Method and Apparatus for Surface Treatinei~ot f Materials
Utilizing M~iltipleC oinbined Energy Sources
CROSS-REFERENCE TO RELATED APPLICATION(S)
This application claims filing date benefit from US 611501,874 filed 61281201 1
TECHNICAL FIELD
The inventiot~r elates to surfacc trcatmcnt of matcrials and various substrates, lnorc patticularly
such as textiles, and n~orcp articularly to treatment of the lnaterials with coillbined multiple
diverse encrgy sources, typically one of which may be an atmospheric plasma (AP).
BACKGROUND
Dcvelopment of "smart textiles" has been an activc area of interest to improvc various propctties
such as stain rcsistancc, waterproofing, colorfasti~essa nd other charactcristics achievable through
advanced treatment using plasma technologies, microwave energy sources and in somc cases,
chcinical treatments.
Atmospheric Plasma Treatment (APT) improves fiber surface properties such as hydrophilicity
without affecting the bulk propcrtics of thcsc fibcrs, and can bc used by textile manufacturers
and converters to inlprovc thc surface propciiics of natural and synthetic fibers to i~nprove
adhesion, wcttability. printability_ dycability, as well as to reduce material shrinkagc.
Atmospheric-pressurc plasma (or AP plasura or normal pressurc plasma) is the nairle given to thc
spccial case of a plasma in which thc pressurc approxitnatcly matches that of the surrounding
atmosphere. AF plasmas have prominent technical significancc hccause in contrast with lowprcssure
plasma or high-pressure plasma no cost-intensive reaction vessel is i~ecdedto ensurc the
maintenance of a pressurc level differing from atmospheric pressurc. Also, in many cases thcsc
AP plasmas can be easily incorporated into the production line. Various forms of plasma
excitation are possible, including AC (alternating current) cxcitation, DC (dircct currcnt) and
low-frequency cxcitation, excitation by means of radio wavcs and microwave cxcitation. Only
AP plasmas with AC cxcitation, howcver, have attained any notcworthy industrial significance.
Generally, AP plasmas are generated by AC excitation (corona discharge) and plasma jcts. In
the plasma jet, a pulsed electric arc is generated by means of high-voltage discharge (5-1 5 kV,
10-100 kHz) in the plasma jet. A proccss gas, such as oil-free compressed air flowing past this
discharge section, is excited and converted to the plasma state. This plasma thcn passes through a
jet head to arrive on the surface of the material to be treated. The jet head is at carth potential and
in this way largcly holds back potential-carrying parts of the plasma stream. In addition, the jet
head detelmines the geo~net~oyf the emcrgcnt bcam. A plurality of jet heads may be used to
interact with a corresponding area of a substrate being treated. For example, sheet materials
having treatment widths of several meters can be treated by a row of jcts.
AP and vacuum plasma mcthods have been utilized to clean and activate surfaces of materials in
preparation for bonding, printing, painting, polymerizing or other functiorial or decorative
coatings. AP processing may be preferred over vacuum plasma for continuous processing of
material. Another su~.facetr eatment method utilizes microwave energy to polymerize precursor
coatings.
SUMMARY
Thc invention is gcncrally directed to providing improved techniques for treatment (such as
surface treatment and modification) of materials, such as substrates, more particularly such as
textiles (including woven or knitted textiles and non-woven fabrics), and broadly involves the
combining of various additional energy sources (such as laser irradiation) with high voltage
generated plasma(s) (such as atmospheric pressure (AP) plasmas) for performing the treatments,
which may alter the core of the material being treated, as well as the surface, and which may use
introduced gases or precursor materials in a dry environment. Combinations of various energy
sources are disclosed.
An ernbodimcnt of thc invention broadly comprises mcthod and apparatus to treat and producc
technical textilcs and other materials utilizing at Icast two combined mutually interacting cnergy
sources such as laser and high voltage gencrated atmospheric (AP) plasma.
The techniques disclosed herein may readily be incorporated into a system for thc automated
processing of textile materials. Functionality tray be achieved through non-aqueous cleaning likc
ctching or ablating, activating by way of radical formation on the surface(s) and simultaneously
and selectivcly increasing or dccrcasing desired functional properties. Properties such as
hydrophobicity, hydrophilicity firc rctardcncy, anti-microbial propcrtics, shrink rcduction, fiber
scouring, watcr rcpclling, low tcmpcrature dyeing, increased dye take up and coloifastness, rnay
be cnablcd or enhanced, increased or decreased, by the process(es) which produces chemical
andfor morphological changcs, such as radical formation on thc surface ofthe material. Coatings
of material, such as nano-scale coatings of advanced materials composition may bc applied and
proccsscd.
Combining (or hybridizing) AP plasma energy with one or more additional (or secondaly)
eileugy sources such as a laser, X-ray, electrou beam, rnicrowave ol. other diverse eriergy sources
may create a rnore effective (and commercially viable) energy milieu for substrate treatment. The
sccondary encrgy source(s) inay be applied in combination (concert, simultaneously) with andor
in scquence (tandem, selectively) with the AP plasma energy to achieve desired properties.
Secondary energy sourccs may act upon the separately generated plasma plume and produce a
Inore effective, energctic plasma milieul while also having the ability to act directly on tlre
surface and in some cases, the core of the material subjected to this hybrid treatment.
The tcchniqucs disclosed herein may bc applicable, but not limited to the treatmcnt of textilcs
(both organic and inorganic), paper, synthetic paper, plastic and other similar materials which arc
typically in flat shcct form ("yard goods"). The techniques discloscd herein may also be applied
to the processing of plastic or metal extrusion, rolling mills, injection molding, spinning, carding,
weaving, glass making, substrate etching and cleaning and coating of any material as well as
applicability to practically any material proccsr;ing techniquc. Rigid materials such as flat shccts
of glass (such as for touch screcns) may be treatcd by the techniqucs disclosed herein.
According to one aspect of the present invention, there is provided a mcthod for trcatment of a
substrate (102,402,404) comprising:
crcating a plasma in a treatment region (124) comprising two spaced-apart clcctrodcs (01102;
2121214; 4121414; 4521454);
directing at lcast one second energy source which is different than the first energy source
into the plasma to interact with the pkasma, resulti~lgin a hybrid plasma; and
causing thc hybrid plasma to interact with tllc substrate in a treatment region (124).
In another aspcct, the present invention encompasses an apparatus (100, 400.4, 400B, 400C,
400D, 400E, 400F, 400G) for treating materials comprising:
two spaced-apart electrodes (eIle2; 2121214; 4121414) for generating a plasma in a
treatmcnt region ( I 24);
one or more lasers (130) directing corresponding one or more beams (132) into the treatment
area to interact with at least onc of the plasma and the material being treated.
In a further aspect, the present invention comprehends a use of the apparatus described herein for
treating a textile substrate
I11 a different aspect, the present invention envisages a tcxtile ~naterial obtained by thc method
described herein.
111 yet a further aspect, the present invention co~~templatcas rt~etliodo f creating a plasma for
material trcatment comprising
Some advantages ofthe present invention may include, without limitation, a method of crcating a
morc energetic and effective plasma to clean and activate surfaces for subsequent processing or
finishing. For examplc, ultra-violet (UV) laser radiation, either continuous wave (CW) 01
pulscd, may be combined with elcctrornagnetically gencratcd AP plasma to crcatc a morc highly
ionized and cncrgetic rcaction milieu for treating surfaccs. Thc rcsulting hybridized energy may
have effects that are greater than the sum of its individual parts. Pulscd laser energy may be used
to drive thc plasma, crcating waves, and the lascr energy accelerates the rcsultant plasma waves
which act upon the substrate like waves crashing on the beach.
The accelerated and more energetic plasma may initiate radicals in the fiber or surfacc of thc
treated substrate and attach ionized groups to the initiated radicals. Atkachment of such
functional groups as carboxyl, hydroxyl or others attach lo the surface increasing polar
characteristics may result in grcatcr hydrophilieity and other desirable functional properties.
The invention advantageously cornbincs cncrgy sources in a controlled atmospheric cnvironnlent
in the prcscnce of a material substrate. Thc net result may be conversion and material synthesis
in thc surfacc of the substrate - the substrate rnay be physically changed, in contrast with simply
being coated.
In an exemplary embodiment, a high frequency RF plasma is created in an envelope (or cavity,
or clianlber) fon~led between rotating and drivcn rollcrs which extend across the width of thc
processing window. The plasma field generated is consistent across the width of a treatment
arca, and may operate at atmospheric pressure. A high power Ultra Violet UV) laser is provided
for interacting with the plasma andor thc matcrial being treated. The beam from the laser may
be shaped lo have a rectangular cross-section exhibiting a consistent power density over the
entire treatment area. A gas delivery system may be used to combine any combinatiori of a
plurality (such as 4) of environmental gases and precursors into a single feed which populates thc
hybrid plasma chamber. Additionally, a spray or misting delive~y system may be provided,
capable of applying a thin, consislenl layer of sol-gel or process accelera~itsto the material being
treated, either pre- or post- processing.
The process of combining plasma and photonics (such as W lascr) is dry, is carried out at
atmospheric pressures and uses safe and inert gases (such as Nitrogen, Oxygen, Argon & Carbon
Dioxide). Changing the power intensity of the laser and the plasma, and then va~ying the
cnvironmcntal gases or thc addition of sol-gels andlor othcr organic or inorganic prccursors -
i.c., changing the "recipe" -allows the system to generate a wide variety of proccss applications.
Thcrc arc at scvcral applications for thc proccss, including: clcaning, preparation and
performance enhancement of materials.
- For cleaning, thc lascr may intcnsify the cffcctivc power of the plasma as well as acting
on thc substratc material in its own right.
- For preparing the substrate material for secondary proccssing, such as dyeing, thc surface
of the fibc~sm ay be ablated in a controlled manner, thereby incrcasing thc hydrophilicity
of thc material (such as a textile material). Additionally, be introducing environmental
gases into the proccss zonc ofthc systcm, chemistries niay bc creatcd at the surface of thc
material (e.g., fabric) which may result in chemistries that rcact with a dyeing media to
effect a more efficient dye penetration or a more intense coloring proccss or reduction of
dye temperature. For example, prcparing the fibers of the textile to give a bcttcr
controllcd uptakc of chrome oxidc dycs to improve the illtensity of black achicvcd. There
is, therefore, potential for this proccss to rcducc the chemical content of dycs which could
rcducc both ncgativc cnvironmcntal impact and proccssing costs.
- For Pcrformancc Enhancement, the proccss may achieve matcrial synthcsis in the surface
of the substratc. By altering thc lascr and plasma frequcncics and thc power intensities,
and introducing othcr materials into thc proccss environment, the system ablatcs thc
surface of the substratc and a series of chemical reactions bclwccn thc substratc and the
environmental gases synthesize new materials in thc surface of the fibers in the textilc
web.
BRIEF DESCRIPTION OF THE DRAWINGS
Rcfercncc may be niadc in detail to embodiments of thc disclosure, some non-limiting cxamples
of which may he illustrated in thc accompanying drawing figurcs (FIGS). Thc figures are
generally diagrams. Some elemcrits in the figures may be cxaggcratcd, others may bc omitted,
for illustrative clarity. The relationship(s) between different elements in the iigures may be
referred to by how thcy appear and are placed in the drawings, such as "top", "bottom", "lefi",
"right", "above", "below", and the like. It should be understood that the phraseology and
terminology employed herein is not to be construed as limiting, and is for descriptive purposes
only.
FIG. 1 is a diagram of a treatment system, according to an embodiment oftlie invention.
FIG. 2 is a partial perspective view of a plasma region of the treatment system of FIG. 1.
FIG. 2A is a partial pcrspcctive view of a plasma region ofthe trcatmcnt system of FIG. 1
FIG. 3 is a partial perspective view of a pre-treatment region, plasma region and post-treatment
region ofthe trcatmcnt system of FIG. 1, according to some embodiments of the invention.
FIGS. 4A - 4G are diagrams of elements in a treatment region of the trcatmcnt system of FIG. 1,
according to some embodiments of the invcntion.
DETAILED DESCRIPTION
The invention relates generally to treatmcnt (such as surface treatment) of materials (such as
textiles) to modify their properties.
Various embodiments will be described to illustrate teachings of the invention(s), and should bc
construed as illustralivc rather than lirnitirig. Although the invention is generally dcscribed in the
context of various exemplary embodiments, it should be understood that it is not intended to
limit the invcntion to these particular embodiments. An cmbodiment may be an example or
implcmcntation of onc or more aspects of the invention(s). Although various features of the
invention(s) may be described in the context of a single embodiment, the features may also be
provided separately or in any suitable combination with one another. Conversely, although the
invcntion(s) may be dcscribcd in thc context of sepasate embodimcnts, the invcntion(s) may also
bc implemcntcd in a single cmbodimcnl.
In the main hcrcinaftcr, surface trealmcnt of suhslratcs which may be textilcs supplied in roll
form (long shccts of matcrial rolled on a cylindrical core) will he discussed. One or morc
treatments, including but not limited to material synthesis, may be applied to one or both
surfaces of the tcxtilc substratc, and additional materials may be introduced. As used herein, a
"substratc" may be a thin "sheet" of matcrial having two sn~faccsw, hich may hc tcrmed "fiont"
and "hack" surfaces, or "top" and "bottom" surfaces.
Some Embodiments of the isvention
Thc following embodimcnts and aspects thcrcof may be describcd and illuslralcd in conjunction
with systcms, tools and methods which arc meant to be cxcmplary and illustrative, not limiting in
scope. Specific configurations and delails may he set forth in ordcr to provide an understanding
of the invcntion(s). However, it should bc appascnl lo one skilled in the arl that thc invcntion(s)
may be practiced without some of the specifi c details being presented herein. Furthermore, wcllknuwrl
feaiurcs rrlay be urr~iiicd or simplified in order not to obscure the descriptions of the
invention(s).
FIG. 1 shows an overall surfacc trcatmcnt system 100 and method of performing trcalmenl, such
as a surfacc trealmcnt ofa substratc 102. In the figures prescnled hcrcin, the substrate 102 will
be shown advancing from right-to-left through the system 100.
Thc substratc 102 may for example be a tcxtile material and may bc supplied as "yard goods" as
a long sheet on a roll. For cxamplc, the substratc lo be treated may bc Gb~uub LexLilc material
such as cottonlpolycster, approximately 1 meter wide, approximately lmm thick, and
approximately I00 meters long.
A section 102A, such as a lm x lm section of the substratc 102 which is not yet treated is
illustrated paying out from a supply reel R1 at an input section IOOA of the system 100. From
the input section 100A, the substratc 102 passes through a trcatmcnt section 120 of thc apparatus
100. After being trcated, the substrate 102 cxirs the Ireatmcnt apparatus 120, and may bc
collected in any suitable manner, such as wound up on a take-up rccl R2. A section 102B, such
as a 1 m x I m scction of the substrate 102 which has bccn treated is illustrated being wound onto
an Lakeup recl R1 at an output section lO0A of thc systcm 100. Various rollers "R may be
provided between (as shown) and within (not shown) thc various sections of thc system 100 to
guide the material through the system.
The trcatmcnt scction 120 may generally comprise thrce regions (or arcas, or zones):
- optionally, a pre-treatment (or precursor) region 122,
- a trcatmcnt (or plasma) region 124, and
- optionally, a post-trcatmeut (or finishing) rcgion 126.
The treatment rcgion 124 may corny~ise componcnts for gcncrating a high voltagc (HV)
alternating current (AC) atmosphcric plasma (AP), thc elements of which arc gcncrally well
known, some of which will bc described in some detail he~einbelow.
A laser 130 may bc providcd, as the secondary cncr-yy source, for providing a beatii 132 which
interacts with the AP in the main treatment rcgion 124, and which may also impinge on a surface
of the substrate 102.
A controller 140 may be provided for controlling the operation of the various components and
clcmcnts dcscribcd hcleinabove, and may be provided with the usual human interfaces (input,
display, ctc.).
FIG. 2 shows a portion of and some operative elements within thc main treatment region 124.
Three orthogonal axes x, JJ and z are illustrated. (In FIG. 1, the corresponding x and y axes are
illustrated.)
Two elongate electrodes 212 (el) and 214 (e2) arc shown, one of which may be considered to be
a cathode, the other of which may bc considered to be an anode. These two electrodes e l and e2
may be disposcd generally parallel with one another, extending parallcl to they axis, and spaced
apart from onc another in thc x direction. For cxample, thc clcctrodcs el and e2 may be formcd
in any suitable manner, such as in thc hrm of a rod, or a tube or othcr rotatable cylindrical
electrode material, and spaced apart %om one another nominally, a distance sufficient to allow
for clcarancc of the thickness of the ~naterial processed. Thc electrodcs el and c2 may be
disposed approximately 1 mm above the top surface 102a of the substrate 102 being treated.
Thc clcctrodcs el and e2 may be energized in any suitablc manner to create an atmospheric
plasma (AP) along the length of the resulting cathodeidnode pair in a space bctwecn and
immediately surrounding the elcctrodcs el and e2, which nay bc referred to as a "plasma
reaction zonc".
As mentioned above, a laser bcam 132 may be directed into the main treatment region 124, and
may also impinge on a surface of tbe substrate 102. Here, the laser bcam 132 is shown being
directed approximately along the y axis, approximately parallel to and between the electrodes el
and c2, and slightly above the top surface 102a of the substratc 102, so as to interact with thc
plasma (plume) generated by the two electrodes el and e2. In an exempla~ya pplication, the
bcarn footprint iuay be a rectangle approximately 30mm x 15mm. The beam may be oricntcd
vcrtically or horizontally to best achicve the desired interaction of plasma and/or direct substratc
irradiation
The laser beam 132 may be directed minutely but sufficiently "off angle" to directly irradiate the
substrate 102 to be treated as it coincidently reacts with the plasma bcing generated by thc two
electrodcs el and e2. More pa~ficularly, thc laser beam 132 may make an angle of "a" which is
approximately 0 degrees with the top surface 102a of the substrate 102 so as not to impinge on
its surface 102a. Alternatively, the lascr bear11 132 may niake an angle of "a" which is
approximately less than 1 - 10 dcgrces with the top surface 102a of the substrate 102 so as to
impinge on its surface 102a. Other orientations of the beam 132 are possible, such as
perpendicular ("(I" = 90 degrees) with the surface 102a of the substrate 102. The laser beam
132 may be scanned, using conventional galvanometers and the like, to interact with any selected
portion of the plasma generated by the two electrodes el and c2 or the substrate 102, or both.
The plasma nlay be crcatcd using a first encrgy source such as high voltage (HV) altcrnating
current (AC). A sccond, different cncrgy source (such as laser) may be causcd to interact with
the plasma, resulting in a "hybrid plasma", and the hybrid plastr~am ay be causcd to interact (in a
trcatmcnt region) with the substrate (matcrial) being treated. In addition to intcracting with the
first encrgy sourcc, the second energy source can bc causcd to also interact dircctly with the
matcrial being treated. The direct interaction with the substrate or other gas (secondary or
recursor or) may produce its' own laser sustaincd plasma which in turn may further interact with
the high voltage generated plasma to more highly energize the reaction milicu.
The substrate 102 (material being trcatcd) may be guided by rollers as it passcs through thc main
trcatnlent region (area) 124. FIG. 2A illustrates that orle of these rollers 214 may scrvc as the
anode, and the othcr roller 212 may scrvc as thc cathode (or vice-vcrsa) of a cathode/anodc pair
for generating thc plasma. It may be noted that in FIG. 2, the substratc 102 is disposed to one
side of (below, as viewed) both of the two electrodes el and e2, and in FIG. 2A the substrate 102
is disposcd bctween thc two elcctrodcs el and e2. In both cases, the plasma crcatcd by the
electrodes el and e2 acts on at least one surface of the substratc 102. The anodes and cathodes
may bc coatcd with an insulating material, such as ceramic.
It should bc understood that the invention is not limited to any particular arrangement or
configuration of electrodes el and e2, and that the examples set fotlh in FIGS. 2,2A arc intended
to be merely illustrative of some of the possibilities. Furthermore, for example, as an alternative
to using two electrodes el and e2, a row of plasma jets (not shown) dclivcring a plasma may bc
provided to create the desir-ed plasma abovc the surface 102a of the substratc 102.
FIG. 3 sl~owsth at iin the pic-treatment region (area) 122, a row of spray licads (nozzles) 322
covering the full width of the material to be treated, or other suitable means, may be used to
dispensc precursor materials 323 in solid, liquid or gaseous pl~ase onto the substratc 102 to
enable the proccssing of7for specific properties such as antimicrobial, firc retardant or superhydrophobic/
hydropliilic characteristics.
Thcrc may bc an intcrmcdiate "buffer" zone bctwcen the pre-treatment rcgion (arca) 122 and the
main treatment region (arca) 124, to allow time for the materials applied in pre-treatment to soak
into (be absorbed by) tlic substrate. The proccss still runs a single length of material, but the
buffer may hold, for example, up to 200n1 of fabric. For example, when material being treatcd
(such as yard goods) is feeding through the systcm at 20 meterslmin, this would allow for several
minutes "drying time" between prc-treatment (122) and hybrid plasma treatment (124), without
stopping the flow of rnaterial through thc systcm.
Similarly, in the post-treatment region 'rea) 126, a row of spray heads (nozzles) 326 covcring
the full width of the matcrial which was trcated (124), or other suitable means, may be used to
dispense finishing materials 327 in solid, liquid or gaseous phasc onto the substrate 102 to imbue
it with desired charactcristics.
Some embodiments of the trcatment recrion (1241
FIGS. 4A - 4G illustralc various embodiments ofelemerlts in the trcatmcnt region 124.
FIG. 4A illustrates arl embodiment 400A wherciil:
- A fiist ("top") roller 412 is opcrative to function as an electrode e l , and may havc a
diameter of approximately 10cm, and a length (into the page) of 2 meters. The roller 412
may havc a metallic corc and a ceramic (electrically insulating) outer surface.
- A second ("bottom") roller 414 is operative to function as an electrode c2, and may havc
a diameter of approximately 15cm, and a length (into the page) of 2 meters. The roller
414 may havc a mctallic core and a ceramic (clcctrically insulating) outer surface.
- The second roller 414 is disposed parallel to and directly underneath (as viewed) the first
roller 412, with a gap therebetween correspondilig to (sucli as slightly less thau) the
thickness of the substrate material 402 (compare 102) being fed between the rollers 412
and 414. The direction of material travel may be right-to-left, as indicated by the arrow.
The substrate 402 has a top surface 402a (comparc 102a) and a bottom surface 402b
(compare 102b).
The first roller 412 may serve as thc "anodc" of an anodeicathode pair, having high
volvage (HV) supplied thereto. The second roller 414 may serve as the "cathode" of the
anodeicathode pair, and 11~abyc grounded.
A fils1 ("right") nip or fccd roller 416 (111) is disposed adjacent a bottom-right (as
viewed) quadrant of the first roller 412, and against a top-right (as vicwcd) quadrant of
the sccond rollcr 414. The roller 41 6 may havc a diameter of approximately 12cm, and a
lcngth (into the page) of 2 meters. The outer surfaec of the rollcr 416 may engage the
outer surface of the roller 412. A gap bclwcen thc outer surface of the roller 41 6 and the
outer surface of the roller 414 corresponds to (such as slightly less than) the thickness of
the substrate material 402 (compare 102) bcing fcd between the rollers 416 and 414.
A second ("left") nip or feed roller 418 (112) is disposcd adjaccnt a bottom-lcfi (as
viewed) quadrant of the first rollcr 412, and against a top-lefl (as viewed) quadrant of the
second roller 414. The roller 418 may have a diameter of approxin~ately 12cm, and a
length (into the page) of2 meters. The outer surface of the roller 418 may engage the
outer suriBce of the roller 41 2. A gap bclwccn the outer surfacc of the rollcr 4 18 and thc
outer surface ofthe roller 414 corrcsponds to (such as slightly less than) the thickness of
thc substratc matcrial402 (eomparc 102) bcing fcd between the rollers 418 and 414.
Generally, the nip or feed rollcrs 416,418 should have an insulating outer surface so as to
avoid shorting the anode and cathode 412,414.
With such an arrangement of rollcrs 412,414, 416, 418, a semi-airtight cavity ("440") may be
formed between the outer surfaces of the four rollers 412, 414, 416, 418 for defining the
treatment region 124 aud containing the plitsnla. The overall cavity 440 may comprise a first
("right") portion 440a in the spacc between the top, right and bottom rollers 412,416,414 and a
second ("lei?") portion 440b in the space bctwce~tlh e top, lefi and bottom rollers 412, 41 8,414.
The filled circle at the end of the lead linc for the right portion 440a of the cavity 440 represents
gas flow into the cavity. The filled reetarigle at the cnd of the lead line for the left portion 440b
of the cavity 440 represents the laser beam (132).
Thc plasma generated in the cavity 440 may be an atmospheric pressure (AP) plasma.
Therefore, scaling of the cavity 440 is not nccessaly. However, end caps or plates (not shown)
may bc disposcd at thc ends of thc rollers 412, 414, 416, 418 lo contain (scmi-cnclose) arid
control the gas flow in and out of thc cavity 440.
FIG. 4B illustratcs at1 cmbodimcnt 400B wherein the left and right rollers 416 and 418 are
moved slightly outward fiom the rollers 412 and 414, thcreby opening up the cavity 440 to allow
for thickcr and lor stiffer substrates to be processed . This would however require independcnt or
direct drive of each clcctrodc, anode and cathodc. Thc material would be driven through thc
reaction zone by outsidc fccding and take up rollers.
FIG. 4C illustratcs an cmbodimcnt 400C wherein a gencrally inverted U-shaped shield 420 is
uscd instcad of thc lcft and right rollcrs (416 and 418) to dcfine the cavity 440 having right and
lcft portions 440a and 440b. The shicld 420 is disposed substantially complctcly around one
roller 412 (except for whcrc the material feeds through), and at least partially around the other
roller 414. An additional shield (not shown) could be disposed under thc bottom rollcr 414.
FIG. 4D illustrates an embodiment 400D adapted to treat rigid substratcs. Thc substrate 402
dcscribed abovc was flcxiblc, such as textile. Rigid substratcs such as glass for touchscreen
displays may also be trcated with a hybrid plasma and precursor materials. A rigid substrate 404
having a top surface 404a and bottom surface 404b passes through the top rollcr (el) 412 and the
bottom roller (e2) 414. A row of nozzles 422 (compare 322) may be arranged to provide
precursor material, such as in liquid, solid or atomized form. A shield (not shown) such as 420
(rcfcr to FIG. 4C) may bc incorporated to contain the hybrid plasma.
FIG. 4E shows an arrangement 400E incorporating a row of HV plasma nozzles Qcts) 430,
rather than the cylindrical clcctrodes el and e2. For example, ten jets 430 spaced at 20cn1
intervals in the treatment region 124. A rigid substrate 404 is shown. A row of nozzles 422
(compare 322) may bc arranged to provide precursor material, such as in atomized form, onto the
substrate 404, in a pre-treatmcnt rcgion 122, before it is exposed to the hybrid plasma. For
examplc, tcn nozzles 422 spaced at 20cm intervals in the pre-treatment region 122. A shield
(not shown) such as 420 (refer to FIG. 4C) may be incorporated to contain the hybrid plasma.
This arrangement enables treatment of metallic or othcr condnctivc substrates.
FIG. 4F illustrates an cnlbodimcnt 4001: a first ("top") roller 412 operative to function as an
clcctrode el (or anode), a sccond ("bottom") roller 414 operative lo function as an clcctrode e2
(or cathodc), and two nip rollcrs 436 and 438 (compare 416 and 418).
In contrast with the embodirnei~t 400A (FIG. 4A), in this ernbodimc~it he rollcrs 436 and 438)
arc spaced outward slightly (such as 1 cm) from the top and bottom rollers 412 and 414.
Therefore, although they will still help contain the plasma, they may not function as feed rollcrs,
and scparate feed rollers (not shown) may need to be providcd .
Thc right roller 436 (compare 416) is shown having a layer or coating 437 on its surface. The
left roller 438 (compare 41 8) is shown having a layer or coating 439 on its surface. For example,
the rollcrs 436 and 438 in the hybrid plasma treatment region 124 may he wrapped with mctallic
foil (or otherwise have a mctallic outer laycr) which may be etched away, in process, by the
highly energetic hybrid plasma and/or by the laser (second energy source) creating a plume
coiikaining reactive illetallic plasma which may readily couple with the substratc surface radicals
to create nano-layer coatings with metallic composition on the substrate material. The metallic
material (foil, layer) may be controllably ctchcd or ablated by the plasma, and the effluent
metallic constituents may react with thc plasma and be deposited on thc substratc, such as in
nano-scale layers.
Thc metallic material coating the rollers 436 and 438 mliy comprise any otie or cornbination of
titanium, copper, aluminum, gold or silver, for example. One of the rollers may be coated with
one material, the other of the rollers may be coated with another rnaterial. DiEcrciil portions of
the rollers 436 and 438 may be coated with different matcrials. Generally, when these matcrials
are ablated, they form vapor precursor material, in the treatment region 124 (and may therefore
be contrasted with the nozzles 322 and 422 providing precursor material in the pre-treatment
region 124.)
FIG. 4C illustrates a11 embodiment 400G using two flat shcet, platc electrodes 452 and 454,
rathcr than rollers (412, 414), spaced apart from onc another to form a treatment region
(reaction/synthesis zone) 124 through which a sheet of material 404 may be fed. Gas feed to the
treatment rcgion is indicated by the circle 440a, thc laser beam is indicated by the rectangle
440b. Nozzles 422 may be provided to delivcr precursor material(s) in thc prc-trcalmcnt zonc
122. Nozzles 426 may be providcd to deliver finishing material(s) in thc post-trcatmcnt zonc
126.
Additional Fcatures
Although not specifically shown, finishing materials dispensed onto the substrate 102 afier
hybrid energy treatment (124) may be subjected to an immediate secondary plasma or hybrid
plasma exposure to dry, seal or react finishing materials which have been dispcnscd following
activation of the surface by the hybrid plasma.
Although not specifically shown, it should be undcrstood that various gases, such as 02, N2, H,
C02, Argon, Hc, or compounds such as silane or siloxane hascd materials may be introduced
into the plasma, such as in the trcatment region 124, to impart various dcsired charactcristics and
properties to the treated substrate.
To impart anti-microbial properties to the malcrial being treated, precursor materials may be
introduced such as non-silver based silaneslsiloxanes and the aluminum chloride family such as
3 (trihydroxylsilyl) propylditnethyl octadecyl, amrnonium chloride. Other Silane/Siloxanc
groups may be used to affect hydrophobicity as well as siloxones and ethoxy silancs (lo incrcase
hydrophilicity). Hcxamcthylidisiloxane applied in the gaseous phase in tlle plas~nalu ay smooth
the surface of tcxtilc fibers and increase the corltact anglc which is an indication of the level of
hydrophobicity.
Negative draft or atmospheric partial vacuum may be employed to draw plasma constituents into
and hrthcr penetrate the thickness of porous substrates. FIG. 3 shows that suction means, such
as platen (bed) 324 over which the substrate 102 passes, in the tlreatment area 124, may be
provided with a plurality of holcs and connected in a suitablc manner to suction mcans (not
shown) to create the desired effect. The platen 324 may function as onc of the electrodes for
generating the plasma. Alternativcly, a roller or the like could rcadily be modificd (wit11 holes
and connectcd with suction means) to pcrfoim this function.
It should be undcrstood that the process is dry and has a low environmcntal impact, and that
lcftovcr or byproduct gascs or constituents are inherently safe and may be cxhaustcd from thc
system and recycled or disposed o f in an appropriatc manncr.
There is thus provided a method of treating materials with at lcast two encrgy sources, wherein
the two encrgy sources comprise (i) an AP plasma produced by various gases passing through a
high energy electromagnetic field and (ii) at lcast one laser interacting with said plasma to create
a "hybrid plasma". The laser may opcrate in the ultra-violet wave length rangc, at 308nm or
less. The laser may comprise an excimer laser operating with at least 25 watts of output power,
including more than 100 watts, more than 150 watts, morc than 200 watts. Thc lascr may bc
pulsed, such as at a frequency o f 25Hz or higher, such as 350-400 Hz, including picosecond and
femtosecond lasers. Although only onc laser has bccn described interacting with the plasma (and
the substrate), it is within the scope of the invcution that two or more lasers may he used.
Somc exemplary paramcters for generating the plasma in the treatmcnt region are I - 2 Kw
(kilowatts) for the HV generated plasma and 500mjoules, 350Hz for the 308nm W laser, in an
80% argon, 20% Oxygen or C02 gas mix.
As an alternative to or in addition to using a laser, an ultraviolet (UV) source such as a UV lamp
or an ai-ray o f high powered UV LEDs (light-emitting diodes) disposed along thc length of the
treatment area may he used to direct energy into the AP plasma to create the hybrid plasma, as
well as to interact with (such as to etch, react and synthesize upon) the matcrial being treated..
In the main, hereinabove, treating one surface 102a of a substrate material 102 was illustrated,
and some exemplary treatments were described. It is within the scope of the invention that thc
opposite bottom surface 102b of the matcrial 102 may also be treated, such as by looping the
material 102 back through the treatment region 124. Different energy sources and milieus,
precursor and finishing materials may be used to treat the second surface of the matcrial. In this
manner, both surfaces of the material nray be treated. It should also be understood that the
treatments may extend to within the surface of the material being trcatcd to alter or cnhancc
properties of the inner (core) material. In some cases, both top and bottom surfaces as well as
the core of the material may be effectively trcatcd from one side.
The system can be used to treat materials which are in other than shcct form. For example, the
system may be used for improving optical and morphological properties of organic light-emitting
diodes (OLEDs) by hybrid energy annealing. These discrete items may be transported
(conveyed) through the system in any suitablc manner.
Other types of energy may be applied in combination or in sequence with each other to create
enhanced processing capabilities. For example, a method of treating materials may utilize the
combination of at least two energy sources such as ~nicrowavc and laser, or microwavc and
electromagnetically generated plasma, or plasma and microwave, or various combinations of
plasnla, laser and pulsable microwave electron cyclotron rcsonancc (ECR).
The two cncrgy sourccs may comprise (i) an atmospheric plasma, utilizing various ionized gases
passcd through high energy electromagnetic fields, arid (ii) an ultra violet (UV) source
generating and directing radiation into the highly ionized plasma and directly at the surface to be
treated. The UV source may comprise an array of high powercd UV LEDs (light-emitting
diodes) disposed along the extent of the treatrnerit arm. The high powered ultra-violet LEDs
may interact with the plasma to more highly energize the plasma, as well as acting directly on the
substrate to etch or react said substrate.
An automated material handling system may controllably feed material through the energy fields
produced by combination energy sourccs.
A series of process steps may be performed, such as:
step 1 - (optional) precursor application,
step 2 - cxposurc to hybrid energy,
step 3 - (optional) precursor or finishing material application and,
step 4 - cxposurc to hybrid encrgy.
in which all steps are acconlplishcd in scrial fashion irnmcdialcly within the systcm
It is within the scope of thc invention to introduce into the process a delivery system capable of
adding gaslvapor phase precursor materials dircctly in to the plasma rcaction zone.
Some Exemplary Treatmel~Pt rocess Parameters
Trcatment 1 - Hydrophilicity
Precursor material
polydimcthylsiloxanc hydroxycut (PMDSO Hydroxycut)
alt: copolymcr (Dimcthylcsiloxanc and/or witli blcnd of dirnethylcsilanc)
Laser
Frequency 250Hz
Powcr 380 mJ
Plasma
Carrier Gas Argon . . . SO%
Reactivc Gas 02 . . . 20%
Flow rate 15 literlmin Prcssurc: slightly above 1 bar
Powcr 2 KW
Trcatment 2 - Dycability
Precursor
Either no precursor or otlier precusor catalysts
Laser
Frequency 250Hz
Power 380 mJ
Plasma
Carrier Gas Argon . . . 80%
Reactive Gas 02 or N2 . . . 20%
Flow ratc 15 literlmin Pressure: slightly above I bar
Powcr 2 KW
T11eat1n.ent3 - Hydrophobicity
Precursor octarnethylcyclotetrasiloxane/polyditncthylsilarieb lend (watcr soluablc,
hydrogen methyl polysiloxaric ~nixcdw ithpolydimethylsiloxanc with polyglycolethcr (water
soluable) or combination of the above with polydimethylsiloxane. Using water soluble blends
allows for diluting the ~naterialsw ith dc-ionised water to the required concentrations based on
the application, cost effectiveness and output pcrfor~nancere sults. Water soluble blcnds may be
produced with relevant additives - these are esscntially methods for mixing oil with water to - produce etnulsions, generally described by thc sizc of the etnulsion dispersant, i.c. macro or
micro (macro is >I00 microns, tnicro<30 microns).
alt: copoly~ne(rD imethylesiloxane and/or with blend of dimethylesilanc)
Laser
Frequency at least 350Hz
Powcr at least 450 tnJ
Plasma
Carrier Gas Nitrogen, Argon, Helium . . . 80%
Reactive Gas C02 or N2 . . . 2-20%
Flow rate 10-40 literlrnin Pressure: slightly above 1 bar
Power 0.5 - I KW
Trealmcnt 4 - Fire rctardancy
Plcculsol
Copolymcrs and Terpolyrners based on siloxanelsilane and polyborosiloxarle with key
inorganic compounds, essentially transition oxides of titanium, silicon and zirconiu~n and
boron. Also included, Boron containing siloxane Copolytners and Te~polymers, such as
organosiliconloxycthyl tnodificd polyborosiloxane. Some limited matcrial composition
based reccnt new phosphorous blends may be used, based on the substrate material typcs
and output requirements. octa~nethylcyclotetrasiloxane/polydimetliylsia~b~lce nd (watcr
soluable) mixcd with polydimcthylsiloxane with ~~olyglycolcthe(rw ater soluhlc) or
comination of the above with polydirnethylsiloxarlewith additives oC
- calciuni metaborbate additive to silanclsiloxane .
- Silicon oxidc additivc to silanc /siloxanc .
- Titanium isopropoxide additive .
- Titanium dioxide (routile).
- Animonium phosphate,
- Aluminum oxide.
- Zinc borate,
- Boron phosphate containing prcceramic oligomores.
- Acrogels and hydrogels, low or high dcnsity cross linkedpolyacrylatcs:
- nanolmicro encapsulated con~positions.
Example: dimcthylsiloxane andlor with dirnethylsilane with polyborosiloxane, with
added transition oxides, range 5 to 10% volume of oxides such as Tio2, sio2 (fbmcd, gel
or amorphous), A1203, ctc. Thc precursor materials sct forth hcrcin may cnhancc firc
retardency of materials in the system described herein utilizing a hybrid plasma (e.g.,
with lascr). It is within thc scopc of the invention that the precursor materials set forth
herein may enhance firc rctardcncy (or othcr properties) of materials in a material
treatment systcm utilizing a non-hybrid plasma (e.g., without the laser).
Laser
Frequency at lcast 350Hz
Power at least 450 inJ
Plasma
Carrier Gas Nitrogen, Argon, Helium . . . 80%
Rcactive Gas C02 or N2 . . . 2-20%
Flow rate 10-20 literlmin Pressure: slightly above 1 bar
Power 0.5 - 1 KW
Treatmeut 5 - Anti Microbial
Precursor
siloxane/silane blends as pcr hydrophobicity platform, with thc addition of
octadecyldimethyl (3triethoxysilpropyl) ammonium chloridc.
octa~nctl~ylcyclotetrasiloxanc/polydimethylsilabnlee nd (water solub1c)mixed
withpolydimcthylsiloxanc with polyglycolcther (watcr soluble) or comination of abovc with
polydimethylsiloxancwith additives of:
- octadecyldimethyl(3-trimethoxysilylpropyl)ammmonium chloride),
- Chitosan
Lascr
Frequency at least 350Hz
Power at least 450 mJ
Plasma
Carrier Gas Nitrogen, Argon, Helium . . . 80%
Reactive Gas C02 or N2 ... 2-20%
Flow rate 10-20 literlmin Pressure: slightly above 1 bar
Power 0.5 - 1 KW
Whilc the invention(s) has been described with respcct to a limitcd number of cmbodimcnts,
thesc should not bc construed as limitations on thc scopc of the invention(s), but rathcr as
examples of some of the embodimcnts. Those skilled in thc art may envision other possible
variations, modifications, and implementations that are should also be considered to bc within
the scope ofthe invention(s), bascd on the disclosure(s) set forth herein, and as may he claimed.

CLAIMS
What is clai~ncdis :
I. A tnetl~od for treatmnerlt of a substrate (102,402, 404) comprising:
creating a plasma in a treatment region (124) comprising two spaccd-apamt electrodes (clle2;
2121214; 4121414; 4521454);
directing at least onc sccond energy source which is differcnt than the first cncrgy source
into the plasma to interact with the plasma, resulting in a hybrid plasma; and
causing thc hybrid plasma to interact with the substrate in a trcatlnent rcgion (124).
2. The ~netl~oodf claim 1, wherein:
thc first energy sourcc coinprises high voltage alternating current (AC); and
the second cncrgy sourcc comprises radiation from a lascr.
3. The method of claim 2, wherein the lascr interacts with the plasma, and also acts directly
upon the material being treatcd.
4. The method of claim 2 or 3, whercin the laser has at least one of the following
characteristics:
the laser comprises an exei~nerla scr;
the laser operates in tlic ultra-violct (UV) wave lengtll range;
thc laser operates with at least 25 watts of output power.
5. The method of any preceding claim 2, wherein:
the plas~nac o~npriscsa n at~nospheripc ressure (AP) plasma.
6. The method of any preceding claim, krther comprising:
prior to treating the substrate, dispensing (122,322,422) precursor materials (323,437) onto
the substrate.
7. The method of any preceding claim, further comprising:
after treating the substrate, dispensing (126, 326, 426) finishing materials (327, 439) onto
thc substratc.
8. Thc mcthod of any preceding claim, wherein:
thc plasma comprises a high voltage (HV) atmospheric pressure (AP) plasma.
9. The method of any preceding claim, wherein:
the electrodes (elIe2) comprise rollers (2121214; 412i414)
10. The method of any preceding claim, whercin the substrate is a nlaterial
11. Thc method of any preceding claim, wherein the substrate is a synthctic textile material.
12. The method of claim 11, wherein the synthetic textile material is polyester.
13. Thc method of any of claims 1 to 10, wherein the substrate is an organic material.
14. The method of a claim 13, wherein the organic material is at least one selected from cotton
and wool.
15. Apparatus (100, 400.4, 400B, 400C, 400D, 400E, 400F, 400G) for trcating materials
comprising:
two spaced-apart electrodcs (elie2; 2121214; 4121414) for generating a plasma in a
treatment rcgion (124);
one or more lasers (130) directing corresponding one or more beams (132) into the treatment
area to interact with at least one of the plasma and the material being ircated.
16. The apparatus of claim 15, wherein the two spaced-apart electrodes (eIle2) comprise first
and second rollers (4121414), and hrthcr comprising:
(FIGS. 4A, 4R, 4F) third and fourth rollers (4161418) disposed adjacent the first and sceond
rollers and forming a semi-airlight cavity (440) between thc outer surfaces of the first, second,
third and fourth rollers (412, 414, 416, 418) for dcfining the treatment region (124) and for
containing the plasma.
17. Thc apparatus of claim 16, wherein:
(FIG. 4F) at least one of the third and fourth rollers (436, 438) comprise a rnetallic outcr
layer (437,439).
18. Thc apparatus of any of claims 15 to 17, wherein the two spaced-apart clectrodes (e11e2)
comprise first and sceond rollers (4121414), and further comprising:
(FIG. 4C) a shield (420) disposed around the first and sceond rollers (412,414) lo define the
cavity (440).
19. Thc apparatus of any of claims 15 to 18, fuithcr comprising at least onc of.
(FIG. 4D, 4E) nozzlcs (322, 422) for delivering precursor material, in liquid, solid or
utomizcd foim; and
(FIG. 3) nozzles (326) for dispensing finishing matcrial (327) onto the malerial being
treated.
20. The apparatus of any of claims 15 to 19, wherein:
(FIG. 4G) thc two spaced-apart cleetrodes (elle2) comprise first and second plates (452,
454).
21. Use of the apparatus according to any of claims 15 to 20 for treating a textile substrate.
22. The use of claim 21, wherein the textile substrate is a synthetic textile material,
23. Thc use of claim 22, wherein the synthetic textile material is polyester.
24. The use of claim 21, wherein the substrate is an organic material.
25. Thc use of claim 24, wherein the organic matcrial is at least onc selected fiom cotlon and
wool.
26. A textilc matcrial obtained by the xncthod according to any of claims 1 to 14.
27. A method of crating a plasma for material treatment comprising:
combining at least two diffccrent cncrgy sourccs selected fiom high voltage, playma, lascr,
UV lamp and pulsablc microwavc clcctron cyclotron resonancc (ECR).
28. Thc mcthod of claim 27, wherein:
one of the at least two different energy sources crcatcs an atmospheric pressure (AP) plasma.
29. The method of claim 27, wherein:
one cncrgy sourcc is plasma; and
the other energy sourcc is a laser beam directed inlo the plasma.
30. The method of claim 27 or 28, wherein:
the lascr bcam is directcd at the material being treatcd.
31. The method of any of claims 27 to 30, wherein:
thc plasma is provided by plasma nozzles.
Dated this ~ 3Da'y ~of J anuary 2014 Of Anand And Anand Advocates
Agent for the Applicant