NZ620033B2 - Method and apparatus for surface treatment of materials utilizing multiple combined energy sources - Google Patents
Method and apparatus for surface treatment of materials utilizing multiple combined energy sources Download PDFInfo
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- NZ620033B2 NZ620033B2 NZ620033A NZ62003312A NZ620033B2 NZ 620033 B2 NZ620033 B2 NZ 620033B2 NZ 620033 A NZ620033 A NZ 620033A NZ 62003312 A NZ62003312 A NZ 62003312A NZ 620033 B2 NZ620033 B2 NZ 620033B2
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- New Zealand
- Prior art keywords
- plasma
- substrate
- treatment
- electrodes
- rollers
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 127
- 238000004381 surface treatment Methods 0.000 title description 7
- 210000002381 Plasma Anatomy 0.000 claims abstract description 138
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 25
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/005—Laser beam treatment
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
Abstract
Material treatment is effected in a treatment region (124) by at least two energy sources, such as (i) an atmospheric pressure (AP) plasma and (ii) an ultraviolet (UV) laser directed into the plasma and optionally onto the material being treated. Precursor materials may be dispensed before, and finishing material may be dispensed after treatment. Electrodes (el, e2) for generating the plasma may comprise two spaced-apart rollers (212/214). Nip rollers adjacent the electrode rollers define a semi-airtight cavity, and may have a metallic outer layer. shing material may be dispensed after treatment. Electrodes (el, e2) for generating the plasma may comprise two spaced-apart rollers (212/214). Nip rollers adjacent the electrode rollers define a semi-airtight cavity, and may have a metallic outer layer.
Description
Method and Apparatus for e Treatment of Materials
Utilizing Multiple Combined Energy Sources
CROSS-REFERENCE TO RELATED APPLICATION(S)
This application claims filing date benefit from US 61/501 ,874 filed 011.
TECHNICAL FIELD
The invention relates to surface treatment of materials and various substrates, more particularly
such as textiles, and more particularly to treatment of the materials with combined multiple
diverse energy sources, typically one of which may be an atmospheric plasma (AP).
BACKGROUND
Development of “smart textiles” has been an active area of interest to e various properties
such as stain resistance, waterproofing, colorfastness and other characteristics achievable through
ed treatment using plasma technologies, microwave energy sources and in some cases,
chemical ents.
Atmospheric Plasma Treatment (APT) es fiber surface ties such as hydrophilicity
without affecting the bulk properties of these fibers, and can be used by textile manufacturers
and converters to improve the surface properties of natural and synthetic fibers to e
adhesion, wettability, printability, dyeability, as well as to reduce material age.
Atmospheric-pressure plasma (or AP plasma or normal pressure plasma) is the name given to the
special case of a plasma in which the pressure approximately matches that of the surrounding
atmosphere. AP plasmas have prominent technical significance because in contrast with low-
pressure plasma or high-pressure plasma no cost-intensive reaction vessel is needed to ensure the
nance of a pressure level differing from atmospheric pressure. Also, in many cases these
AP plasmas can be easily incorporated into the production line. Various forms of plasma
excitation are possible, including AC (alternating t) excitation, DC (direct current) and
low-frequency excitation, excitation by means of radio waves and microwave excitation. Only
AP plasmas with AC excitation, however, have attained any noteworthy industrial significance.
Generally, AP plasmas are generated by AC tion (corona discharge) and plasma jets. In
the plasma jet, a pulsed electric arc is ted by means of high-voltage discharge (5–15 kV,
–100 kHz) in the plasma jet. A process gas, such as oil-free compressed air flowing past this
discharge n, is excited and converted to the plasma state. This plasma then passes through a
jet head to arrive on the e of the material to be d. The jet head is at earth potential and
in this way largely holds back potential-carrying parts of the plasma stream. In addition, the jet
head determines the geometry of the emergent beam. 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 jets.
AP and vacuum plasma methods have been utilized to clean and activate surfaces of materials in
preparation for bonding, printing, painting, polymerizing or other functional or decorative
coatings. AP processing may be preferred over vacuum plasma for continuous processing of
material. Another surface treatment method utilizes microwave energy to polymerize precursor
coatings.
It is an object of the invention to at least e the public with a useful choice.
SUMMARY
The invention is generally directed to providing ed techniques for treatment (such as
surface treatment and modification) of materials, such as ates, more particularly such as
textiles (including woven or knitted textiles and non-woven s), and broadly involves the
combining of s 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 s energy
sources are disclosed.
An ment of the invention y comprises method and apparatus to treat and produce
cal textiles and other materials utilizing at least two combined mutually interacting energy
sources such as laser and high voltage generated atmospheric (AP) plasma.
The techniques disclosed herein may readily be incorporated into a system for the automated
processing of textile materials. Functionality may be achieved through non-aqueous cleaning like
etching or ablating, activating by way of l ion on the surface(s) and simultaneously
and selectively sing or decreasing desired fianctional properties. Properties such as
hydrophobicity, hydrophilicity fire ency, anti-microbial properties, shrink reduction, fiber
scouring, water repelling, low temperature , increased dye take up and colorfastness, may
be enabled or enhanced, increased or sed, by the process(es) which produces chemical
and/or morphological changes, such as radical formation on the surface ofthe al. Coatings
of material, such as nano-scale coatings of advanced materials composition may be applied and
processed.
Combining (or hybridizing) AP plasma energy with one or more additional (or secondary)
energy sources such as a laser, X-ray, electron beam, microwave or other diverse energy sources
may create a more effective (and commercially viable) energy milieu for substrate ent. The
secondary energy source(s) may be applied in combination (concert, simultaneously) with and/or
in sequence (tandem, selectively) with the AP plasma energy to achieve d properties.
Secondary energy sources may act upon the separately generated plasma plume and e a
more effective, energetic plasma milieu, while also having the ability to act directly on the
surface and in some cases, the core of the material subjected to this hybrid treatment.
The ques disclosed herein may be applicable, but not limited to the treatment of textiles
(both organic and inorganic), paper, synthetic paper, plastic and other similar materials which are
typically in flat sheet form (“yard goods”). The techniques disclosed herein may also be applied
to the processing of plastic or metal extrusion, rolling mills, injection molding, spinning, carding,
weaving, glass , substrate etching and cleaning and coating of any material as well as
applicability to practically any al processing technique. Rigid materials such as flat sheets
of glass (such as for touch screens) may be treated by the techniques disclosed herein.
According to one aspect of the present invention, there is provided a method for treatment of a
substrate (102, 402, 404) sing:
creating a plasma in a treatment region (124) comprising two spaced-apart electrodes (e1 /e2 ;
212/214; 412/414; 452/454) wherein the electrodes are provided as s with one roller being
disposed substantially parallel to the other , with a gap therebetween, to allow the substrate
material to be fed n the rollers;
directing at least one second energy source which is different than the first energy source
into the plasma to interact with the plasma, resulting in a hybrid plasma; and
causing the hybrid plasma to interact with the substrate in a treatment region (124).
In another aspect, the present invention encompasses an apparatus (100, 400A, 400B, 400C,
400D, 400E, 400F, 400G) for ng materials comprising:
two spaced-apart electrodes (e1 /e2 ; 212/214; 412/414) for generating a plasma in a
ent region (124);
wherein the two electrodes are first and second rollers disposed substantially parallel to each
other with a gap therebetween, to allow the substrate material to be fed between the rollers; and
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 treated.
In a further aspect, the present invention comprehends a use of the apparatus described herein for
treating a textile ate.
In a different aspect, the present invention envisages a textile material obtained by the method
described herein.
In yet a further aspect, the present invention plates a method of creating a plasma for
material ent comprising providing two electrodes in the form of a rod, or a tube or other
rotatable cylindrical electrode material, spaced apart from one another a distance sufficient to
allow for clearance of the thickness of a material being processed; energizing the electrodes in
any le manner to create an atmospheric plasma along their length in a ent region
(followed by page 4a)
between and immediately surrounding the electrodes; directing a laser beam into the treatment
, approximately parallel to and between the electrodes so as to interact with the plasma
generated by the two electrodes.
Some ages of the present invention may include, t limitation, a method of creating a
more energetic and effective plasma to clean and activate surfaces for subsequent processing or
finishing. For example, ultra-violet (UV) laser radiation, either continuous wave (CW) or
pulsed, may be combined with electromagnetically generated AP plasma to create a more highly
(followed by page 5)
ionized and energetic reaction milieu for ng surfaces. The resulting hybridized energy may
have effects that are greater than the sum of its individual parts. Pulsed laser energy may be used
to drive the plasma, creating waves, and the laser energy accelerates the resultant plasma waves
which act upon the substrate like waves crashing on the beach.
The accelerated and more energetic plasma may te radicals in the fiber or surface of the
treated substrate and attach ionized groups to the initiated radicals. Attachment of such
functional groups as carboxyl, hydroxyl or others attach to the surface increasing polar
characteristics may result in greater hydrophilicity and other desirable functional ties.
The invention advantageously es energy sources in a controlled atmospheric environment
in the presence of a material substrate. The net result may be conversion and material synthesis
in the surface of the substrate - the substrate may 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 chamber) formed n rotating and driven rollers which extend across the width of the
processing window. The plasma field generated is consistent across the width of a treatment
area, and may e at heric pressure. A high power Ultra Violet UV) laser is provided
for interacting with the plasma and/or the material being treated. The beam from the laser may
be shaped to have a gular cross-section exhibiting a consistent power density over the
entire ent area. A gas delivery system may be used to combine any combination of a
plurality (such as 4) of environmental gases and precursors into a single feed which populates the
hybrid plasma r. Additionally, a spray or misting delivery system may be provided,
capable of applying a thin, consistent layer of sol-gel or process accelerants to the material being
d, either pre- or post- processing.
The process of combining plasma and photonics (such as UV laser) 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 varying the
environmental gases or the addition of ls and/or other organic or inorganic precursors -
i.e., changing the “recipe” - allows the system to generate a wide y of process applications.
There are at several ations for the process, including: cleaning, preparation and
performance enhancement of materials.
- For cleaning, the laser may intensify the effective power of the plasma as well as acting
on the substrate material in its own right.
- For preparing the ate material for secondary processing, such as dyeing, the surface
of the fibers may be ablated in a controlled manner, thereby increasing the hydrophilicity
of the material (such as a textile material). Additionally, be introducing environmental
gases into the process zone of the system, chemistries may be created at the surface of the
material (e.g., fabric) which may result in chemistries that react with a dyeing media to
effect a more efficient dye ation or a more intense ng process or reduction of
dye temperature. For e, preparing the fibers of the textile to give a better
controlled uptake of chrome oxide dyes to improve the intensity of black achieved. There
is, therefore, ial for this process to reduce the chemical content of dyes which could
reduce both negative environmental impact and processing costs.
- For Performance Enhancement, the process may achieve material synthesis in the surface
of the substrate. By altering the laser and plasma frequencies and the power intensities,
and introducing other materials into the process environment, the system ablates the
surface of the substrate and a series of chemical reactions between the substrate and the
environmental gases synthesize new materials in the surface of the fibers in the textile
web.
Unless the t clearly requires otherwise, throughout the ption and claims the terms
“comprise”, “comprising” and the like are to be construed in an inclusive sense, as opposed to an
exclusive or exhaustive sense. That is, in the sense of ding, but not limited to”.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference may be made in detail to embodiments of the disclosure, some non-limiting examples
of which may be illustrated in the accompanying drawing figures . The figures are
generally diagrams. Some elements in the s may be exaggerated, others may be omitted,
for illustrative clarity. The relationship(s) between different elements in the figures may be
referred to by how they appear and are placed in the drawings, such as "top", m", "left",
"right", "above", "below", and the like. It should be understood that the ology and
terminology employed herein is not to be construed as limiting, and is for descriptive purposes
only.
is a diagram of a treatment system, according to an embodiment ofthe ion.
is a partial perspective View of a plasma region of the treatment system of
is a partial perspective View of a plasma region ofthe treatment system of
is a partial ctive View of a eatment region, plasma region and post-treatment
region ofthe ent system of according to some embodiments of the invention.
FIGs. 4A - 4G are diagrams of elements in a treatment region of the ent system of
according to some embodiments ofthe invention.
DETAILED DESCRIPTION
The invention relates generally to ent (such as surface treatment) of materials (such as
textiles) to modify their properties.
s embodiments will be described to illustrate teachings of the ion(s), and should be
construed as illustrative rather than limiting. Although the invention is generally described in the
context of various exemplary embodiments, it should be understood that it is not intended to
limit the invention to these particular embodiments. An embodiment may be an example or
implementation of one 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
invention(s) may be described in the context of separate ments, the invention(s) may also
be implemented in a single embodiment.
In the main hereinafter, surface treatment of substrates which may be textiles supplied in roll
form (long sheets of material rolled on a cylindrical core) will be discussed. One or more
treatments, including but not limited to material synthesis, may be applied to one or both
surfaces of the textile substrate, and additional materials may be introduced. As used herein, a
“substrate” may be a thin “sheet” of al haVing two surfaces, which may be termed “front”
and “back” surfaces, or “top” and m” surfaces.
Some Embodiments of the Invention
The following embodiments and aspects thereof may be described and illustrated in conjunction
with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in
scope. Specific configurations and details may be set forth in order to provide an understanding
of the invention(s). However, it should be apparent to one d in the art that the invention(s)
may be practiced without some of the specific details being presented herein. Furthermore, well-
known es may be omitted or simplified in order not to e the descriptions of the
invention(s).
shows an overall surface treatment system 100 and method of performing treatment, such
as a surface ent of a substrate 102. In the figures presented herein, the substrate 102 will
be shown advancing from right-to-left through the system 100.
The ate 102 may for example be a textile material and may be ed as “yard goods” as
a long sheet on a roll. For example, the substrate to be treated may be fibrous textile material
such as cotton/polyester, approximately 1 meter wide, approximately 1mm thick, and
approximately 100 meters long.
A section 102A, such as a 1m x 1m n of the substrate 102 which is not yet treated is
illustrated paying out from a supply reel R1 at an input section 100A of the system 100. From
the input section 100A, the substrate 102 passes through a treatment section 120 of the apparatus
2012/051516
100. After being treated, the substrate 102 exits the treatment apparatus 120, and may be
collected in any suitable manner, such as wound up on a take-up reel R2. A section 102B, such
as a 1m x 1m section of the substrate 102 which has been treated is illustrated being wound onto
an takeup reel R1 at an output section 100A of the system 100. Various rollers “R” may be
provided between (as shown) and within (not shown) the s sections of the system 100 to
guide the material through the system.
The treatment section 120 may generally comprise three regions (or areas, or :
- optionally, a eatment (or precursor) region 122,
- a ent (or plasma) region 124, and
- optionally, a post-treatment (or finishing) region 126.
The treatment region 124 may comprise components for generating a high voltage (HV)
alternating current (AC) heric plasma (AP), the elements of which are generally well
known, some ofwhich will be described in some detail hereinbelow.
A laser 130 may be provided, as the secondary energy source, for providing a beam 132 which
interacts with the AP in the main treatment region 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
elements described hereinabove, and may be provided with the usual human interfaces (input,
display, etc.).
shows a portion of and some operative elements within the main treatment region 124.
Three orthogonal axes x, y and z are illustrated. (In the corresponding x and y axes are
illustrated.)
Two elongate electrodes 212 (el) and 214 (e2) are shown, one of which may be considered to be
a cathode, the other of which may be ered to be an anode. These two electrodes el and e2
may be disposed lly parallel with one another, extending parallel to the y axis, and spaced
apart from one another in the x ion. For example, the electrodes el and e2 may be formed
in any suitable manner, such as in the form of a rod, or a tube or other rotatable cylindrical
electrode al, and spaced apart from one another nominally, a distance sufficient to allow
for clearance of the thickness of the material processed. The electrodes el and e2 may be
disposed approximately 1 mm above the top surface 102a of the substrate 102 being treated.
The electrodes el and e2 may be energized in any suitable manner to create an atmospheric
plasma (AP) along the length of the resulting cathode/anode pair in a space between and
immediately surrounding the electrodes el and e2, which may be referred to as a “plasma
reaction zone”.
As mentioned above, a laser beam 132 may be directed into the main ent region 124, and
may also impinge on a surface of the substrate 102. Here, the laser beam 132 is shown being
directed approximately along the y axis, imately parallel to and between the electrodes el
and e2, and slightly above the top surface 102a of the substrate 102, so as to interact with the
plasma (plume) generated by the two electrodes el and e2. In an exemplary application, the
beam footprint may be a rectangle approximately 30mm x 15mm. The beam may be oriented
vertically or horizontally to best achieve the desired interaction of plasma and/or direct substrate
ation
The laser beam 132 may be directed ly but sufficiently “off angle” to ly irradiate the
substrate 102 to be treated as it coincidently reacts with the plasma being generated by the two
electrodes el and e2. More particularly, the laser beam 132 may make an angle of “a” which is
imately 0 degrees with the top surface 102a of the substrate 102 so as not to impinge on
its surface 102a. Alternatively, the laser beam 132 may make an angle of “a” which is
approximately less than 1 - 10 degrees with the top e 102a of the substrate 102 so as to
impinge on its surface 102a. Other orientations of the beam 132 are possible, such as
perpendicular (“a” = 90 degrees) with the e 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 e2 or the substrate 102, or both.
WO 01306
The plasma may be created using a first energy source such as high voltage (HV) alternating
current (AC). A second, different energy source (such as laser) may be caused to interact with
the plasma, resulting in a “hybrid plasma”, and the hybrid plasma may be caused to interact (in a
treatment ) with the substrate (material) being treated. In addition to interacting with the
first energy , the second energy source can be caused to also interact directly with the
material being treated. The direct interaction with the substrate or other gas (secondary or
precursor) may produce its’ own laser ned plasma which in turn may further interact with
the high voltage generated plasma to more highly energize the reaction milieu.
The substrate 102 (material being treated) may be guided by rollers as it passes through the main
treatment region (area) 124. illustrates that one of these rollers 214 may serve as the
anode, and the other roller 212 may serve as the cathode (or vice-versa) of a cathode/anode pair
for generating the plasma. It may be noted that in the substrate 102 is disposed to one
side of (below, as viewed) both of the two electrodes el and e2, and in the substrate 102
is disposed between the two electrodes el and e2. In both cases, the plasma created by the
electrodes el and e2 acts on at least one surface of the substrate 102. The anodes and cathodes
may be coated with an insulating material, such as ceramic.
It should be understood that the invention is not limited to any particular arrangement or
configuration of electrodes el and e2, and that the examples set forth in FIGs. 2, 2A are 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) ring a plasma may be
ed to create the desired plasma above the surface 102a ofthe substrate 102.
shows that in the pre-treatment region (area) 122, a row of spray heads (nozzles) 322
covering the filll width of the material to be treated, or other le means, may be used to
dispense precursor materials 323 in solid, liquid or s phase onto the substrate 102 to
enable the processing of/for specific ties such as antimicrobial, fire retardant or super-
hydrophobic/hydrophilic characteristics.
There may be an intermediate “buffer” zone between the pre-treatment region (area) 122 and the
main treatment region (area) 124, to allow time for the materials applied in pre-treatment to soak
into (be absorbed by) the substrate. The process still runs a single length of material, but the
buffer may hold, for example, up to 200m of fabric. For example, when material being treated
(such as yard goods) is feeding through the system at 20 meters/min, this would allow for several
minutes “drying time” between pre-treatment (122) and hybrid plasma ent (124), without
stopping the flow of material through the system.
Similarly, in the post-treatment region (area) 126, a row of spray heads (nozzles) 326 covering
the full width of the material which was d (124), or other suitable means, may be used to
dispense finishing materials 327 in solid, liquid or gaseous phase onto the substrate 102 to imbue
it with desired characteristics.
Some embodiments of the ent region ( 124)
FIGS. 4A - 4G illustrate various embodiments of elements in the treatment region 124.
rates an embodiment 400A wherein:
- A first (“top”) roller 412 is ive to fiJnction as an electrode el, and may have a
diameter of approximately 10cm, and a length (into the page) of 2 meters. The roller 412
may have a metallic core and a ceramic (electrically insulating) outer surface.
- A second (“bottom”) roller 414 is operative to fiJnction as an electrode e2, and may have
a diameter of approximately 15cm, and a length (into the page) of 2 . The roller
414 may have a metallic core and a ceramic (electrically insulating) outer surface.
- The second roller 414 is disposed parallel to and directly underneath (as viewed) the first
roller 412, with a gap therebetween corresponding to (such as slightly less than) the
thickness of the substrate material 402 (compare 102) being fed n the rollers 412
and 414. The ion of material travel may be right-to-left, as indicated by the arrow.
The ate 402 has a top surface 402a (compare 102a) and a bottom surface 402b
(compare 102b).
- The first roller 412 may serve as the “anode” of an anode/cathode pair, having high
voltage (HV) supplied thereto. The second roller 414 may serve as the “cathode” of the
anode/cathode pair, and may be grounded.
- A first (“right”) nip or feed roller 416 (n1) is disposed nt a bottom-right (as
viewed) quadrant of the first roller 412, and against a top-right (as viewed) quadrant of
the second roller 414. The roller 416 may have a diameter of approximately 12cm, and a
length (into the page) of 2 meters. The outer surface of the roller 416 may engage the
outer surface of the roller 412. A gap n the outer surface of the roller 416 and the
outer surface of the roller 414 corresponds to (such as slightly less than) the thickness of
the substrate material 402 (compare 102) being fed n the rollers 416 and 414.
- A second (“left”) nip or feed roller 418 (n2) is disposed adjacent a bottom-left (as
viewed) quadrant ofthe first roller 412, and against a top-left (as viewed) quadrant of the
second roller 414. The roller 418 may have a diameter of approximately 12cm, and a
length (into the page) of 2 meters. The outer surface of the roller 418 may engage the
outer surface of the roller 412. A gap between the outer surface of the roller 418 and the
outer surface of the roller 414 corresponds to (such as slightly less than) the thickness of
the substrate material 402 (compare 102) being fed n the rollers 418 and 414.
- Generally, the nip or feed rollers 416, 418 should have an insulating outer surface so as to
avoid shorting the anode and cathode 412, 414.
With such an arrangement of rollers 412, 414, 416, 418, a irtight cavity (“440”) may be
formed between the outer surfaces of the four rollers 412, 414, 416, 418 for defining the
treatment region 124 and containing the plasma. The overall cavity 440 may comprise a first
(“right”) n 440a in the space between the top, right and bottom s 412, 416, 414 and a
second (“left”) portion 440b in the space n the top, left and bottom rollers 412, 418, 414.
The filled circle at the end of the lead line for the right portion 440a of the cavity 440 represents
gas flow into the cavity. The filled rectangle at the end of the lead line for the left portion 440b
of the cavity 440 represents the laser beam (132).
The plasma generated in the cavity 440 may be an atmospheric pressure (AP) plasma.
Therefore, sealing of the cavity 440 is not ary. However, end caps or plates (not shown)
may be ed at the ends of the rollers 412, 414, 416, 418 to contain (semi-enclose) and
control the gas flow in and out of the cavity 440.
illustrates an embodiment 400B wherein the left and right rollers 416 and 418 are
moved slightly outward from the rollers 412 and 414, thereby opening up the caVity 440 to allow
for thicker and /or stiffer substrates to be processed . This would however require independent or
direct drive of each electrode, anode and cathode. The material would be driven through the
reaction zone by outside feeding and take up rollers.
illustrates an embodiment 400C wherein a generally inverted U-shaped shield 420 is
used d of the left and right rollers (416 and 418) to define the caVity 440 haVing right and
left portions 440a and 440b. The shield 420 is disposed substantially completely around one
roller 412 (except for where the material feeds h), and at least partially around the other
roller 414. An additional shield (not shown) could be disposed under the bottom roller 414.
illustrates an embodiment 400D adapted to treat rigid substrates. The substrate 402
described above was flexible, such as textile. Rigid substrates such as glass for touchscreen
displays may also be treated with a hybrid plasma and sor materials. A rigid substrate 404
haVing a top surface 404a and bottom surface 404b passes through the top roller (e1) 412 and the
bottom roller (e2) 414. A row of nozzles 422 (compare 322) may be arranged to provide
sor material, such as in liquid, solid or atomized form. A shield (not shown) such as 420
(refer to ) may be incorporated to contain the hybrid .
shows an arrangement 400E incorporating a row of HV plasma s (jets) 430,
rather than the cylindrical electrodes el and e2. For example, ten jets 430 spaced at 20cm
intervals in the treatment region 124. A rigid substrate 404 is shown. A row of nozzles 422
(compare 322) may be arranged to e precursor material, such as in atomized form, onto the
substrate 404, in a pre-treatment region 122, before it is exposed to the hybrid plasma. For
example, ten nozzles 422 spaced at 20cm intervals in the eatment region 122. A shield
(not shown) such as 420 (refer to ) may be incorporated to contain the hybrid plasma.
This arrangement enables ent of metallic or other conductive substrates.
illustrates an embodiment 400F a first (“top”) roller 412 operative to fianction as an
electrode e1 (or anode), a second (“bottom”) roller 414 operative to fianction as an ode e2
(or cathode), and two nip s 436 and 438 (compare 416 and 418).
In contrast with the embodiment 400A (), in this embodiment the rollers 436 and 438)
are spaced outward slightly (such as 1 cm) from the top and bottom rollers 412 and 414.
Therefore, gh they will still help contain the plasma, they may not fianction as feed rollers,
and separate feed rollers (not shown) may need to be ed .
The right roller 436 (compare 416) is shown having a layer or coating 437 on its surface. The
left roller 438 (compare 418) is shown having a layer or coating 439 on its surface. For example,
the rollers 436 and 438 in the hybrid plasma treatment region 124 may be wrapped with metallic
foil (or otherwise have a metallic outer layer) which may be etched away, in process, by the
highly energetic hybrid plasma and/or by the laser (second energy source) creating a plume
containing reactive metallic plasma which may readily couple with the substrate surface ls
to create nano-layer coatings with metallic composition on the substrate material. The metallic
al (foil, layer) may be controllably etched or ablated by the plasma, and the effluent
metallic constituents may react with the plasma and be deposited on the substrate, such as in
cale layers.
The metallic material coating the s 436 and 438 may comprise any one or combination of
titanium, copper, aluminum, gold or silver, for example. One of the rollers may be coated with
one al, the other of the rollers may be coated with another material. Different portions of
the rollers 436 and 438 may be coated with different materials. Generally, when these materials
are ablated, they form vapor sor 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.)
illustrates an embodiment 400G using two flat sheet, plate odes 452 and 454,
rather than rollers (412, 414), spaced apart from one another to form a treatment region
ion/synthesis zone) 124 through which a sheet of material 404 may be fed. Gas feed to the
treatment region is indicated by the circle 440a, the laser beam is ted by the rectangle
440b. Nozzles 422 may be provided to deliver precursor material(s) in the pre-treatment zone
122. Nozzles 426 may be provided to deliver finishing material(s) in the post-treatment zone
126.
Additional Features
Although not specifically shown, finishing materials dispensed onto the substrate 102 after
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 dispensed following
activation ofthe surface by the hybrid plasma.
Although not specifically shown, it should be understood that various gases, such as 02, N2, H,
CO2, Argon, He, or compounds such as silane or siloxane based materials may be introduced
into the plasma, such as in the treatment region 124, to impart various desired characteristics and
properties to the treated substrate.
To impart anti-microbial properties to the al being treated, precursor als may be
introduced such as non-silver based silanes/siloxanes and the aluminum chloride family such as
3 (trihydroxylsilyl) propyldimethyl octadecyl, ammonium chloride. Other Silane/Siloxane
groups may be used to affect hydrophobicity as well as siloxones and ethoxy s (to increase
hydrophilicity). Hexamethylidisiloxane applied in the gaseous phase in the plasma may smooth
the surface of textile fibers and increase the contact angle which is an indication of the level of
hydrophobicity.
Negative draft or atmospheric partial vacuum may be employed to draw plasma constituents into
and filrther penetrate the thickness of porous ates. shows that suction means, such
as platen (bed) 324 over which the substrate 102 , in the treatment area 124, may be
2012/051516
ed with a plurality of holes and connected in a suitable manner to suction means (not
shown) to create the desired . The platen 324 may function as one of the electrodes for
generating the plasma. Alternatively, a roller or the like could readily be modified (with holes
and connected with suction means) to perform this fianction.
It should be understood that the s is dry and has a low nmental impact, and that
leftover or byproduct gases or constituents are inherently safe and may be exhausted from the
system and recycled or disposed of in an appropriate manner.
There is thus provided a method of treating als with at least two energy sources, wherein
the two energy s comprise (i) an AP plasma produced by s gases passing through a
high energy electromagnetic field and (ii) at least one laser interacting with said plasma to create
a “hybrid plasma”. The laser may operate in the ultra-violet wave length range, 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, more than 200 watts. The laser may be
pulsed, such as at a frequency of 25Hz or higher such as 350-400 Hz, including picosecond and
femtosecond lasers. Although only one laser has been described interacting with the plasma (and
the substrate), it is within the scope of the ion that two or more lasers may be used.
Some exemplary parameters for generating the plasma in the treatment region are l - 2 Kw
(kilowatts) for the HV generated plasma and 500mjoules, 350Hz for the 308nm UV laser, in an
80% argon, 20% Oxygen or CO2 gas mix.
As an alternative to or in addition to using a laser, an ultraviolet (UV) source such as a UV lamp
or an array of high powered UV LEDs (light-emitting diodes) disposed along the length of the
treatment area may be 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 material being treated..
In the main, hereinabove, treating one surface 102a of a substrate material 102 was illustrated,
and some exemplary treatments were bed. It is within the scope of the invention that the
opposite bottom surface 102b of the material 102 may also be treated, such as by looping the
al 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 material. In this
manner, both es of the material may be treated. It should also be understood that the
treatments may extend to within the surface of the material being treated to alter or enhance
properties of the inner (core) al. In some cases, both top and bottom surfaces as well as
the core ofthe material may be effectively treated from one side.
The system can be used to treat materials which are in other than sheet 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 le manner.
Other types of energy may be applied in combination or in sequence with each other to create
ed processing capabilities. For example, a method of treating als may utilize the
combination of at least two energy sources such as ave and laser, or microwave and
electromagnetically ted plasma, or plasma and microwave, or various combinations of
plasma, laser and pulsable microwave electron cyclotron resonance (ECR).
The two energy sources may comprise (i) an atmospheric plasma, utilizing various ionized gases
passed through high energy electromagnetic fields, and (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 powered UV LEDs (light-emitting
diodes) disposed along the extent of the treatment area. 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 sources.
A series ofprocess steps may be performed, such as:
step 1 - nal) sor application,
step 2 - re to hybrid energy,
step 3 - (optional) precursor or ng material application and,
step 4 - exposure to hybrid energy.
in which all steps are accomplished in serial fashion immediately within the system.
It is within the scope of the invention to uce into the process a delivery system capable of
adding gas/vapor phase precursor materials directly in to the plasma reaction zone.
Some Exemplary Treatment Process Parameters
Treatment 1 - Hydrophilicity
Precursor material
polydimethylsiloxane hydroxycut (PMDSO Hydroxycut)
alt: copolymer (Dimethylesiloxane and/or with blend of dimethylesilane)
Laser
Frequency 250Hz
Power 380 mJ
Plasma
Carrier Gas Argon 80%
ve Gas 02 20%
Flow rate 15 liter/min Pressure: slightly above 1 bar
Power 2 KW
Treatment 2 - Dyeability
Precursor
Either no precursor or other precusor sts
Laser
Frequency 250Hz
Power 380 mJ
Plasma
Carrier Gas Argon 80%
Reactive Gas 02 or N2 20%
Flow rate 15 min Pressure: ly above 1 bar
Power 2 KW
Treatment 3 - Hydrophobicity
Precursor octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluable,
hydrogen methyl polysiloxane mixed withpolydimethylsiloxane with polyglycolether (water
soluable) or combination ofthe above with polydimethylsiloxane. Using water soluble blends
allows for diluting the materials with de-ionised water to the required concentrations based on
the application, cost effectiveness and output performance results. Water soluble blends may be
produced with nt additives - these are ially methods for mixing oil with water to
produce emulsions, generally described by the size of the emulsion dispersant, i.e. macro or
micro (macro is >100 microns, micro<30 microns).
alt: copolymer (Dimethylesiloxane and/or with blend of dimethylesilane)
Laser
Frequency at least 350Hz
Power at least 450 mJ
Plasma
Carrier Gas Nitrogen, Argon, Helium 80%
Reactive Gas CO2 or N2 2-20%
Flow rate 10-40 liter/min Pressure: slightly above 1 bar
Power 0.5 — 1 KW
ent 4 - Fire retardancy
Precursor
Copolymers and Terpolymers based on siloxane/silane and rosiloxane with key
inorganic compounds, essentially transition oxides of um, silicon and zirconium and
boron. Also included, Boron containing siloxane Copolymers and Terpolymers, such as
organosilicon/oxyethyl modified polyborosiloxane. Some limited material composition
based recent new phosphorous blends may be used, based on the substrate material types
and output requirements. octamethylcyclotetrasiloxane/polydimethylsilane blend (water
W0 01306 2012/051516
soluable) mixed with polydimethylsiloxane with polyglycolether (water soluble) or
comination of the above with polydimethylsiloxaneWith additives of:
- calcium metaborbate additive to silane/siloxane -
- Silicon oxide additive to silane /siloxane -
- Titanium isopropoxide additive '
- Titanium dioxide (routile)'
- Ammonium ate
- Aluminum oxide-
- Zinc borate'
- Boron phosphate containing preceramic oligomores'
- Aerogels and hydrogels, low or high density cross linked polyacrylates.-
- nano/micro encapsulated compositions.
Example: dimethylsiloxane and/or with dimethylsilane with polyborosiloxane, with
added transition oxides, range 5 to 10% volume of oxides such as Tio2, sio2 (filmed, gel
or amorphous), A1203, etc. The precursor materials set forth herein may enhance fire
retardency of materials in the system described herein utilizing a hybrid plasma (e.g.,
with . It is Within the scope of the invention that the precursor materials set forth
herein may enhance fire retardency (or other properties) of materials in a material
treatment system utilizing a non-hybrid plasma (e.g., Without the laser).
Laser
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 liter/min Pressure: slightly above 1 bar
Power 0.5 — 1 KW
ent 5 - Anti Microbial
Precursor
ne/silane blends as per hydrophobicity platform, with the addition of
octadecyldimethyl (3triethoxysilpropyl) ammonium chloride.
octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble)mixed
Withpolydimethylsiloxane with polyglycolether (water soluble) or comination of above With
polydimethylsiloxanewith additives of:
- octadecyldimethyl(3-trimethoxysilylpropyl)ammmonium chloride),
- Chitosan
Laser
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 min Pressure: slightly above 1 bar
Power 0.5 - 1 KW
While the invention(s) has been described with respect to a limited number of embodiments,
these should not be construed as tions on the scope of the invention(s), but rather as
examples of some of the embodiments. Those skilled in the art may envision other possible
variations, modifications, and implementations that are should also be considered to be Within
the scope of the invention(s), based on the sure(s) set forth herein, and as may be claimed.
Claims (30)
1. A method for treatment of a substrate comprising: creating a plasma by using a first energy source in a treatment region comprising two spaced-apart electrodes wherein the electrodes are provided as rollers with one roller being disposed substantially parallel to the other , with a gap therebetween, to allow the substrate al to be fed between the rollers; directing at least one second energy source which is different than the first energy source into the plasma to ct with the , resulting in a hybrid plasma; and causing the hybrid plasma to interact with the substrate in a treatment region.
2. The method of claim 1, wherein: the first energy source comprises high voltage alternating current (AC); and the second energy source ses radiation from a laser.
3. The method of claim 2, wherein the laser interacts with the plasma, and also acts ly upon the material being treated.
4. The method of claim 2 or 3, wherein the laser has at least one of the following characteristics: the laser comprises an excimer laser; the laser operates in the ultra-violet (UV) wave length range; the laser operates with at least 25 watts of output power.
5. The method of any one of the preceding claims, wherein: the plasma comprises an atmospheric pressure (AP) plasma.
6. The method of any one of the preceding claims, further comprising: prior to said ng a plasma, dispensing precursor materials onto the substrate.
7. The method of any one of the preceding claims, further comprising: after said creating a plasma, dispensing ing materials onto the substrate.
8. The method of any one of the preceding claims, wherein: the plasma comprises a high voltage (HV) atmospheric pressure (AP) plasma.
9. The method of any one of the preceding claims, wherein the substrate is a textile material, paper, synthetic paper, plastic, or glass.
10. The method of any one of the preceding claims, wherein the substrate is a synthetic textile material.
11. The method of claim 10, wherein the synthetic textile material is ter.
12. The method of any one of claims 1 to 8, wherein the substrate is an organic material.
13. The method of claim 12, wherein the organic al is at least one selected from cotton and wool.
14. Apparatus for treating materials comprising: two spaced-apart electrodes for generating a plasma in a treatment region; wherein the two electrodes are first and second s disposed substantially parallel to each other with a gap therebetween, to allow the substrate material to be fed n the rollers; and one or more lasers directing ponding one or more beams into the treatment area to interact with at least one of the plasma and the material being treated.
15. The tus of claim 14, further comprising: third and fourth rollers disposed adjacent the first and second rollers and forming a semiairtight cavity between the outer surfaces of the first, second, third and fourth rollers for defining the treatment region and for containing the plasma.
16. The apparatus of claim 15, wherein: at least one of the third and fourth rollers comprise a metallic outer layer.
17. The apparatus of any one of claims 14 to 16, further comprising: a shield disposed around the first and second rollers to define the cavity.
18. The apparatus of any one of claims 14 to 17, further comprising at least one of: nozzles for delivering precursor material, in , solid or ed form; and nozzles for dispensing finishing material onto the material being treated.
19. Use of the apparatus according to any one of claims 14 to 18 for treating a textile substrate.
20. The use of claim 19, wherein the textile substrate is a synthetic textile material.
21. The use of claim 20, n the synthetic textile material is polyester.
22. The use of claim 19, wherein the substrate is an organic material.
23. The use of claim 22, wherein the organic material is at least one selected from cotton and wool.
24. A textile material obtained by the method according to any one of claims 1 to 13.
25. A method of ng a plasma for material treatment comprising: providing two electrodes in the form of a rod, or a tube or other rotatable cylindrical electrode material, spaced apart from one another a distance sufficient to allow for nce of the thickness of a material being processed; energizing the electrodes in any suitable manner to create an atmospheric plasma along their length in a treatment region between and immediately nding the electrodes; directing a laser beam into the treatment , approximately parallel to and between the electrodes so as to interact with the plasma generated by the two electrodes.
26. The method of claim 25, n: the laser beam is directed sufficiently “off angle” to directly ate the material being treated as it coincidently reacts with the plasma being generated by the two electrodes.
27. The method of any one of claims 25 to 26, further comprising coating the electrodes with ceramic.
28. A method for treatment of a substrate substantially as herein bed with reference to any one of the embodiments illustrated in the anying drawings, other than figures 3, 4E and
29. An apparatus for treating materials substantially as herein described with reference to any one of the embodiments illustrated in the accompanying drawings, other than figures 3, 4E and
30. A method of creating a plasma for material treatment substantially as herein described with reference to any one of the embodiments illustrated in the accompanying drawings, other than figures 3, 4E and 4G.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161501874P | 2011-06-28 | 2011-06-28 | |
US61/501,874 | 2011-06-28 | ||
PCT/GB2012/051516 WO2013001306A2 (en) | 2011-06-28 | 2012-06-28 | Method and apparatus for surface treatment of materials utilizing multiple combined energy sources |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ620033A NZ620033A (en) | 2015-11-27 |
NZ620033B2 true NZ620033B2 (en) | 2016-03-01 |
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