Note: Descriptions are shown in the official language in which they were submitted.
.~ ~ 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
--2--
~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.
--4--
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
L2
~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)
14
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;
