CA1252005A - Ptfe coating process - Google Patents

Abstract

PTFE COATING PROCESS Thin, adherent coatings of PTFE are formed by rubbing dry, discrete particles of PTFE across the surface of a substrate, preferably on the surface of a fabric or felt polishing wheel. The particles are preferably smaller than 30 microns diameter. The peripheral speed of the wheel may be, for example, from 5 m/sec to 100 m/sec.

Description

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.i ~Z5~ 5 , PTFE COA~ING PROGESS
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This invention relates to a process and apparatus ' for coating a substrate with polytetrafluoroethylene I (PTFE), and to PTFE-coated products.
;~` PTFE is extraordinarily resistant to chemical ! 5 attack, and the surface free energy of solid PTFE is very j' low. This means t~at liquids do not readily wet the solid, and other solids do not adhere strongly. These properties ` render PTFE very valuable for forming protective surface coatings, in a wide range of applications from non-stic~
cookware to surgical sutures. However, the very properties which make PTFE so use~ul in such applications also make it very difficult to form PTFE coatings which are sufficiently adherent to their substrates. In practice, PTFE coatings formed hitherto have relied on mechanical keying for their adherence to their substrates. For . example, one common method of forming PTFE coatings is to coat the intended substrate first with a primer and then to implant solid PTFE particles in the primer layer, while the latter is still tacky, so that it can trap the PTFE particles in a mechanical matrix. These PTFE particles then form anchor points for subsequent layers of PTFE
il particles which are attached thereto by sintering at ¦ temperatures of between 350 and 400C, depending on the type of PTFE used.
In an alternative method for forming PTFE coatings, an extruded or sXived PTFE sheet is fibrillated by subjecting it to substantial mechanical stresses. The voids created in the PTFE allow adhesives or other ~ materials to penetrate the PTFE sheet and form a mechanical ¦ 30 bond therewith.
j A still further method employed for coating with I PTFE telomers is to spray, brush or otherwise spread onto . a~

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the substrate a disperslon of low molecular weight solids of PTFE suspended in a suitable liquid such as*Freon or water, and then to evaporate the solvent. Such coatings are sometimes sintered or even buffed in order to increase the uniformity of the coating. However, coatings formed by this method are only poorly adherent and usually intended for single applications such as in mould release applications or as release layers for decalcomanias.
The present invention provides an entirely new method of depositing PTFE films. The method is applicable to forming PTFE coatings on a wide range of substrates, and produces a type of PTFE coating which is believed to be unique.
The present invention is based on the unexpected discovery that PTFE can be made to form films of un-precedented adherence merely by rubbing minute particles of PTFE with sufficient force across the surface of a substrate. It is believed that the bond obtained between the PTFE coating and the material of the substrate when the method of the invention is used ls not merely the result of mechanical keying between the PTEE and micro-scopic rugosities on the surface of the substrate, because friction coatings of the latter type are known to be only very weakly adherent. For example, a method which has been used in the study of friction wearing of PTFE has been to cause a solid rod of PTFE having a pointed end bearing perpendicularly onto a plate of glass to traverse back and forth over the same track until a layer of the desired magnitude is deposited. Coatings formed in this way can be lifted from the surface of the glass merely by immersion in water containing a surfactant.
The difference between the PTFE coating of the present invention and the PTFE friction coating just described is believed to be due to the high energies which Trademark S2~5 . 3 are involved in forming the coatings of the ~nvention.
While the exact mechanism of coating is not knownt it is thought that at sufficiently high energies, the PTFE
particles serve to decontaminate the surface of the substrate, the surface thus being activated in some way so as to be highly receptive to any molecule with which it might come into contact. When a sufficient number of PTFE particles are rubbed across the surface at a sufficient rate, fresh PTFE particles are presented to the decontaminated surface, and thus bond therewith, before recontamination by other molecules can occur.
- A possible alternative mechanism is that under ' the very high energy conditions which obtain at the ¦ interface between the PTFE particle and the substrate, an intimate molecular mixture or complex is fon~d between the PTFE
and the material of the substrate, analogous to a metallic alloy, I notwithstanding that the two materials would not non~ly fonm an j alloy with each other.
j Quite apart from its adherence, the PTFE coating of the present invention has a number of characteristics which are not found, at least in combination, in con-1~ ventional PTFE coatings. Firstly, they are very thin, ¦ being less than 3 microns in thickness. More usually, they are substantially thinner than this, very often being less than 500 nm thick and often less than 200 nmthick. Typical film thicknesses are from 10 to 100 nm thick, for example from 20 to 50 nm thick. A most unusual characteristic of the process of the invention is that the PTFE coatings produced thereby are effectively self-limiting in thickness, in the sense that the coating, once formed, will generally not increase in thickness even when more PTFE powder is rubbed over the surface.
Another characteristic of the PTFE films formed by the process of the invention is that they are substantially ~s~oos non-porous. This is hlghly unexpected in such a thin l PTFE coating.
Yet a further characteristic of the coatings formed by the method of the invention is that they are sub-stantially free of voids. Even sintered PTFE coatings include a sufficient number of voids to brin8 the bulk ; density of the coating down to 1.5 g/cm3 or even less.
In contrast, the coatings formed by the method of the present invention have a bulk density which is at least 1.70 g/cm3, most usually greater than 1.80 g/cm3 and often greater than 1.90 g/cm . Typical coatings according to the invention have a bulk density of

2.0 g/cm3 or greater, for example from 2.1 g/cm3 to j 2.25 g/cm3.
r 15 Accordingly, the present invention provides a methocl of coating a substrate with PTFE, comprising causing discrete, substantially dry particles of PTFE to move , across the surface of the substrate with sufficient ¦ force and at sufficient speed relative to the sur~ace to cause PTFE to become deposited on the surface of the substrate in an adherent film.
Viewed from a different aspect, the present invention provides a method of forming a PTFE coating on a substrate, comprising rubbing discrete, sub-stantially dry particles of PTFE across the surface of the substrate with sufficient force and at sufficient speed relative to the surface of the substrate to cause a PTFE coating of self-limiting thickness to be deposited on the substrate Also provided by the present invention is an apparatus for coating a substrate using the method, said apparatus comprising a support for the substrate,a rotary !

i applicator arranged to bear against a substrate supported on said support, means for delivering a supply of substantially dry particles of PTFE to the surface of Il the applicator, or of the substrate, or both, and means `1~ 5 for rotating the rotary app:Licator to cause the surface thereof to rub said particles against the substrate, whereby to coat the substrate with the coating material.
Further provided by the invention is a substrate having deposited thèreon an adherent substantially non-microporous PTFE film which is less than 3 microns thick.
The application of PTFE to the substrate with the requisite rate of energy input may be achieved by bombarding the intended substrate with particles of PTFE carried on the surface of larger particles of the same or different resilient material such as cork. The carrier particles may be projected at the surface to be ;~ treated by entrainment in a cold or heated high velocity jet of gas. Alternatively, the carrier particles may be caused to vibrate acoustically (ultra-sonically), magnetically or mechanically against a substrate.
Preferably, however, the PTFE particles are rubbed i across the surface of the substrate by means of an applicator having a resilient surface which is in ¦ sliding contact with the substrate. The applicator i, 25 may bel for example, a rotary applicator such as a ¦' roller or wheel.
¦~ A particularly preferred applicator for use in ¦ the method of the invention is a jeweller's buffing wheel.
Suitable buffing wheels include those available from ¦ 30 W. Canning Materials Limited, Great Hampton Street, I Birmingham, England. These buffing wheels generally ¦ comprise a plurality of fabric discs clamped together in a way which allowsthe density of fabric at the periphery of the wheel to be adjusted,or are made of felt.
., s i - 6 -,~ The term "PTFE" as used herein is intended to '' embrace both PTFE homopolymers and polymers formed by copolymerising tetrafluoroethylene with other monomers.
`, Polymers of fluoroethylene containing other halogens ,j 5 are also included, as are mixtures of polymers of different composition. Polymers may be of different chain lengths (molecular weights), molecular weight distribution and crystallinity. Oligomers and telomers of tetrafluoroethylene are also included.
If desired, other particles, such as mineral particles of a pigmentary character, may be included with PTFE particles.
~ The PTFE particles are preferably less than 100 ! microns in diameter, and more preferably less than 50 micror.s in diameter. Particularly preferred are PTFE
particles having a maximum diameter less than 30 microns.
J The PTFE particles may be delivered to the surface !,~ of the applicator in the dry state, but it has been found to be more convenient to deliver the PTFE particles to the surface of the applicator in the form of a liquid dispersion. Preferably, the dispersing solvent is sufficiently volatile to evaporate almost instantly, leaving the particles in a substantially dry state.
A suitable dispersing solvent is trichlorotrifluoroethane, though other low-boiling halogenated hydrocarbons can also be used.
The method of the invention can be used for coating ; virtually any substrate, but it is of particular utility in the formation of thin PTFE films on plastics sheets, foils, tapes and films. Remarkably, the process may also be used to great advantage for coating paper and woven and nonwoven fabrics (whether of natural fibres such as cellulosic fibres, or synthetic fibres such as .~
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polyesters, polyolefins, polyamides and substituted celluloses) and other materials of a soft nature.
When the substrate has an uneven surface 9 such as the surface of a nonwoven-fabric, the coating may be macroscopically discontinuous, in that only the high points of the substrate are coated with a thin, adherent, substantially nonmicroporous film. However, when such substrates are coated by the method of the invention, it is found that both the micro and macro interstices between and within the fibres are ~illed with loosely compacted sub-particulate materials which are thought to be micro platelets and it is thought that these platelets are formed when the PTFE particle is violently scraped across the protruding fibres on the surface of the substrate. It will be understood that the PTFE
deposited on the highlights does not require sintering to ensure an effective and adherent film. Depending on the end use for which the coated substrate is intended, however, it may be desirable to increase the coherence and adherence of the micro platelets which accumulate in the depressions between the highlights. This can be achieved by sub~ecting the coated substrate to a fla~h sintering operation. This flash sintering involves the passing of a coated substrate through a nip where at least one roller is heated, for example to a surface temperature of above ~50~, e.g. 410C. The coated substrate has to pass through rapidly so as not to cause scorching or other structural damage. The thicker the platelet deposits, the longer is the dwell time necessary in the heated nip. Therefore there is a natural restriction on the thickness of sintered coatings which may be formed on substrates which are liable to thermal damage.

~5~ 5 In certain cases, the above-described method of flash sintering will not be appropriate. For example, if a PTFE-coated bank note is flash sintered using heated rollers, the elevated temperature and pressure at the nip of the heated sintering roller cause ink at the raised images produced by the Intaglio process to soften and flatten. Consequently it is appropriate in thls instance to use a non-contact heat source such as high intensity radiation.
In cases where the PTFE coating of the invention is deposited on a relatively une~en surface, the thin film which is formed on the ~igh points of the substrate constitutes an anchor to which further PTFE layers ~ay be bonded by conventional sintering processes.
It will be appreciated that the nature of the present invention is such as to preclude precise enumeration of the appropriate process conditions for forming a PTFE film on a given substrate. This is because coatings can be formed using a wide range of process conditions, which are all dependent on each other. Thus, for example, when a buffing wheel is used to rub the PTFE particles across the substrate, the pressure applied by the wheel, the area of contact between the wheel and the substrate, the peripheral speed of the wheel, and the relative speed between the surface of the wheel and the substrate may all be varied.
However, alteration of any one of these parameters may require that one or more of the other parameters be adjusted in order to compensate. Moreover, the conditions necessary for forming a PTFE coating according to the invention will depend greatly on the physical and chemical nature of both the PTFE and the substrate. In all cases, however, the appropriate process conditions will be readily determinable by the person skilled in the art, _ g _ particularly having regard to the guidelines and specific examples set out below.
Generally, we have found that the more delicate the substrate, the lower the pressure with which the PTFE particles should be pressed against the substrate, in order to avoid damage thereto Thus, for example, a very light~eight nonwoven farb~c may be coated using a 30 cm diameter soft ~abric ~uf~ing wheel, by training the fabric round the buffing wheel, and applying only 10 a slight tension (e.g. from 10 to 100 grams/cm width of fabric, depending on the strength of the fabric). With ~ this arrangement, the pressure with which the wheel bears against the fabric is very low indeed, for example from less than 1 g/cm2 to a few grams/cm2. However, such low pressures are compensated for by the fact that individual PTFE particles are drawn over a very sub-stantial length of the nonwoven fabric, such as from one quarter to three quarters of the circumference of the wheel. In the example first described, the roller can conveniently be rotated at 2000 rpm, while the nonwoven fabric web is drawn through at about 10 metres/
minute.
When the substrate is rather more robust, such as a paper of weight 100 g/m2, a convenient coating technique is to feed the substrate into the nip between a buffing wheel and a retaining roller. In this case, the distance for which individual PTFE particles are in contact with the substrate is very much smaller (generally from 1 to 20 mm, e.g. from 2 to 10 mm), and substantially larger pressures are therefore appropriate.
Conveniently, the static pressure of the roller on the substrate will be at leas-t lOO g/cm2, preferably at least 200 g/cm2, a,nd more preferably from 300 g/cm2 to 10 kg/cm , e.g. from s~os SOO g/cm2 to 2kg/cm2.
Generally the harder the intended substrate, the harder the applicator which may be used. For example, we have coated a 50 micron thick polyester sheet using a soft fabric buffing wheel (see Example 2 below), but it was preferred to use a ha~d felt polishing wheel ( 20 cm x 2.5 cm, 1700 rpm, 3kg/cm2 estimal;ed dynamic nip pressure) for coating aluminium.
Although the factors which determine the appropriate operating conditions for different substrates are imperfectly understood, it will be apparent that identifying the appropriate conditions for a given substrate is merely a matter of trial and error. The operator need only choose a coating technique which is appropriate to the strength and flexibility of the substrate in question, and then increase the applicator pressure and/or applicator speed until a desired coating is formed.
The method of the invention can be used for coating an enormous range of products. Particular exa~ples include the coating of magnetic recording media, such as video recorder tapes, audio recording tapes, computer tapes, computer floppy discs and computer hard discs.
The PTFE coating services to protect both the recording medium itself and the information stored in it against dirt, liquids and other materials which might interfere with proper recording and reading of stored information.
Because the process of the invention results in the formation of a very thin film of PTFE. the recording and reading heads which are used for storing and retrieving ~5;~

information from magnetic recording media can be placed in their normal very close relationship to the surface of the recording medium.
Another area of application for the method of the --invention is in the coating of medical products9 such as bandages, wound dressings, burns dressings, personal hygiene products, surgical needles, staples, sutures, catheters, surgical drapes and surgical gowns. ~ound dressings which are PTFE coated in accordance with the invention are dirt-repellant, and therefore more hygienic, and also non-adherent to wounds. PTFE-coated fabrics in accordance with the invention may b~ used to form water-repellant, but air-permeable gowns and drapes. Needles and staples may be given a low-friction coating to decrease the discomfort caused to the patient by their use, and PTFE-coated sutures according to the invention are more easily removed.
Yet further applications of the invention are in forming anti-soiling coatings for security paper, bank notes, stamps, maps, charts, paper bags, envelopes, food wrappings, cookware, fabrics for curtains, wallpaper, yarns such as carpet yarns, threads and ropes. Still further applications include the formation of low-friction coatings for nip rollers, calenders, process machinery, missile and aircraft s~in coatings, helicopter and air-craft blades, impellers and propellors, boat and shiphulls, low speed bearings, razor blades and conveyor tube coatings. Further applications include the formation of water-repellant coatings for tent fabrics, clothing fabrics, and incontinence products including diapers, and the formation of release coatings for pressure sensitive adhesive tape backings, dry print foils, mould release papers and foils, heat transfers and decalcomanias.

~5~05 , Still further examples of the applications of the , present invention are set out in our earlier British Patent Application ~o. 8401838, filed 24th January 1984 .
and published in EPO Publication No. 0152203A on August 21st, 1985.

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A number of embodiments of the invention will now be particularly described with reference to the accompanying drawings in which:-Figure 1 illustrates diagrammatically a rotary applicator for carrying out the method of thisinvention; and Figure 2 shows diagrammatically the applicator in the context of apparatus for use in carrying ou~
the method of this invention.
The apparatus shown in Figure 2 will be carried within a metal frame of such mass and proportions so as to withstand the loadings and stresses imposed upon it by the operation. A rotary motive power unit, in this case an electric motor (not shown), capable of deli~ering rotational speeds at the torque necessary for the operation, is mounted to drive the apparatus. Within this description we shall consider only the coating of a moving web of approximately 20 cm width. The apparatus therefore also requires the means of conveying the web through the apparatus.
At the heartof the apparatus of the present example are two rollers 10, 11 forming a nip 12 through which the substrate 13 must pass. One of these rollers 10 is the applicator and the other is the retainer 11. The retainer roller rotates in the same direction as the web is travel-ling. The applicator roller is driven and rotates so that its surface in the region of the nip moves in the same direction as the web, but at a different speed, or in the opposite direction, all as indicated by arrows in Figure 2.
~ he two rollers 10, 11 are mounted within the frame in such a way that the centre lines of their axis may be moved relative to each other and possess the necessary facility to be firmly fixed in the desired position after the correct nip pressure has been set.

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-_ 14 Apart from the small segment of its clrcumference at the nip and the aperture required through which the coating material is conveyed or any surplus which may be extracted via a flexible duct 14A, the applicator is contained in an enclosure 14.
The coating material may be applied to the applicator by any means so long as the particulate material is in a dry form when it reaches the nip and it is uniformly deposited over the face of the applicator.
In the present example an airless spray 15 is used to convey the PTFE particles at a nozzle pressure of 480 P.S.I. Although in the above-mentioned airless spray the PTFE particles are dispersed in a sol~ent~
which being FREON ~Registered Trade Mark~ TF is highly volatile and is thought to "flash off" almost completely before the PTFE ~artlcles hit the surface of the applicator, the preferred method is to apply the coating material uniformly in a dry particulate state.
One benefit of using the dry particulate state is to avoid using solvents which are unattractive for commercial and environmental reasons.
The airless spray is equipped with a switch mechanism (not shown) which is operated by a cam which is rotating at 38 RPM and has lifting knobs having an effective operating dwell of 3~ arc on the cam. The number of lifting knobs used is determined by the surface roughness of the substrate and or the quantity of particulate material that is desirable to be deposited on the substrate.
The spray nozzle is adjusted to produce a fan-shaped spray pattern 16 in which the particles are evenly dis-tributed when they contact the applicator roller 10. The applicator roller 10 and the spray cam (not shown) are linked through gearing in such a way that with each squirt s~s _ 15 of the nozzle approximately one quarter of the applicator's surface areaalong its circumference receives a deposit of the coating material and 40 revolutions later the appli-cator receives a second squirt of material which should land on the second quadrant and so forth.
The applicator is made from sheets of cotton fabric 17 cut in 10 cm diameter discs with a~hole in the centre of each disc of 2. 5 cm diameter~, These cotton discs are then pulled onto a threaded steel shaft 18 of 2.5 cm diameter and are retained by 6 mrn thick steel washers 19 of 8.9 cm diameter to form an applicator 30 cm wide. The washers in turn are retained by suitable nuts. The cotton discs are,compacted by tightening the retaining nuts to produce a density at the perimeter face of the compacted cotton mass appropriate to the material to be coated. We have found that delicate substrates require softer rollers than resilient substrates. When using polyester films and other delicate materials the applicator is considered to be of sufficient density ~or use on a polyester film when it cannot be compressed by more than 6 mm when reasonable thumb pressure is applied.
When a softer applicator is desired intermediate ' nuts 18 and ~ashers 20 may be used on the sha~t at say every 1 to 2 cm along the length of the applicator. Alter-natively, the nuts may be tightened further in order tocompact the cotton sheets into a more solid mass.
Once the correct applicator density is achieved it is then ground in by running it at high speed against the retaining roller, the surface of which is closely covered with a sheet or coarse abrasive material such as emery cloth and running in a counter direction to the rotation of the applicator for 1 or 2 hours or until such time as a smooth enough surface corresponding to the con-tours of the retainer roller is produced. Following this operation the coarse abrasive mater~al is rsmoved and the 52~5 the deposition process is ready to commence.
In general, we have found that the rate of energy input required for the best operation of the invention increases with the molecular weight and/or the crystallinity of the PTFE.
The invention is now further illustrated by the following examples:-To coat a common grade of paper we have used the following formulation:-Fluon L168 (PTFE) 150 gm Freon TF (trichlorotri-fluoroethane),-as dispersant 2,750 gm 2,900 gm Fluon is a Trade Mark of ICI, and Freon is a Trade Mark of Du Pont.
In this particular example the paper used was a stencil based paper manufactured by Tullis Russell. It was an uncoated, unsized paper of 105 gm per metre.
The pressure applied by the applicator roller was 0.77 kgs/Sq.cm. The substrate (paper) web moved at 27 metres per minute. The speed of rotation of the appli-cator roller was 1550 rpm but the retainer roller rotated at only 92 rpm.

The same apparatus as in Example 1 was used to coat a polyester film of 50 microns thickness (Melinex S grade polyester sold by ICI). The applicator roller applied pressure was 0.5 kgs/Sq.cm. which was reduced to this level because the substrate is in this case a relatively smooth surface material. It was also found best to use a softer roller for this type of substrate than was used for coating paper. Also the best results on this type of substrate occurred when a low molecular weight PT~E
was used with a formulation of the following proportions:-Vydax AR (20% solid ln Freon) 600 gmsFreon TF 2,900 gms 3,500 gms Vydax fluorotelomers are dispersions of a white, waxy comparatively short-chain telomer of tetrafluoro-ethylene in Freon TF.

Stainless steel surgical wire was coated with PTFE
by rubbing with a felt buffing wheel (20 cm diameter x 2.5 cm) rotating at 3000 rpm, to which the PTFE dispersion described in Example 1 was continuously applied. By way of comparison, a sample of the same wire was coated by the method currently recommended for coating surgical staples. This method is to dip the wire into a dispersion of Vydax AR and Freon, and to allow to dry. The coating is then sintered at 350C until it develops a glossy appearance.
When the wire coated with the conventional method was contacted with acidic ferric chloride solution, it was attacked and etched within seconds. By contrast, when the wire coated with the method of the present invention was contacted with the same ferric chloride solution, it showed no sign of attack even after days.
In order to test the friction properties of wire coated by the two methods, the conventionally coated wire was inserted into a f~abric which is commercially referred to as mole-skin, left in place for 30 minutes at 25C, and then pulled through by an Instron instrument. It showed an initial resistance of 50 gms and a dynamic resistance of 20 gms. When a wire coated with the method *Trademark ~s~
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of the invention was sub~ected to the same test, the corresponding values were 26 gms and 9 gms.

The applicator roller pressures mentioned in the above examples were estimated on the basis of the degree of deformation of the surface of the roller, when station-ary. It is believed, however, that very substantially larger pressures (e.g. from 10 to 50 times the values given above) are developed when the roller rotates against the substrate at the high rotational speeds used for coating, which will typically involve peripheral speeds of from 2 to 200 m/sec, more usually from 5 to 100 m/sec, e.g.
from 10 to 50 m/sec.

It will be understood that the present invention has been described above purely by way of example, and modi-fications of detail may be made without departing fromthe scope of the invention.

Claims (11)

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1. A method of coating a substrate with PTFE
comprising rubbing discrete substantially dry particles of PTFE across the surface of the substrate with sufficient force and at sufficient speed relative to said surface to cause PTFE to become deposited on the surface of the substrate in an adherent film.

2. A method according to claim 1 wherein the PTFE
particles are rubbed across the surface of the substrate by means of an applicator having a resilient surface which is in sliding contact with the substrate.

3. A method according to claim 2 wherein the applicator is a rotary applicator.

4. A method according to claim 2, wherein the PTFE particles are less than 100 microns in diameter.

5. A method according to claim 1, wherein the substrate is a wire, thread, filament, tube or flexible web.

6. A method according to claim 5, wherein the substrate is a woven or nonwoven fabric.

7. A method according to claim 6 wherein the coated substrate is subsequently flash heated.

8. A method according to claim 7 wherein the heating is by means of high intensity electromagnetic radiation.

9. A substrate having deposited thereon an adherent, substantially non-microporous PTFE film which is less than 3 microns thick.

10. A substrate having deposited thereon an adherent substantially void-free coating of PTFE.

11. A substrate according to claim 10, where the PTFE
coating has a bulk density of at least 1.70 g/m3.