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July 12, 1960

A. CAHNE

2,944,917

METHOD OF COATING A METAL EASE WITH POLYTETRAF'LUOROETHYLENE

Filed Dec. a, 1955

10203040

607080!)

I NVENTOR

Armand Ca/m

B/Mm/WM

ATTORNE Y5

2,944,917.
Patented July 12, 1960
2

which favors the gripping or anchoring of the ?lm of

2,944,917

Te?on within the cavities, and, consequently, positively


provides a good anchoring (at least equivalent to a

METHOD OF COATING A METAL BASE WITH

true bound) of the deposited layer of Te?on onthe sur


face to be coated, in spite of the well known character
istics of non-adhesiveness of the Te?on, such result being

POLYIETRAFLUORGETHYLENE

Armand. Cahn, Gif-sur-Yvette, France, assignor, by

due to the formation of roots which are anchored or


embedded within the said cavities and are not exposed to

mesne assignments, to Marc Gregoire, Paris, France

Filed Dec. 8, 1955, Ser. No. 551,875

cracking.

10

Claims priority, application France Dec. 13, 1954


6 Claims. (Cl. 117-49)

In order that the acid attack according to the invention

produces the required cavities, the structure of the metal


or non-metallic surface to be attached must have a certain
heterogeneity so as to provide a differential attack pro

ducing the aforesaid cavities or holes.

In opposition,

The present invention relates to methods for coating 15 some materials, such as pure copper, are uniformly at
surfaces and it particularly has for its object an improved
tacked and the attacked surface remains smooth without
method for coating metal surfaces with a very thin layer

cavities; in such a case, the attack by an acid or a mix


ture of acids does not directly produce an outer layer

of polytetra?uoroethylene.

having cavities and upon which Te?on may be applie


It is known that trials have been made for coating a
'
metal surface with a layer of polytetra?uoroethylene, a 20 according to the invention.
However, in such cases when certain metals are utilized
product known in the trade under the name of Te?on,
to form the base or surface to be coated, and, particularly,
by interposing an intermediary layer between said metal
in the case of copper and copper alloys, a preliminary
surfaces and the Te?on layer. Such known method is
preparation of such surface comprises, according to a
di?icult to carry into practice it is costly and it can only
be applied for coating surfaces having a simple shape. 25 further feature of the invention, depositing an inter
mediary layer, having a thickness of ca. 2-3 hundredths
Moreover, the coating produced by such known method,
of a millimeter or more, of electrolytic zinc or another
does not strongly adhere to the receiving base and, there
suitable metal on said smooth surface, and then attacking
fore, is not very durable. There lies the reason why
said intermediary layer metal by at least one acid accord
such known method is only applied in limited cases in
which the costand the life of the coating have no ma-. 30 ing to the invention, in order to produce the cavities re
terial bearing.

quired for anchoring the desired coating into said inter

It is known that the difficulties encountered for coating

mediary layer.

The invention may also be applied to such metal sur


faces as made of enamel coating ferrous or cuprous

a metal surface with a Te?on layer essentially result from

the speci?c non-adhesivness of the Te?on.


The object of this invention is, therefore, to palliate 35 metals, but the acid attack (preferably, with hydro?uoric
. acid, in that case) is rather made on the primary layer,
or mass'than on the ?nishing layer, i.e. the outermost

the aforesaid drawbacks which are inherent to said


known method for applying a Te?on layer. ' i

layer made of enamel.


It has been ascertained in practice of the invention

More speci?cally, this invention has for its object to


provide an improved method for coating a surface, par

ticularly'a metal surface, and still more specially a sur:


face of aluminum or aluminum alloy, with a Te?on
layer, the thickness of which may vary at will over a

relatively extended range; said layer is strongly anchored

to the surface to be, coated, does notcrack and cannotzbe


stripped off from said surface, for instancebyjmeans
of ayh-ard-edged tool.

, r.

v.

According to the invention, a surface, generally made

40

that such attack of the enamel layer with hydro?uoric


acid breaks the top or cap portion of the spherical globules
of said primary layer, thus producing holesor stitches
(simulating, when observed with a microscope, the tiny
traces left in a mans face by small-pox pustules).
45
It has already been proposed to subject metal surfaces
. to the action of one or several acids preparatory to cer-

tain operations, for instance, before applying a paint or

varnish. However, in the known methods preparatory to


the application of a paint, the thickness of the part to be
preparatory treatment comprising a chemical. attack with
'at least one acid, in order to produce in the outermost 60 treated is increased by the addition'of an intermediary
layer; furthermore, the duration of action, temperature,
layer of said surface cavities or holes having a well pre
nature and concentration of the acids are not critical,"
determine average size, inferior to 20-30 microns. On
since the paint is adhering to the base every time such
the surface thus prepared, Te?on is deposited either as a
preparatory treatment has been performed.v But the
dispersion which is then dried up, or as a powder, the
55 Te?on inherently exhibits a speci?c non-adhesiveness;
resulting deposit subsequently "being fused in situ.
When the desired layer must have a thickness of ca.
- however, when developing the invention, it has been,
found that constant critical conditions, such as the selec-,,
two hundredths of a millimeter, said layer may be pro
tion, concentration, duration of contact and temperature
duced'in a single application of Te?on; however, when
of the acid or acids utilized may be predetermined, in
thicker layers are desired, it is only necessary to repeat
the same operation, while allowing each layer to dry 60 such away that all these factors are coacting and mutu~

of metaL-qto becoated with Te?on is subjected to a

and fusing it before depositing the next layer.


As a matter of fact, according to the invention, it has

been found in practice that, provided the size of'the cavi


ties produced in the surface to be coated by said preparal

ally reacting, with the ?nal result that they produce


cavities having such required size that, according to the
invention, the Te?on particles anchor themselves into said
cavities when thereafter deposited on the base. In par

tory treatment are comprised within the rather severe 65 ticular, these cavities must have a narrow or throttled en

range above de?ned, Te?on in dispersion may be, in a


satisfactory manner, directly deposited on a surface thus
treated and be strongly and durably bound to it.

trance and a general size not exceeding 2~3 hundredths


of a millimeter. Besides, a surface layer must have been

disintegrated, i.e. the thickness in some regions of the


According to the invention, it has also been found that,
partvto be treated must be reduced.
I Comparative tests relating'to the invention have shown
by utilizingan acid or a mixture of acids for the prepara 70
tory chemical attack, the cavities'producedhave the re-.
that, after having been subjected to a sand blast providing
cavities of a relatively large size, i.e. exceeding 3 hun
quired size and have a throttled entrance, a situation

2,944,917
dredths of a millimeter, an attacked surface was suitable

millimeter. The Te?on is allowed to dry and the layer

for receivinga layer of paint exhibiting very good adher

is then fused at- a temperature approximating 370400

ing characteristics; while, when, even with cautious pro


cedures, a skillful operator succeeds in depositing a layer
of- Te?on on the same surface,- said layer quickly works
loose-and comes off, thus- proving that said surface has

C. (700-750 F.).

In this manner is produced a strongly anchored ?lm of


Te?on which has no cracks, shows no tendency to crack
ing in the course of time and cannot be stripped off
either with the nail nor with a hard-edged tool,
not the anchoring and resistance, features? provided by
When a thicker layer is desired,ythe operation is re
the improved proposed treatment, i.e. including the afore
" peated, i.e. that, after a ?rst layer of Te?on has been
said critical conditions. '
i , '
,
Said critical conditions are brie?y described herein 10 fused in situ, aqueous dispersion of Te?on- is; again ap
plied and the coating cycle is repeated as many times as
after." Fo'r treating aluminum and aluminum alloys, and

an elementary ?lm of Te?on is to be deposited.


The aqueous dispersion may be applied to the surface
tration comprised between ca. 10 and 30% should beuti
by any suitable procedure: immersion, dipping, melting,
li'z'd; for bronze and steels, it is advisable to utilize nitric
acidlhaying a concentration in the vicinity of 10% (how 15 trickling or laying-down with a brush. The Te?on may
also be sprayed with a gun upon the surface to be coated.
ever, for some steels, the concentration may reach

also? electrolytic Zinc, hydrochloric acid having a concen

100%); for enameled products, satisfactory results may

Example 2
The surface to be treated is made of an alloy designated
mixturerof sulfuric acid and chromic acid, may also be 20 in the trade under the name of _Duralum'in (an alloy

be'yobtained with hydro?uoric acid at near 15% concen


tration; ?nally, a sulfochromic mixture, that is to say a

utilized for light alloys and ferrous metals.

essentially comprising about 94% aluminum, about 4%

Before attacking the surface with acid, the attack may


be, if desired, facilitated by a preparatory sand blast ap
plied to said surface.

copper with small quantities of manganese and magne


sium).

The duralumin plate is dipped during 1'-2 minutes into

In order that those skilled in the art may better under 25 15% diluted hydro?uoric acid; the plate is washed with
stand how the present invention may be carried into prac
water, then dipped into a 40% solution of hydrochloric
tice' effect, the following illustrated examples are given.
acid at a temperature of 20 C. (68 F.), during 2-5
(the starting acids are technical acids, e.g. technical hy
minutes; the plate is then cooled down, either by taking
drochloric acid at 23 Baurn).
it out of the bath from time to time, or by cooling down
30 the bath. The plate is freed from the chlorides by dip
Example 1

ping it into a solution, concentrated at ca. 40%, of cold

nitric acid.

The metal to be coated is substantially 99.5% pure

Thevplate thereby obtained has a dark grey color which


_ The metal is attacked with an aqueous solution of hy 35 may be caused to turn to a light grey by dipping the plate
again during about 30 seconds into the aforesaid diluted
drochloric acid at 10% concentration, the duration of
solution of hydro?uoric acid, and then into the afore
the treatment being as follows, according to the tem
said bath of nitric acid during a few seconds.
perature of the acid bath:
Thereafter, the treatmentpfollowed is that described in
Example 1, that is to say that the layer of Te?on is then
Temperature of
e
40 applied and fused.
the bath
Time of immer
Example 3
sion of aluminum
in acid
0.
F.
The treatment isperformed exactly as described in Ex

commercial cold-hardened aluminum.

ample 2, with the exception that the solution of hydro


75

167

8, minutes.

60

140

20 minutes.

20-25

6877

0a. 2 hours.

45 ?uoric acid is replaced by a concentrated solution of


soda.

. = .

Example 4

For treating a plate made of Duralinox (an aluminum


When the temperature is lower than 50 C. (122? F.),
the reaction may be more easily initiated by touching'the 50 alloy containing 542% of magnesium and ca. .5% of
manganese) the preparatory _ attack is performed by
aluminum with a piece of iron.
7
'
'meansof a 10% solution of commercial hydrochloric
After the attack with acid, the metal is rinsed with
acid.H The duration ,ofpthe treatment is exempli?ed inthe
water during 14 of an hour, then dried.
In the case of annealed aluminum, the attack should
last a longer time, or nitric acid should be added to the 55
solution of hydrochloric acid. The attack may be per

table below: .

' Bath temperature

formed also at about 20 C. (68 F.) during 10-30 min


utes, according to the annealing treatment, by utilizing the
following mixture:
..

Percent

Hydrochloric acid _________________________ .._30-40


Nitric acid ______________________________ __

Duration of

45? C.
60 0.
20 C.

60

-5-10

immersion

167? F.
140 F.
68 It.

sm'mutes.
20 minutes.
2 hours.

The layer of Te?on is subsequently applied as described

The surface thus prepared is then coated with Te?on


in Example 1.
in the form of an aqueous dispersion made by mixing 1
'
Example 5
volume of water with 1 volume of the solution designated 65
Aluminum
or
aluminum
alloy, such as Dur-alinox or
in the trade by the trade name of TD. 3, comprising
Duralumin, is attacked by a sulfochromic mixture hav
Te?on granules, having a diameter approximating .5 mi
ing the following composition:
cron, dispersed in water to which a wetting agent has been

added.

For a lapse of time comprised between a few seconds 70

Grams
Sulfuric acid _

_......

5O

Chromic acid _.\.._.._-..__ ____ --l-'-----u-_--~*----i--__

20
and a few minutes, theaqueous dispersion of Te?on is
allowed to remain in contact with the metal surface,
which has already been treated as previously mentioned,
The attack is performedat 50-80" C. (:12-2-176" F.)
thus, providing on said metal surface a Te?on layer, the
during ca. ten minutes, and the layer of Te?on is then
thickness of which is in the order of1-3 hundredths of a 75 deposited as described in Example 1.
Water

_.____

150

Example 6

such as the aforesaid TD. 3 dispersion which is diluted


at 50% and containing, in volume, 5% of a sulfochromic

For treating a bronze surface, a 12% solution of nitric


acid is utilized, the immersion lasting 20 minutes at a
temperature of 20 C. (68 F.). The layer of Te?on
isthen deposited as described in Example 1.

mixture, the composition of which is'indicated below:


.

Grams

Sulfuric acid _________________ ___ _________ __;__',,50


Chromic acid _
' ____ __
20

Example 7

Water ; ___________________________________ __ 150

For applying a ?lm of Te?on on. a metal capable of


After said ?rst layer has been fused in situ',\other layers
receiving a mechanically resistant coating, such as cop
per, brass, iron,vsteel, or_ bronze, a layer made of elec 10 of pure Te?on may be deposited;_l1owever, with such
an attack, the whole deposited layer may have only a
trolytic zinc and having a thickness of ca. 2-3 hundredths
small'thickness.
'
Y
of a millimeter may be primarily deposited on said metal.

Example 13

Subsequently, said layer of electrolytic zinc is attacked

with a 15% solution of hydrochloric acid, the immersion


Parkerised or bonderised iron, that is to say iron which
15
lasting 15 minutes at 20 C. (68 F.).
. has been immersed for about one hour or ten minutes,
Te?on is then deposited as described in Example 1,
respectively into a boiling solution of iron and manganese
or by spraying Te?on in powdered form over the at
phosphates, is covered with a ?rst layer as described
tacked surface and subsequently fusing said Te?on at a
in Example 12, but containing only 2% (instead of 5%),
temperature of about 370-400~ C. (700-750 F.).
in volume, of the sulfochromic solution.
.
20
It must be mentioned that in the case of brass, iron,
Then, when the deposited layer hasbeen dried, it is
steel, bronze, the preparatory attack with an acid or a
fused.
suitable mixture of acids may be realized, without pre
Example 14

viously depositing electrolytic zinc, while such zinc de

A metal surface, made, for instance, of steel or of

posit is necessary for copper parts, on account of the

fact, as previously explained, that copper is uniformly 25 an aluminum alloy, is directly treated with a ?rst layer
comprising a Te?on dispersion mixed with 10% of the
attacked by acids.
sulfochromic solution indicated below:
Example 8
Grams
l The metal surface to be treated is a stub steel (with 1%
Sulfuric acid ______________________ -1 ______ __
50
carbon, .5% chromium and .l% vanadium).
30 Chromic acid _____' _______________ __ _______ -_ -20

The attack is performed with a 10% solution of com


mercial nitric acid during 6 minutes at 20 C.
In a modi?ed form of the treatment according to the
invention, the attack may be performed in two phases,
namely.

'

First phase: attack with a solution of commercial nitric


acid at 100% concentration at 20 C. (68 F.) during
about 30-60 seconds; then

>

,1

Water

____________________________________ .._

Thereafter, layers of pure Te?on may be deposited.


The results achieved with such a procedure are not so

35

satisfactory than when the metal has been previously


attacked with an acid because when, later, the coated sur

face comes in contact with boiling water, the coating


thus produced cannot resist.

Second phase: attack, also made at 20 C..(68 F.),


,
~

A plate made of aluminum or duralinox is ?rstly at;


tacked at 60 C. (140 F.) for a few minutes with the

. Te?on is deposited as described in Examples 1 and 2


(Te?on in powdered form).

followingmixture:

Example 9

'

' Example 15

with a solution of commercial nitric acid at 10% con 40


centration during 5 minutes.

150

45

'

Grams

Sulfuric acid _______________________ __"_ ____ __

50

Chromic acid _____________________________ __ 20


A steel, of the so-called B.T.H. type (with 1% car
bon and 1.1% manganese), is treated with a 10% solu
Commercially pure hydrochloric acid ___; _____ __ 10
tion of nitric acid at 20 C. (68 F.), in two phases:
attack during 10 minutes at 20 C. (68 F.), then, a
Then, the plate is subjected to a second attack, at 60
brush cleaning and second attack at 20 C. (68 F.) 50 C. (140 F.) for a few minutes with the following solu
during 5 minutes.
I
Water

--_..-

Example 10
For treating half-cold-hardened low carbon steel hav
ing .10% carbon and .4~.6% manganese, the attack is 55
made with nitric acid at 20 C. (68 F.) during 12

For treating a plate made of hard Siemens-Martin steel


having .5% carbon and .5-.8% manganese, the attack

-._

'

150

tion:

Te?on is deposited as previously described. '

minutes, the acid concentration being 10%.


Te?on is deposited as previously described.
Example 11

__

Grams

Sulfuric acid ______________________________ -._


Chromic acid _____________________________ -._

50
20

Water ___________________________________ .._". 150

Pure Te?on is then deposited as previously-described.


Example 16
A small plate made of an enameled ferrous or cuprous

60 metal is dipped into a 15 %. solution of hydro?uoric acid

for 25 minutes at 20 C. (68 F.).


The acid attack transforms the globular mass of

enamel into a sponge, by breaking off the top portions


of the enamel globules.
The operating procedure is performed in the following 65 It is advantageous to attack the primary layer or mass
of the plate rather than the enamel ?nishingv layer.
manner: the plate is dipped into said solution of nitric
The ?rst layer of Te?on is deposited as hereinbefore
acid during 8 minutes, then brushed and dipped again
described.
into the solution for 4 minutes.
It must be noted that, in each of Examples 1-1l and
Te?on is deposited as previously described.
70 13-15, the surface may be subjected to a sand blast with
Example 12
extremely ?ne sand, preparatory to the acid attack, in
order to facilitate the same.
For treating iron, steel or another ferrous metal, or
a copper alloy, the preparatory treatment comprises sand
In all examples, the acid or mixture of acids may be
applied by means of a cataplasm, or a sponge, made of
blasting the surface with very ?ne sand; then, a ?rst
layer is deposited, which comprises a Te?on mixture, 75 rubber or glass ?bers. When a cataplasm is being uti
is made with a solution of nitric acid at 10% concentra
tion and at a temperature of 20 C. (68 F.).

2,944,917

lized, .it is advantageous to slightly increase the above


mentioned acid concentrations, since the concentrations

polytetra?uoroethylene anchored into said base, compris


ingthe steps of providinganchoring cavities having an
average size less than 30 microns and'a throttled en

the acid or acids are directly brought in contact with the

trance vin said \base by attacking it with a 10% solution


of hydrochloric acid ,in water for a period vof between

indicated inlsaid examples areparticularly suitable when


metal, as, for instance, by dipping.
vIn all examples, the thickness of the whole layer may
be increased by coating, melting, trickling, or by utiliz~
ing a light spraying gun.
When a thick-Teflon coating is desired, it is advan
tageous to -,f,or_m relatively .thin elementary layers one 10

after the other, each deposited elementary layer being


fused before the next elementary layer is deposited.

8 minutes and two hours at a temperatureib'etween 20 C.

and 75 C., the maximum temperature being used for

.the
mumminimum
temperature,
time the
and timeemployed
the maximum for
timeany
forparticular
the
attack varying upward from the lower limit to the up
per limit as the temperature employed varies downward
from its upper limit toward its lower limit, and subse

quently depositing the polytetra?uoroethylene thereon.

In a particular form of carrying the invention into prac

3. A method for coating anialuminum based metal with

tice, the concentration in the successively deposited ele

mentary layers of Te?on increase from one elementary 15 a continuous ?lm consistingessentially ,of'polytetra?uoro
ethyleneanchored into said base comprising the steps of
layer to the next one, so that advantage is taken of the
providing anchoring cavities having an average size less
strong anchoring produced by the diluted innermost ele
than 30 microns and a throttled entrance in said base
mentary layer of Te?on laid on the metal base as well
by ?rst attacking the metal with hydrochloric acid and
as of the high non-adhesiveness or hydrophobic charac
teristic given to the whole layer of Te?on by the more 20 then with a sulfochromic solution containing, by weight,

concentrated outermost elementary layer of Te?on; In

substantially 5 parts of sulfuric acid, ,2 parts of chromic

this manner, for producing the same coating having a


predetermined thickness, the number of necessary ele

acid, and 15 parts of water, at a temperature between

mentary layers may be reduced together with the fabrica

ethylene on said base andjfus'ing it in situ.


25 4. A. method of coating a ferrous metal base with a

1 tion costs.

3b9ut50 C, and 180, C., depositing the polytetra?uoro

.The coating method according to the invention pro

?lm consisting essentially polytetra?uoroethylene which

vides a Te?on layer the Whole thickness of which may

comprises the steps of ?rst applying to said base a thick


enamel coating, attacking the enamel coating with a 15%

be, for instance, comprised between 2 and 10 hundredths


solution of hydro?uoric acid, to produce cavities having
of a millimeter, and said layer does not peel off, nor
crack, and cannot be stripped off with the nail or a cut 30 an average size less than 30 microns and a throttleden

ting tool. Said layer can stand the squaring test, which
comprises tracing two perpendicularly disposed groups of

trance depositing the polytetra?uoroethylene thereon,


and fusing said polytetra?uoroethylene in situ.

lines on a Te?on coated surface by means of a cutting tool


so as to form a corresponding pattern indentedinto the

marily of aluminum with a continuous ?lm consisting

ly anchored to the treated surface up to the sublimation

base, which comprises the steps of creating anchoring

temperature of the Te?on deposited.


The accompanying drawing diagrammatically shows in

throttled entrance in said base by attacking it with ~hydro

5. A method of coating a metallic base consisting pri

exposed surface; ?nally, the ?lm of Te?on remains strong 35 essentially of polytetra?uoroethylene anchored into said

cross-section various forms of cavities provided in a sur

cavities less than 30 microns in diameter andhaving a

chloric acid, subsequently depositing the polytetra?uoro

face by an attack treatment according to the invention,

ethylene on said base and fusing the polytetra?uoro

together with .a substantially corresponding measuring

ethylene in situ.

scale.

'

While only the main objects of the invention have been


described and only some examples for carrying the said
invention into practice have been given in the above speci
?cation, it will be understood, of course, that the present
invention is not limited thereto, since many modi?ca
tions may be made and the appended claims intend to

6. A methodof coating a metallic *base consisting pri


marily of aluminum with a continuous ?lm consisting
essentially of polytetra?uoroethylene anchored to said

base, which comprises, the'steps of creating anchoring


cavities less than 30 microns in diameter and not vary
ing in depth in excess of 30 microns in said base and

having a throttled entrance, by attacking it with hydro

chloric acid, subsequently depositing the polytetrafluoro


cover such modi?cations as fall within the true spirit and
50 ethylene on said base and fusing the polytetra?uoro
scope of the invention.
ethylene in situ, said material having a minimum thick- >
I claim:
ness which is not less than 20 microns.
1. A method for coating a base selected from the
group consisting of iron and aluminum with a continuous
?lm of polytetrafiuoroethylene anchored into said base,
comprising the steps of providing anchoring cavities hav
ing an average size less than 30 microns and a throttled
entrance in said base by attacking it with at least one
acid, subsequently depositing an aqueous dispersion con

sisting essentially of polytetra?uoroethylene thereon in 60


a succession of elementary layers, and drying and fusing
each layer in situ before the next is deposited, the con

centration of polytetra?uoroethylene in each successive


layer being greater than thatin the layer previously de

posited.

2. A method for coating a base of aluminum-based 65


metal with a continuous ?lm consisting essentially of

References Cited in the ?le of this patent


UNITED STATES PATENTS

2,199,227

Marks ______________ __ Apr. 30, 1940

2,562,117

- Osdal _____' ___________ __ July 24, 1951

2,567,162
2,691,814
2,731,360
2,762,694

2,776,918
2,777,783

Sanders ______________ __ Sept. 4,


Tait ________________ __ Oct. 19,
Love ________________ __ Jan. 17,
Newman ____________ __ Sept. 11,
Bersworth __________ _..\__ Jan. 8,
Welch _______________ _._ Jan. 15,

1951
1954
1956
1956

1957
1957

FOREIGN PATENTS
657,085

Great Britain ________ __ Sept. 12, 1951