution.

6. A process according to Claim 1 wherein the phosphate coating solution is a manganese phosphate coating solution.

7. A process according to Claim 5 wherein the zinc is present in the phosphate coating solution at a level of about 0.25 percent to about 7.5 percent by weight.

8. A process according to Claim 7 wherein the zinc is present in the phosphate coating solution at a level of about 0.75 percent to about 5.5 percent by weight.

9. A process according to Claim 8 wherein the zinc is present in the phosphate coating solution at a level of about 1.0 percent to about 3.0 percent by weight.

10. A process according to Claim 5 wherein the phosphate is present in the phosphate coating solution at a level of about 0.5 percent to about 8.0 percent by weight.

11.A process according to Claim 10 wherein the phosphate is present in the phosphate coating solution at a level of about 1.0 percent to about 7.0 percent by weight.

12. A process according to Claim 11 wherein the phosphate is present in the phosphate coating solution at a level of about 1.5 percent to about 4.0 percent by weight.

13. A process according to Claim 7 wherein the zinc phosphate coating solution contains nitrate ions at a level of about 0.5 percent to about 10 percent by weight.

14. A process according to Claim 13 wherein the zinc phosphate coating solution contains nitrate ions at a level of about 1.0 percent to about 7.5 percent by weight.

15. A process according to Claim 14 wherein the zinc phosphate coating solution contains nitrate ions at a level of about 3.0 percent to about 7.0 percent by weight.

16. A process according to Claim 13 wherein the quotient of the concentration of nitrate over the concentration of phosphate is about 0.3 to about 6Ø

17. A process according to Claim 16 wherein the quotient is about 0.5 to about 5Ø

18. A process according to Claim 17 wherein the quotient is about 0.9 to about 4.5.

19. A process according to Claim 16 wherein ferrous iron is present in the phosphate coating solution at a level of about 0.05 percent to about 0.6 percent by weight.

20. A process according to Claim 1 wherein the lubricating phosphate is deposited upon the surface of the metal article at a weight of about 250 mg to about 6000 mg of metal phosphate per square foot of metal surface.

21. A process according to Claim 20 wherein the lubricating phosphate is deposited upon the surface of the metal article at a weight of about 350 mg to about 4500 mg of metal phosphate per square foot of metal surface.

22. A process according to Claim 21 wherein the lubricating phosphate is deposited upon the surface of the metal article at a weight of about 500 mg to about 3500 mg of metal phosphate per square foot of metal surface.

23. A process according to Claim 7 wherein the phosphate coating solution contains nickel at a level of about .005 percent to about 0.1 percent by weight.

24. A process according to Claim 1 wherein the lubricating phosphate coating solution is controlled at a temperature of about 130°F to about 205°F when contacting the metal article.

25. A process according to Claim 24 wherein the lubricating phosphate coating solution is controlled at a temperature of about 160°F to about 190°F when contacting the metal article.

26. A process according to Claim 24 wherein the lubricating phosphate coating solution is controlled at a pH of about 1.8 to about 2.5.

27. A process according to Claim 26 wherein both ferrous and ferric ians are present in the phosphate coating solution.

28. A process according to Claim 1 wherein the hydroxylamine is present in the phosphate coating solution at a level of from about 0.01 percent to about 10.0 percent by weight.

29. A process according to Claim 28 wherein the hydroxylamine is present in the phosphate coating solution at a level of from about 0.01 percent to about 3.0 percent by weight.

30. A process according to Claim 29 wherein the hydroxylamine is present in the phosphate coating solution at a level of from about 0.05 percent to about 1.0 percent by weight.