Device for the continuous coating of a metallic material in motion with a polymer deposition having a composition gradient

The subject of the invention is a process of continuous coating, with a polymer deposition, of a metallic material in motion inside a chamber under a reduced pressure, in which process the monomer of the said polymer is injected, in the gaseous state, into the said chamber and the conditions for forming a cold plasma are created so as to cause coating of the said material with the said polymer deposition, which comprises, in at least one region of the said chamber, the said material being made to pass through a magnetic field so as to cause a variation in the composition of the said polymer deposition in the said region. The subject of the invention is also a device for the implementation of this process, and a product obtained thereby.

FIELD OF THE INVENTION 
The present invention relates to the coating of metallic materials with 
organic polymers, such as polysilanes or polysiloxanes, especially for the 
purpose of protecting these products from corrosion. 
PRIOR ART 
The coating of metallurgical products with polymers by means of processes 
using a cold plasma created in an atmosphere under reduced pressure 
containing their monomers is currently well known. The depositions 
obtained may possess the functions of protecting the metallic substrate 
from corrosion, or of promoting the adhesion, on the said product, of a 
paint layer or of another polymer deposited by another technique. To this 
end, polymers formed from oxygen-containing monomers, such as silanes or 
siloxanes, can be used. These polymers are particularly advantageous in 
that the monomer molecules in the plasma are dissociated to a greater or 
lesser extent depending on the temperature and pressure conditions in the 
chamber under reduced pressure in which the treatment takes place, and 
also depending on the electrical parameters governing the formation of the 
plasma. In the case of a strong dissociation, the polymer which is 
deposited on the substrate possesses a pronounced "inorganic" character, 
that is to say the Si--O bonds are particularly numerous. Conversely, in 
the case of a weak dissociation, the polymer possesses a very predominant 
"organic" character, with Si--O bonds hardly more extensive than in the 
monomer. 
It may be desired to deposit several superimposed polymer layers on the 
product to be coated, each of these layers being of a different nature. 
This is fairly easy when the product is a single component held fixed 
during the coating steps: all that remains to be done, when the deposition 
of one layer is deemed to be complete, is to vary the treatment parameters 
(composition of the atmosphere, electrical parameters, etc.) in an 
appropriate manner in order to produce the deposition of the next layer. 
In particular, it is known to produce successively a polysilane or 
polysiloxane deposition and then a silica deposition by introducing into 
the treatment chamber firstly a pure silane or siloxane monomer, in order 
to form the polymer layer, and then by mixing the said monomer with oxygen 
in order to form the silica layer. On the other hand, when the product is 
a strip in motion which has to be continuously coated, this is possible, 
according to the known processes (see, for example, French Patent 
Application FR 91 13720), only by passing the product successively through 
several chambers. Conditions suitable for the deposition onto the product 
of a layer of specified nature are established inside each of these 
chambers, and these chambers have to be separated from each other in a 
sealed manner. This involves constructing relatively complicated 
installations. In addition, the latter do not make it possible to produce 
a gradual change in the composition of the deposition, since the boundary 
between the various layers is always defined in a clear-cut manner. 
However, such a gradual change may be desired so as to obtain maximum 
adhesion of a given layer to the previously deposited layer. This problem 
arises, for example, when it is desired to deposit several layers of the 
same base polymer, the said layers possessing an alternating organic and 
inorganic character. 
SUMMARY OF THE INVENTION 
The object of the invention is to propose a means for carrying out, inside 
the same chamber, the deposition of several successive layers, of dominant 
inorganic or organic character, of the same polymer onto a metallic 
product in motion. 
To this end, the invention is a process of continuous coating, with a 
polymer deposition, of a metallic material in motion inside a chamber 
under a reduced pressure, in which process the monomer of the said polymer 
is injected, in the gaseous state, into the said chamber and the 
conditions for forming a cold plasma are created so as to cause coating of 
the said material with the said polymer deposition, which comprises, in at 
least one region of the said chamber, the said material being made to pass 
through a magnetic field so as to cause a variation in the composition of 
the said polymer deposition in the said region. 
The subject of the invention is also a device for the continuous coating, 
with a polymer deposition, of a metallic material in motion, of the type 
having a sealed chamber fitted with means for obtaining therein and 
maintaining therein a reduced pressure, means for progressively moving the 
said material inside the said chamber, means for introducing the monomer 
of the said polymer, in the gaseous state, into the said chamber, means 
for creating the conditions for forming, inside the said chamber, a cold 
plasma over the path of the said material in motion, which also comprises 
means for superimposing a magnetic field on the said cold plasma over a 
fraction of the said path of the said material in motion. 
Finally, the subject of the invention is a product obtained by the process 
according to the invention. 
As will have been understood, the invention consists in making the product, 
while it is progressing through the treatment chamber containing the 
monomer of the polymer to be deposited, pass through several successive 
zones in each of which it is exposed to a cold plasma leading to a polymer 
deposition onto its surface. In one of these zones at least, the influence 
of a magnetic field is superimposed on that of this plasma. This magnetic 
field substantially modifies the conditions under which the monomer 
molecules react, to the point of changing the chemical nature of the 
deposition which, in the zone in question, is formed on the product. 
Compared to the usual processes for forming, on the metallic substrate, 
several layers of different natures from the same monomer, this invention 
does not require the atmosphere in the chamber to be modified, and the 
various depositions may thus be continuously carried out in the same 
chamber.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S) 
The invention will be better understood upon reading the description which 
follows, referring to the single figure which shows, diagrammatically, an 
example of a device according to the invention. 
In this single figure, the product to be coated is in the form of a strip 1 
made of metal such as bare steel or galvanized steel, set into progressive 
movement by conventional means (not shown). Here, it is desired to coat it 
on one of its faces with an organic polymer, the monomer of which contains 
silicon and oxygen atoms. This polymer is capable of exhibiting a fairly 
pronounced inorganic character, that is to say of possessing a greater or 
less proportion of Si--O bonds compared to Si--Si, Si--C and Si--H bonds. 
A polysilane or a polysiloxane complies with these criteria. To this end, 
the strip 1 is made to penetrate into a sealed chamber 2. The strip 1 
penetrates into the chamber 2 through an inlet orifice 3 and the strip 1 
leaves the chamber 2 through an outlet orifice 4. These two orifices 3 and 
4 are fitted with sealing means, not shown, so as to isolate the chamber 2 
from the outside even when the strip 1 is engaged therein. Attached to the 
chamber 2 is also a pipe 5, connecting it to the outside via a pump 6. 
This pump 6 makes it possible to maintain a specified reduced pressure, of 
the order of 0.1 to 1,000 Pa, or even less if necessary, in the chamber 2. 
Finally, another pipe 7 is connected via a valve 8 to a bottle 9 
containing the monomer of the polymer to be deposited, this monomer being 
under temperature and pressure conditions such that it can escape from the 
bottle 9 in order to penetrate into the chamber 2 in the vapor state. The 
installation also includes an AC generator 10, one of the poles of which 
is connected to earth and it will be seen later which members the other 
pole of which generator is connected up to. 
After its penetration into the chamber 2, the strip 1 comes into contact 
with a first roller 11, which is free to rotate or is driven about its 
axis 12. The role of this first roller 11 is twofold. Firstly it guides 
the strip 1 and it contributes to maintaining it in a suitable state of 
tension and planarity. On the other hand, it is connected to one of the 
poles of the generator 10 and imparts its potential to the strip 1. After 
having left the first roller 11, the strip 1 passes in front of a first 
electrode 13 connected to earth, defining with the strip 1 a space 29. 
Next, the band 1 comes into contact with a second roller 14. This second 
roller, made of non-magnetic material, is constructed in two parts: a 
stationary core 15 and an outer shell 16 which, by virtue of appropriate 
means, not shown, such as bearings, can rotate on the surface of the 
stationary core 15 when this shell is driven by the strip 1 with which it 
is in contact. This second roller 14 is connected to the same pole of the 
generator 10 as the first roller 11, and also contributes to the 
imposition of the potential of the generator 10 to the strip 1. Integrated 
into the stationary core 15 are permanent magnets 17, 18, 19, 20, 21, 22, 
23 distributed over the circumference of the stationary core 15 in the 
vicinity of its surface, opposite the zone of the circumference of the 
shell 16 which is in contact with the strip 1. Facing a part of this zone 
at least, and opposite the permanent magnets 17 to 23, is arranged a 
second electrode 24 which is connected to earth and which defines, with 
the strip 1, a space 25 of substantially constant width (although this is 
not strictly speaking absolutely necessary). After having left the second 
roller 14, the strip 1 moves progressively in front of a third electrode 
26 identical to the first electrode 13, and it also is connected to earth. 
The strip 1 and the third electrode 26 define a space 30. Next, it passes 
over a third roller 27, which is free to rotate or is driven about its 
axis 28, and is connected to the same pole of the generator 10 as the 
other two rollers 11, 14. Its role is comparable to that of the first 
roller 11. Next, the strip 1 leaves the chamber 2 through the orifice 4. 
The installation is used as follows. Firstly, the beginning of the strip 1 
is introduced into the chamber 2. Next, the chamber is put under reduced 
pressure and the monomer of the polymer to be deposited, for example 
hexamethyldisiloxane (HMDS), is introduced therein so as to maintain a 
partial pressure of HMDS of the order of 10 to 100 Pa, for example. Next, 
the progressive movement of the strip 1 is initiated and the generator 10 
set to operate at a frequency of the order of 50 kHz with a power of a few 
tens of watts. In this way, the strip 1 is biased, the strip behaving as 
cathode while the three electrodes 13, 24, 26 behave as anodes. The effect 
of the potential difference existing between the strip 1 and the 
electrodes 13, 24, 26 is to create a low-temperature plasma within the 
spaces 25, 29, 30 which separate them. The effect of this plasma is to 
dissociate the HMDS molecules and these are deposited in the form of a 
polymer of the polysiloxane type onto the face of the strip 1 which 
progressively moves in front of the electrodes. 
As has been stated, this polysiloxane may exhibit a fairly pronounced 
inorganic character. However, the presence in the stationary core of the 
second roller 14 of the permanent magnets 17 to 23 very substantially 
modifies the operating conditions in the space 25, compared to those 
existing in the spaces 29 and 30. In fact, conditions of the "magnetron 
sputtering" type are obtained therein which are known to cause very 
extensive dissociation of the monomer molecules and particularly high 
rates of deposition of the polymer. Moreover, these conditions go hand in 
hand with an accentuated inorganic character for the said polymer 
deposition. It is therefore possible, by using the installation which has 
just been described, to carry out in succession the deposition of three 
alternating polymer layers onto the strip 1: 
a first layer, predominantly organic, deposited facing the first electrode 
13; 
a second layer, having a more pronounced inorganic character, deposited 
facing the second electrode 24, while the magnetic field created by the 
permanent magnets 17 to 23 is superimposed on the electric field existing 
between the strip 1 and the electrode 24; 
a third layer, predominantly organic, deposited facing the third electrode 
26. 
By way of example, the following operating conditions may be used: 
generator 10 having a power of 80 W and a frequency of 50 kHz; 
HMDS pressure in the chamber 1: 0.3 mbar; 
magnetic field between the second electrode 24 and the second roller 14: 
intensity of the order of 1000 G. 
Under these conditions, when facing the two electrodes 13 and 26 which are 
not affected by a magnetic field, a rate of growth of the polymer layer of 
approximately 0.3 .mu.m/min is observed. On the other hand, when facing 
the second electrode 24, under the influence of the magnetic field, a rate 
of growth of the polymer layer of approximately 2.4 .mu.m/min is observed. 
Moreover, as has been stated, this layer exhibits a stronger inorganic 
character than the other two. 
It is possible to produce polymer layers of greater or lesser respective 
thicknesses as a function of the time which the strip 1 spends in the 
various parts of the installation (and therefore as a function of the 
speed of progressive movement of the strip 1 and of the length of the 
electrodes 13, 24, 26). The particularly high rates of deposition 
observed, especially for the zone subjected to the magnetic field, render 
this process compatible with an industrial operation in which the strip 1 
would move progressively at a speed of 25 to 50 m/min in a reactor which 
would only be 2 to 4 m in length. It would thus be possible to obtain 
depositions of 2000 to 2500 .ANG. in thickness, knowing that they 
constitute good corrosion barriers on steel products coated with 
zinc/nickel alloy and other galvanized products. 
In the example described, a first, predominantly organic, polysiloxane 
layer, a second, predominantly inorganic, polysiloxane layer and a third, 
predominantly organic polysiloxane layer would therefore be obtained. The 
advantage of such a multilayer product compared to a product which would 
exhibit only a single polysiloxane layer having an inorganic or organic 
character, is that such a multilayer deposition constitutes a better 
corrosion barrier than a monolayer deposition of equivalent thickness. 
Moreover, it is thus possible to benefit simultaneously from the 
advantageous properties of the two types of coating: for example, from the 
better mechanical strength of the depositions having a strong inorganic 
character compared to the predominantly organic depositions, and from the 
more hydrophobic character of the latter which render them more capable of 
receiving a paint layer. 
Of course, it is possible to imagine numerous variants of the installation 
which has just been described. For example, it is possible to use only a 
single, large-sized permanent magnet, or any other device for imposing a 
magnetic field. It is also possible to impose progressive variations in 
the magnetic field within the space 25, which field, for example, would 
increase from the magnet 17 to the magnet 20, and then decrease once again 
down to the magnet 23. Thus, a progressive variation in the 
organic/inorganic character of the polymer deposition would be obtained 
which would guarantee excellent cohesion of the deposition. Likewise, it 
is possible to provide only a single zone with deposition not enhanced by 
a magnetic field, and therefore a deposition of only two differentiated 
polymer layers; or, conversely, to increase the number of electrodes in 
order to be able to increase accordingly the number of layers, or even to 
coat both faces of the strip by making these move progressively, in 
succession, in front of as many electrodes as necessary. Finally, instead 
of employing a conventional AC generator, it is possible to employ a 
radiofrequency generator operating at 13.56 MHz, as is commonly used in 
the field of plasma treatments. It would also be possible to employ a DC 
generator. However, in the latter case, there would be a constraint which 
limits the deposited thickness of the polymer to only a few thousands of 
.ANG., since beyond this the insulating character of the deposition would 
lead to breakdown phenomena which would damage the coating. On the other 
hand, it is possible to provide separate electrical power supplies for 
each electrode. 
Likewise, any device other than the roller 14 which has just been described 
may be used if it provides functions comparable to those of the roller, 
namely the formation of a cold plasma superimposed with a magnetic field 
over a fraction of the travel of the strip 1 in the chamber 2. 
Finally, the applications of the invention are not limited to the 
deposition of polysilanes or polysiloxanes, but to the deposition of any 
polymer whose composition is influenced by the superimposition of a 
magnetic field on the cold plasma which causes the polymerization.