COMPOSITIONS LIQUIDES AQUEUSES RENFERMANT DES COMPOSES DE PERFLUOROPOLYETHER ET POUVANT SERVIR DE LUBRIFIANT DANS LA PLASTURGIE DES METAUX

LIQUID AQUEOUS COMPOSITIONS COMPRISING PERFLUOROPOLYETHEREAL COMPOUNDS AND SUITABLE AS LUBRICANTS IN THE PLASTIC PROCESSING OF METALS

Abrégé anglais

Aqueous compositions containing from 1% to 40% by
weight of a perfluoropolyethereal compound having a molecular
weight ranging from 400 to 5,000 and containing carboxylic end
groups, which are salified with an organic or inorganic base,
said compositions being useful as lubricating/refrigerating
liquids in the plastic cold processing processes of metals, in
particular rolling, dishing, drawings and the like.

Revendications

28
WE CLAIM:
1. Use of aqueous compositions containing from 1 to 40% by
weight of perfluoropolyethereal compound having an average
molecular weight ranging from 400 to 5,000, with end groups of
the perfluoropolyethereal chain consisting of perfluoroalkyls
and/or of functional groups, in particular salified carboxylic
groups, as lubricating/refrigerating liquids in the cold plastic
processing processes of metals in general, in particular rolling,
dishing, drawing, wherein the perfluoropolyethereal compound is
selected from the group comprising:
1 ) <IMG>
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R'f, like or different from each other,
are-CF3-, -C2F5, -C3F7, or-COOH, -CF2COOH, and m, n, p
have a value which results in the perfluoropolyethereal
compound having said average molecular weight;
2) RfO(CF2CF20)n(CF20)mR'f, with a random distribution of the
perfluorooxyalkylene units, wherein Rf and R'f, like or
different from each other, are -CF3 or -C2F5, or -COOH,
-CF2COOH and m and n have a value which results in the
perfluoropolyethereal compound having said average
molecular weight;
<IMG>
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R'f, like or different from each other,
are -CF3, -C2F5 or -C3F7, or one of the above-indicated

29
carboxylic radicals, and m, n, p, q have a value which
results in the perfluoropolyethereal compound having said
average molecular weight;
4)
<IMG>
wherein Rf or R'f, like or different from each other, are
-C2F5 or -C3F7 or one of the above-indicated carboxylic
radicals, and n has a value which results in the
perfluoropolyethereal compound having said average
molecular weight.
5) RfO(CF2CF20)nR'f wherein Rf and R'f, like or different from
each other, are -CF3, -C2F5, or one of the above-indicated
carboxylic radicals, and n has a value which results in the
perfluoropolyethereal compound having said average
molecular weight;
6) RfO(CX2CF2CF20)n-R'f wherein Rf and R'f, like or different
from each other, are -CF3, or -C2F5, -C3F7 or one of the
above-indicated carboxylic radicals, X is F or H, n having a
value which results in the perfluoropolyethereal compound
having said average molecular weight;
7) T--O <IMG> CRR' -- Y
wherein X is F or CF3, R is F or C1 or Br or 1, R', like or
different from R, is also F or C1 or Br or 1, Y is a -COOH
group or a perfluoroalkyl group, T is a perfluoroalkyl group
containing one or two atoms of C1 or Br or 1; in particular it
may be Alog CF2-, Alog <IMG> where Alog is C1 or Br or 1,

n ranges from 1 to 15, the m/n ratio ranging from 0.01 to
0.5.
2. The use according to claim 1 of aqueous compositions, in which
the perfluoropolyether has carboxylic end groups which are
salified with ammonia or triethanolamine.
3. The use according to claim 1 of aqueous compositions, in which
the perfluoropolyether is in the form of a microemulsion.
4. The use according to claim 1 or aqueous compositions of
perfluoropolyethers having an average molecular weight ranging
from 600 to 2,000.
5. A lubricating and cooling liquid fro use in plastic cold processing
of metals, comprising an aqueous composition form 1-40% by
weight of a perfluoropolyethereal compound having an average
molecular weight of at least 400 with end groups of the
perfluoropolyethereal chain consisting essentially of
perfluoroalkyls and/or functional groups, and at least 60% water,
wherein the perfluoropolyethereal compound is selected from the
group comprising:
<IMG>
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R'f like or different from each other,
are-CF3-, -C2F5, -C3F7, or-COOH, -CF2COOH, and m, n, p
have a value which results in the perfluoropolyethereal
compound having said average molecular weight;
2) Rf0(CF2CF20)n(CF20)mR'f, with a random distribution of the
perfluorooxyalkylene units, wherein Rf and R'f, like or

31
different from each other, are -CF3 or-C2F5, or -COOH,
-CF2COOH and m and n have a value which results in the
perfluoropolyethereal compound having said average
molecular weight;
<IMG>
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R'f, like or different from each other,
are -CF3, -C2F5 or -C3F7, or one of the above-indicated
carboxylic radicals, and m, n, p, q have a value which
results in the perfluoropolyethereal compound having said
average molecular weight;
4)
<IMG>
wherein Rf or R'f, like or different from each other, are
-C2F5 or -C3F7 or one of the above-indicated carboxylic
radicals, and n has a value which results in the
perfluoropolyethereal compound having said average
molecular weight.
5) RfO(CF2CF20)nR'f wherein Rf and R'f, like or different from
each other, are -CF3, -C2F5, or one of the above-indicated
carboxylic radicals, and n has a value which results in the
perfluoropolyethereal compound having said average
molecular weight;
6) RfO(CX2CF2CF20)n-R'f wherein Rf, and R'f, like or different
from each other, are -CF3, or -C2F5, -C3F7 or one of the
above-indicated carboxylic radicals, X is F or H, n having a

32
value which results in the perfluoropolyethereal compound
having said average molecular weight;
7) T-O CRR' - Y
<IMG>
wherein X is F or CF3, R is F or CI or Br or I, R', like or
different from R, is also F or CI or Br or I, Y is a -COOH
group or a perfluoroalkyl group, T is a perfluoroalkyl group
containing one or two atoms of CI or Br or I; in particular it
may be Alog CF2-, Alog <IMG> where Alog is CI or Br or I,
n ranges from 1 to 15, the m/n ratio ranging from 0.01 to
0.5.

Description

1336s9s
The present invention related to a liquid water-
-based composition useful as a lubricating and refrigerating
liquid in the plastic processing of metals, which comprises,
as a basic ingredient, a perfluoropolyethereal compound.
The composition according to the invention is suit-
able in particular for rolling, dishing, drawing, press-
c$

- 2 - 1336595
ing of metals in general, of the iron and non-iron type such
as steel, copper, aluminium and alloys thereof.
The use of liquids acting as lubricants in the
af~ Lioned metal ~ P~s;ng ~L~PssP~ h~s been well known for a long ti~.
me liquids, which generally consist of hydrocarbon oils with
various additives for improving the performances thereof un-
der severe operating conditions (high pressures, high temper-
atures), exhibit the drawback of being inflammable.
In recent times, the use of aqueous emulsions com-
prising matters endowed with lubricating properties has been
suggested: such products, besides being practically unaffected
by the drawback of being inflammable under the operat-
ing conditions, satisfactorily fulfil also the task of
cooling the materials under processing. Lubricating com-
positions of this type are described for example in European
patent 48216 (Alusuisse),Canadian patent 987,655 (Exxon), U.S.
patent 4,585,565 (Alcoa), U.S. patent 4,618,441 (Alcoa). Al-
though many compositions in the form of aqueous emulsions have
been suggested, it should be borne in mind that it is very dif-
ficult to prepare a composition which exhibits excellent per-
formances as regards lubrication and cooling, a low friction
coefficient (in order to achieve high reduction ratios) and
which, furthermore, is endowed with good lubricating proper-
ties at high pressure and at the same time is free from var-

- 3 - 1336~9~
ious drawbacks such as instability of the emulsion which can
undergo a demixing under the operating conditions.
The known compositions always require specific ad-
ditives depending on the fields of use,in order to reach
good values of the specific properties which are of major in-
terest for the expected use.
The compositions of the invention, besides exerting
a very good lubricating action, which penmits one to obtain, in
the rolling process, a large thickness reduction in a single
or_pass,
run Veffect an efficacious cooling of the material being pro-
cessed by virtue of the high water content of the composition,
such content being of at least 60% by wieght and preferably of
at least 80% by weight.
Furthermore, they do not leave harmful product re-
sidues on the processed material, so that in sc~e cases it is Fos-
sible to avoid a subsequent washing. The compositions accord-
ing to the invention possess a high chemical stability and,
if they are in the form of microemulsions, an unlimited physic-
al stability; moreover, the residues remaining after water
evaporation are nonflammable.
An essential component of the lubricating-refriger-
ating compositions according to the invention is a perfluoro-
polyether having an average molecular weight of at least 400
and preferably not higher than 5,000, with end groups of the

~ 4 ~ 133659a
perfluoropolyethereal chain of neutral type ( perfluoroalkyl
groups) and/or of polar functional type, said perfluoropoly-
ethereal compound being present in the aqueous composition
either in the form of solution when the average molecular
weight does not exceed 1,000 and the end groups are partic-
ularly hydrophilic(carboxylic groups), or in the form of micro-
emulsions when the molecular weight exceeds 1,000 or also in
the presence of low molecular weights when the end groups are
neutral (perfluoroalkyl groups). The term "microemulsion" de-
signates a liquid, macroscopically single-phase composition,
which is limpid or slightly opalescent, optically isotropic,
indefinitely stable in a defined temperature range comprising
the temperature at which said composition is used.
The microemulsions of both neutral and functional
perfluoropolye.her are prepared according to prior art
application EP-A- 250766-(published January 7, 1988).
Perfluoropolyethereal compounds which are particular-
ly suitable as basic components of the aqueous composition of
the present invention are those having a carboxylic end
group suitably salified with organic or inorganic bases, in
particular with ammonia or triethanolamine.
The amount of total perfluoropolyethereal compounds
in the lubricating composition according to the invention rang-

- 5 - 1336595
es from 1% to 40% by weight, preferably from 2% to 20%.
The perfluoropolyethers suited to from the lubricating
compositions which are the object of the present invention are in
particular those which aven an average molecular weight from
400 to 5,000 and preferably from 600 to 2,000 and belong in
particular to one or more of the following classes:
1) RfO(CF--CF20)n(CFO)m(CP~O)pR',
CF3 CF3
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R~f, like or different from each other,
are -CF3-, -C2F5, -C3F7, or-COOH, -CF2COOH, and m, n, p
have a value which results in the perfluoropolyethereal
compound having said average molecular weight;
2) RfO(CF2CF20)n(CF20)mR'f, with a random distribution of the
perfluorooxyalkylene units, wherein Rf and R'f, like or
different from each other, are -CF3 or -C2F5, or -COOH,
-CF2COOH and m and n have a value which results in the
perfluoropolyethereal compound having said average
molecular weight;
3) RfO ( CF2CF2 ) n ( CF20 ) m ( CFO ) p ( CF--CF20 ) q~R ~ f
CF3 CF3
with a random distribution of the perfluorooxyalkylene
units, wherein Rf and R'f, like or different from each other,
are -CF3, -C2F5 or -C3F7, or one of the above-indicated
carboxylic radicals, and m, n, p, q have a value which
results in the perfluoropolyethereal compound having said
average molecular weight;

- 6- 133659~)
4) RfO ( CF--CF20 ) --R ' f
wherein R, or R'" like or different from each other, are
-C2F5 or -C3F7 or one of the above-indicated carboxylic
radicals, and n has a value which results in the
perfluoropolyethereal compound having said average
molecular weight.
5) Rf0(CF2CF20)nR', wherein R, and R'" like or different from
each other, are -CF3, -C2F5, or one of the above-indicated
carboxylic radicals, and n has a value which results in the
perfluoropolyethereal cornpound having said average
molecular weight;
6) RfO(CX2CF2CF20)n-R'f wherein R, and R'f, like or different
from each other, are -CF3, or -C2F5, or -C3F7 or one of the
above-indicated carboxylic radicals, X is F or H, n having a
value which results in the perfluoropolyethereal compound
having said average molecular weight;
7) T--O (~F2 CFO) CFO ) CRR Y
wherein X is F or CF3, R is F or Cl or Br or 1, R', like or
different from R, is also F or Cl or Br or 1, Y is a -COOH
group or a perfluoroalkyl group, T is a perfluoroalkyl group
containing one or two atoms of Cl or Br or l; in particular it
may be Alog CF2-, Alog CF2CF- where Alog is Cl or Br or 1,
CF3
n ranges from 1 to 15, the m/n ratio ranging from 0.01 to
0.5.

7 1~36595
Y is a -COOH group or a perfluoroalkyl group,
T is a perfluoroalkyl group containing one or two atoms
, of Cl or Br or I; in particular it may be Alog CF2-,
Alog CF2CF; where Alog is Cl or Br or ~,
n ranges from 1 to 15, the m/n ratio ranging from 0.01
to 0.5.
Perfluoropolyethers of class 1) are commercially
known under the trademark Fomblin ~ Y or Galden ~ ; the ones
of class 2) are commercially known under the trademark Fom-
blin ~ Z, all of them being produced by Montedison.
Products of class 4), which are known on the market
are the Krytox ~ (du Pont). Products of class 5) are des-
cribed in U.S. patent 4,523,039 or in J. Am. Chem. Soc. 1985,
107, 1197-1201.
Products of class 6) are described in European
patent EP 148,482 in the name of Daikin.
The products of class 3) are prepared according to
U.S. patent 3,665,041.
The products of class 7) are described in c~pen~ing
Canadian patent applications Nos. 598,194 and 598,195 in the
name of the Applicant.
A second non-essential but still very useful in-
gredient, in particular in order to increase the stability

! -- 8 1 3 3 6 5 9 S
of the aqueous microemulsion when it contains non functional (neutral) PFPE, is a
hydrogenated aliphatic alcohol, in particular isoplupanol, or a i~uorinated alcohol such
as a perfluoropolyether with end group -OH and a low molecular weight ( ~ 450).
The alcohol amount in the aqueous composition may reach even 20%
by weight, usually it does not exceed 10%. Useful data in this regard are contained
in the already cited patent application EP-A- 250766 (published January 7, 1988).
The lubricating compositions according to the invention may
furthermore contain small amounts of conventional additives endowed with
anticorrosive, antiwear properties, surfactants, EP additives, depending on the specific
use for which they are inten~led.
The formulations of a few lubricating compositions according to the
invention are indicated in the following examples, which are given for merely
illustrative purposes. In example 13 (Rolling and PSCT, alloys and mechanical
characteristic thereof are disclosed e.g. in "Registration records of International alloy
de~ign~tion. Chemical Composition Limits for wrought aluminium and wrought
alloy". Aluminium Association - Dusseldorf, Washington.
Example 1
Composition:
23.0 g of a monocarboxylic acid with perfluoropolyethereal structure belonging
to class 1, having an average equivalent weight equal to 668;
. .~

- 9 1336595
- 7. rill of an anlrilonia aqueous solution at 10,' by ~,Jeisht of
arnrnoni a;
- 53 ml of isopropyl alcohol;
- 384 ml of bidistilled water.
The sample contained 4.6% by weight of fluorinated substances
and had a viscosity equal to 1.16 cst at 40C and an almost
neutral pH (product reference: LR.i).
Example 2
Composition:
- 9.4 9 of ammonium salt of the monocarboxylic acid with
perfluoropolyethereal structure belonging to class 1, hav-
ing an average equivalent weight equal to 636;
- 1.3 9 of a monofunctional alcohol having perfluoropoly-
ethereal structure belonging to class 1, having an average
equivalent weight equal to 600;
- 0.2 9 of triethanolamine sebacate dissolved in 4.2 9 of
normal-butyl alcohol;
- 2.7 9 of the PFPE having perfluoroalkyl end groups belong-
ing to class 1 and having an average molecular weight equal
to 650;
- 82.2 9 of bidistilled water.
The resulting 0/W microemulsion contained 13.5% by weight of
fluorinated substances and contained 0.2% of triethanol-
amine sebacate (product reference: 6/87).

- 10 -
Example 3 133659S
Composition:
- 17.17 9 of~onocarboxylic acid with perfluoropolyethereal
structure belonging to class 1, having an average equival-
ent weight equal to 441;
- 8.8 ml of an ammonia aqueous solution at 10% by weight of
3i
- 284 ml of bidistilled water.
The solution contained 5.0% by weight of fluorinated subs-
tances and had a viscosity of 0.75 cst at 40C; the pH was
equal to 8.2 (product reference: LR.3).
Example 4
Composltion:
- 150.4 9 of~monocarboxylic acid with perfluoropolyethereal
structure belonging to class 1, having an average equival-
ent weight equal to 443 and a narrow molecular weight dis-
tribution;
- 52.1 9 of an ammonia solution at 10% by weight of ammonia;
- 10.8 9 of a perfluoropolyether having an average molecular
weight equal to about 1,200;
- 32.4 9 of a fluorinated alcohol having a perfluoropoly-
ethereal structure and a molecular weight equal to 678;
- 23.0 9 of isopropyl alcohol;
- 293.1 ml of bidistilled water.

"- 1336595
The resulting microemulsion contained 6.5% by weight of
fluorinated substances and had a pH equal to 4.4 (product
reference: LR.17).
Example 5
Composition:
- 18.39 g of a monocarboxylic acid having perfluoropoly-
ethereal structure belonging to class 7, having a chloro-
fluoroalkyl end group for each molecule and having an
average equivalent weight of about 850 and a wide distrib-
ution of the molecular weights;
- 6.44 9 of an aqueous ammonia solution at 10% by weight of
NH3;
- 338 9 of bidistilled water.
The obtained solution contained 5.1% by weight of chloro-
fluorinated substances and had a pH equal to 8.3 (product
reference: LR.15).
Example 6
Composition:
- 19.8 9 of a perfluoropolyether belonging to class 1 hav-
ing carboxylic end groups and an average molecular weight
equal to 4170;
- 14.6 9 of isopropyl alcohol;
- 2.2 g of monocarboxylic acid having perfluoropolyethereal
structure,belonging to class 1, having an average equival-

- 12 - 1336595
ent weight of 668;
- 63.4 9 of aqueous phase containing the ammonia which is
necessary to salify the carboxylic groups.
The 0/W microemulsion obtained by mixing the above-listed
components was a fluid, limpid between 25 and 75C, cont-
aining 22% by weight of fluorinated substances and exhibit-
ing a viscosity of 38 cst at 40C (product reference: LR.A).
Example 7
Composition:
- 5.3 9 of ~unctionalized perfluoropolyether belonging to
class 1, having carboxylic end groups and an average mol-
ecular weight equal to 2080;
- 19.2 9 of isopropyl alcohol;
- 75.5 9 of an aqueous solution containing the ammonia which
is necessary to salify the carboxylic groups.
The 0/W microemulsion obtained by mixing the abovesaid com-
ponents was a fluid, limpid between 25 and 50C, containing
5.3% by weight of fluorinated substances and having a vis-
cosity of 2.25 cst at 40C (product reference: LR.C).
Example 8
Composition
- 25.2 9 of~onocarboxylic acid having perfluoropolyethereal
structure, belonging to class 1, having an average equiv-
alent weight equal to 668 and a wide distribution of the

- 13 - 1336~9~
molecular weights;
- 9.1 ml of an aqueous ammonia solution at 10% by weight of
ammonia;
- 1.4 ml of a perfluoropolyether having perfluoroalkyl end
groups, belonging to class 1 and having an average molecul-
ar weight equal to 650;
- 28 ml of isopropanol;
- 280 ml of bidistilled water.
The sample was stable in the whole temperature range taken
into examination, contained 8.2% by weight of fluorinated
substances and had a viscosity of 1.2 cst at 40C, the pH be-
ing equal to 8 (product reference: LR.5).
Example 9
Composition:
- 55.0 9 of a monocarboxy~lic acid~-~avin`g~perfluoropolyethereal
h~ ging to class 7,
structureV having.a chlorofluoroalkyl end group per mol-
ecule and having an average equivalent weight of about 478
and a wide molecular weight distribution;
- 62.14 9 of triethanolamine;
- 10 14 g of bidistilled water.
The resulting solution contained 4.86% by weight of chloro-
fluorinated substances and had a pH equal to 8.36 (product
reference: LR.15 TEA).
Example 10

- 14 - 1336595
Composition:
- 26.18 g of aMmonium salt of the acid belonging to class
1, having an average equivalent weight equal to 441;
- 1.4 g of a perfluoropolyether of class 1, having perfluoro
alkyl end groups and an average mo1ecular weight of about
650;
- 5.6 ml of isopropyl alcohol;
- 293 ml of bidistilled water.
The system was limpid in the whole temperature range. It
contained 8.8% by weight of fluorinated substances and had
a viscosity of 0.85 cst at 40C; it was brought to a pH = 8
by adding thereto 0.15 ml of an ammonia solution at 10% by
weight of ammonia (product referénce: LR.7).
Example 11
Composition:
- 35.1 9 of~monocarboxylic acid of perfluoropolyethereal
structure belonging to class 1, having an average equiv-
alent weight equal to 668 and a wide distribution of the
molecular weights;
- 5.4 9 of ~monocarboxylic acid of perfluoropolyethereal
structure belonging to class 1, having an average equival-
ent weight equal to 443 and a narrow distribution of the
molecular weights;
- 11.3 9 of ammonia solution at 10%;

- 15 - 1336595
- 2.8 9 of ~erfluoropolyether of class 1, having perfluoro-
alkyl end groups and an average molecular weight of about
1,200;
- 23.6 9 of isopropyl alcohol;
- 300 ml of bidistilled water.
The microemulsion so obtained was stable in the whole tem-
perature range. It contained 11.4% by weight of fluorinated
substances and had a pH equal to 7.4. (Product reference:
LR.9).
The following examples describe the preparation
of additive-containing microemulsions.
Example 12
Composition:
- 108.0 9 of~monocarboxylic acid with perfluoropolyethereal
structure belonging to class 1, having an average equiv-
alent weight equal to 668;~
- 1.8 9 of ~ onocarboxylic acid with perfluoropolyethereal
structure belonging to class 1, having an average equiv-
alent weight equal to 443 and a narrow distribution of
the molecular weights;
- 33.7 9 of ammonia solution at 10%;
- 33.4 9 of perfluoropolyether having an average molecular
weight of about 1,200;

-- 1336S95
. 16 -
- 23.6 9 of a solution of triethanolamine sebacate in iso-
propanol, at 10.2% by weight;
- 3.1 9 of isopropanol;
- 240 ml of bidistilled water.
The resulting 0/W microemulsion contained 32.3% by weight
of fluorinated substances and 0.6% by weight of triethanol-
amine sebacate, and had a pH equal to 7.6 (product refer-
ence: LR.10).
Example 13
90.3 9 of the sample described in the preceding example 12
were diluted with 250 ml of water.
The resulting 0/W microemulsion contained 8.6% by weight of
fluorinated substances and 0.2% by weight of triethanol-
amine sebacate, the pH being equal to 5.3 (product refer-
ence: LR.ll).
The utilization characteristics of the lubricating
compositions according to the invention, with reference to
specific applications, are illustrated in detailed herein-
after.
Rolling
The lubricating compositions under examination were subject-
ed to the "Plane Strain Compression Test" (paper 2015 by
R.D. Guminski and J. Willis - Journal of the Institute of
rletals, 1959-60, vol. 88). The Plane Strain Compression Test

- 17 - 133659a
is ~n.improve"ment of the BIS~A Compression Test (see The
Rolling of lletals by L.R. Underwood, pages 116-119 - Chap-
man and Hall - London 1952) and is well indicative of the
thickness reduction capacity of the lubricants in the cold-
-rolling of aluminium: the data determined in the plane
strain compression test are in good correlation with the behaviour
in use exhibited by the lubricating mixtures.
Further literature sources on the P.S.C.T., which extend
the validity of the test also to steel, are : Kubie and
Delamare - Journal of Lubrication Technology, pages 538-
551 - 1982, vol. 104).
The test carried out according to Guminski/Willis was the
following : A 50x2.52x150 mm strip of aluminium alloy 3003
- H22 was subjected, after wetting with the lubricant, to
5 successive compressions between two vertical plates meas-
uring 75x6.20 mm in a press mounted in a traction/com-
pression machine, the whole in accordance with the indic-
ation given by Guminski and Willis, with the exception that
the applied load was of 6,800 kg in order to make the
test more selective.
The fluids of the present invention can be applied to the
metal surface according to conventional methods such as im-
mersion, spraying, and by means of jets, brushes, wiping,
rollers or the like.

1336S95
In ~he following examples,the application by means of
brush was utilized.
The results are reported in the following Table 1.
Table
Product Thickness reduction (%)
Oil Lamium ~ 54
Example 1 (LR.l) 65
Example 2 (6/87) 67
Fxample 7 (LR.C) 60
Exam?le 11 (LR.9) 62
Lamium ~ is a rolling oil, which is usually utilized and
is based on isoparaffin mineral oil with 5-6% of lauryl al-
cohol and minor amounts of fatty acids and of antioxidants
(CRODA, ~.K., BC21).
Another typical known product is Somentor N. 35 produced
by Esso, which gives equivalent results.
Determination of the friction coefficient by means of the
Plane Strain Compression Test (PSCT), as is described by
Kubie and Delamare in the above-cited literature.
Also this test, which provides the friction coefficient
values, permits to evaluate the reduction ratios obtain-
able in the rolling process.
Metal test-piece (20x300 mm sheet thickness: about 0.6 mm),
applicated load: 10,000 kg :

1336595
- 19 -
a~ steel at 0.03% of C and 1% of l,n, annealed;
b) Al/~g alloy 5052 0, anneale~.
The test-pieces were degreased by means of acetone before
being tested.
Tested lubricants:
a) composition of example 1 (LR.l);
b) composition of example 5 (LR.15);
c) composition example 7 (LR.C) ;
d) composition of example 9 (LR.15 TEA);
e) rolling oil for the steel referred to as Q.27, a com-
mercial product having the following composition:
- esters of nonylphenols + ethoxylated
nonylphenols 3.95% by weight
- antioxidant 0.50% " "
- antistain agent 5.00% " "
- animal fats 40.00% " "
- naphthenic mineral oil 50,00Z " "
- triethanolamine (TEA) 0.55% " "
f) emulsion of preceding product Q.27 at 10% by weight of
water;
g) palm oil;
h) product ` aqueous emulsion at 4% by weight of the
following oily composition:
- saturated acids C18 8.0% by weight

133659~
- 20 -
- alcohols C8-C18 5.0% by weight
- alcohlS C16 C18 2.5%
- emulsifier 11.0% " "
- polyisobutane dissolved
in C17/C18 mixture 73.5% " "
The tests on steel were carried out with a load corres-
ponding to a thickness reduction of about 30%; the tests
on Al alloy were conducted at a pressure corresponding to
a thickness reduction of about 60%.
The results are indicated in Tables 2 and 3.

-
- 21 - 1336595
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133659~
- 22
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- 23 -
1~36595
Dishing
Dishing is the process by means of which a metal plateis
plast~c
subjected to permanent~deformation by buckling between two
surfaces (die and punch).
The lubricant must have good EP characteristics (high pres-
sures), i.e. it must secure the sliding between two metal
surfaces (sheet iron to be deformed and dies) under a high
pressure, and that is achieved by lubricants which do
not exhibit any film rupture under such conditions.
A wide variety of different lubricants are ~ e~ at present, de-
pending on the type of dishing to be carried out and
on the materials to be worked; said lubricants may be a
differently constituted mineral oi1, ~ os~ tions as well as soap baths,
emulsions, and
V waxes, greases, fluoride ~ hosphate baths, chloroparaffins,
polymeric resins, graphite or MoS2 in oil, etc.
The PFPE-based aqueous compositions according to the present
invention are suited also as lubricants for the dishing
process. -
Said products are novel in this application, they are suited
to the dishing of metals as they permit the obtaining of a dish-
ing ratio comparable to the ones obtainable with whole
oils based on hydrocarbons, while remarkably reducing
the necessity to degrease the sheets - for the subsequent
processings.

- 1336595
- 24 -
-- further
The fluids in ques~ion may ~V'~ contain minor amounts of
additives, if these should result to be necessary in part-
icular operative conditions.
Such additives may be corrosion inhibitors, antistatic
agents, surfactants, slippage -agents.
Examples
The fluids of the invention were subjected to the Erichsen
test (UNI 8341) on steel FE Po4~(UNI).
The fluids of the present invention are applied to the
metal surface by means of conventional methods such as dip-
ping, spraying, wiping, by brUShes, roller or the like.
The results, which are reported on the following Table 4
indicate the depth of penetration, in tenths of mm, of the
punch into a sheet-steel having a roughness of 0.8 microns.
Table 4
Erichsen values
test-piece I
in dry conditions 116.3+0.5
standard oil (*) Metalform ~ 126.7+1
LR 5 (example 8) 124-123.7+ 0.7
LR A (example 6) 126.7+0.5
LR C (example 7) 124-125.7+1.5
(*) The oils for dishing usually utilized at present
are based on mineral oil and additioned fatty acids
(antioxidants etc.).

- 25 - 133659~
Lubricating ?roperties of the fluids according to ~he in-
vention.
For the fluids utilized in several plastic processings of
metals, good EP characteristics may be required.
In order to determine the EP characteristics of the micro-
emulsions and aqueous solutions of perfluoropolyethers and
derivatives thereof, "Shell 4 balls" tests(~P 239/79)
were carried out.
The "Shell 4 balls" tests were always carried out using
balls made of steel UNI 100 Cr6.
Examples
The fluids according to the invention were subjected to
the "Shell 4 balls" test (IP 239/79 ASTM D2783).
The results are indicated in the following Table 5:

- 26 - 1336595
T a b 1 e
Ex. ref. seizure welding average load
beginning test load Hertz
%(**) (Ks) (Kg) (Kg)
1 LRl 4,6 178 178 55
3 LR3 5 89 282 78
LR15 5,1 2G0 224 70
6 LRA 22 100 178 48
7 LRC 5,3 251 251 87
8 LR5 8,2 126 178 56
LR7 8,8 100 251 71
11 LR9 11 178 178 56
14 LR17 6,5 251 251 79
12 LR10 32,6 178 178 58
13 LRll 8,6 178 178 62
19 LR15TEA 4,8~ 251 316 98
(*) O.C.E. 6 158 178 60
O.C.E. 10 178 178 61
(*) Commercial, highly additioned emulsifiable oil composed
of : 50% of mineral oil, 3% of chlorinated paraffin,
4% of non-ionic emulsifier, 1% of antistain agent,
0.5~ of biocide, 40% of animal fat oils, 0.5X of anti-
foaming agent, 1% of corrosion inhibitors and other

~ - 27 - 133659~
agents.
(**) % by weight of product in the aqueous emulsion.
The reported data show that the compositions according to
the invention possess satisfactory properties in EP cond-
itions also ~ithout additives, these properties being comp-
arable with those of commercial products containing a high
amount of specific additives.