NZ703898B2 - Treating materials with combined energy sources - Google Patents
Treating materials with combined energy sources Download PDFInfo
- Publication number
- NZ703898B2 NZ703898B2 NZ703898A NZ70389812A NZ703898B2 NZ 703898 B2 NZ703898 B2 NZ 703898B2 NZ 703898 A NZ703898 A NZ 703898A NZ 70389812 A NZ70389812 A NZ 70389812A NZ 703898 B2 NZ703898 B2 NZ 703898B2
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- NZ
- New Zealand
- Prior art keywords
- plasma
- treated
- treatment
- substrate
- fibers
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/145—After-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
- D06M10/005—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/12—Contacts characterised by the manner in which co-operating contacts engage
- H01H1/14—Contacts characterised by the manner in which co-operating contacts engage by abutting
- H01H1/24—Contacts characterised by the manner in which co-operating contacts engage by abutting with resilient mounting
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/34—Details, e.g. electrodes, nozzles
Abstract
Material treatment is effected in a treatment region by at least two energy sources, such as (i) an atmospheric pressure plasma and (ii) an ultraviolet 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 (e1, e2) for generating the plasma may comprise two spaced-apart rollers. Nip rollers (n1, n2) adjacent the electrode rollers define a semi-airtight cavity, and may have a metallic outer layer. Loose fibers and fragile membranes may be supported on a carrier membrane, which may be doped. Individual fibers may be processed. Electrostatic deposition may be performed. Topographical changes may be effected. Various laser configurations and parameters are disclosed. ay be dispensed after treatment. Electrodes (e1, e2) for generating the plasma may comprise two spaced-apart rollers. Nip rollers (n1, n2) adjacent the electrode rollers define a semi-airtight cavity, and may have a metallic outer layer. Loose fibers and fragile membranes may be supported on a carrier membrane, which may be doped. Individual fibers may be processed. Electrostatic deposition may be performed. Topographical changes may be effected. Various laser configurations and parameters are disclosed.
Description
TREATING MATERIALS WITH COMBINED ENERGY SOURCES
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 improve various
properties such as stain resistance, waterproofing, colorfastness and other characteristics
achievable through advanced treatment using plasma technologies, microwave energy sources
and in some cases, chemical treatments.
Atmospheric Plasma Treatment (APT) improves fiber surface properties 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 improve adhesion, wettability, printability, dyeability, as well as to reduce material
shrinkage.
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 maintenance 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 current) 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 excitation (corona discharge) and plasma jets.
In the plasma jet, a pulsed electric arc is generated by means of high-voltage discharge (5–15
kV, 10–100 kHz) in the plasma jet. A process gas, such as oil-free compressed air flowing
past this discharge section, is excited and converted to the plasma state. This plasma then
passes through a jet head to arrive on the surface of the material to be treated. 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.
SUMMARY OF THE INVENTION
The invention is generally 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 embodiment of the invention broadly comprises method and apparatus to treat and
produce technical textiles and other materials utilizing at least two combined mutually
interacting energy sources such as laser and high voltage generated atmospheric pressure (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 radical formation on the surface(s) and
simultaneously and selectively increasing or decreasing desired functional properties.
Properties such as hydrophobicity, hydrophilicity fire retardency, anti-microbial properties,
shrink reduction, fiber scouring, water repelling, low temperature dyeing, increased dye take
up and colorfastness, may be enabled or enhanced, increased or decreased, by the process(es)
which produces chemical and/or morphological changes, such as radical formation on the
surface of the material. 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
treatment. 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 desired properties.
Secondary energy sources may act upon the separately generated plasma plume and produce 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 techniques 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 making, substrate etching and cleaning and coating of any
material as well as applicability to practically any material 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
textile material comprising: creating a high voltage alternating current atmospheric pressure
plasma in a process chamber having a treatment region between two spaced-apart electrodes,
wherein the two electrodes are first and second rollers disposed substantially parallel to each
other with a gap therebetween, to allow the material to be fed between the rollers; directing a
laser beam into the plasma, approximately parallel to and between the electrodes, wherein the
laser beam interacts with the plasma, resulting in a hybrid plasma, and the laser beam also
acts directly upon the material being treated; feeding the material being treated through the
treatment region; and disposing the material being treated on a carrier membrane which is
driven through the process chamber.
The method may further comprise feeding the material being treated to the process chamber
through a twitcher system.
In an embodiment, the material being treated comprises strands of fibers or yarns.
In another embodiment, the material being treated comprises pieces of fabric material
disposed on the carrier membrane. The method may further comprise, prior to feeding the
fabric material through the process chamber, applying precursors or accelerants to the carrier
membrane as either (i) a spray, (ii) through roller deposition, (iii) through electrostatic
discharge or (iv) a bath through which the substrate is passed.
The treatment may comprise one or more of:
reacting the precursors or accelerants in the treatment region, to become incorporated
with (into or onto) the fabric material;
reacting the precursors or accelerants directly with the fabric material; and
reacting gases and chemistry in the plasma with the fabric material.
For each of the treatments, different process parameters may be employed to selectively
achieve desired results. Moreover, different sequences and combinations of the process
parameters may be employed on a given material being treated.
The method may further comprise using electrostatic deposition to dope fabrics or yard goods
materials with dopants before they enter the process chamber. In an embodiment, the dopants
comprise oxide powders or natural or synthetic fibers applied to the surface of the material
being treated. The method may further comprise applying oriented fibers or pre-doped fibers
to the surface of the material being treated.
The method may further comprise changing the topographical structure of materials which
comprise individual fibers or fibers or yarns within a woven or knitted fabric.
The method may further comprise performing different treatments on each side of a material
being treated.
The method may further comprise passing the material being treated several times through the
treatment region. In an embodiment, different precursors or different process parameters are
used at least some of these times.
The method may further comprise using a bank of laser beams impinging on the plasma.
There is also disclosed herein an apparatus for treating materials comprising:
two spaced-apart electrodes for generating a plasma in a treatment region; and
one or more lasers directing corresponding one or more beams into the treatment area to
interact with at least one of the plasma and the material being treated.
Some advantages of the present invention or embodiments thereof may include, without
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 ionized and energetic
reaction milieu for treating 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 initiate 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 properties.
The invention advantageously combines energy sources in a controlled atmospheric pressure
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 between 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 operate at atmospheric 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 rectangular cross-section exhibiting a consistent
power density over the entire treatment 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 chamber. 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 treated, 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 sol-gels and/or other organic or inorganic
precursors - i.e., changing the “recipe” - allows the system to generate a wide variety of
process applications.
There are at least several applications 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 substrate 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 penetration or a more intense coloring
process or reduction of dye temperature. For example, 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, potential 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.
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 (FIGs). The
figures are generally diagrams. Some elements in the figures may be exaggerated (not to
scale with respect to other elements), 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", "bottom", "left", "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.
is a diagram of a treatment system, according to an embodiment of the invention.
is a partial perspective view of a plasma region of the treatment system of
is a partial perspective view of a plasma region of the treatment system of
is a partial perspective view of a pre-treatment region, plasma region and post-
treatment region of the treatment system of according to some embodiments of the
invention.
FIGs. 4A - 4G are diagrams of elements in a treatment region of the treatment system of according to some embodiments of the invention.
shows a treatment system for fabric substrates supported by a carrier membrane, with
a “twitcher” system at the infeed.
FIGs. 5A, 5B are diagrammatic plan views of fabric substrate pieces supported on a carrier
membrane for transport through the treatment system.
is a diagram of a treatment system for strands of material.
FIGs. 6A, 6B, 6C are diagrams of treatment regimes for fabric substrates on doped carrier
membranes.
FIGs. 7A, 7B, 7C are diagrams of an embodiment of an MLSE system.
DETAILED DESCRIPTION OF EMBODIMENT(S) OF THE INVENTION
The invention relates generally to treatment (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
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
embodiments, 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 material having two surfaces, which may be termed
“front” and “back” surfaces, or “top” and “bottom” 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 skilled
in the art that the invention(s) may be practiced without some of the specific details being
presented herein. Furthermore, well-known features may be omitted or simplified in order not
to obscure the descriptions of the invention(s).
shows an overall surface treatment system 100 and method of performing treatment,
such as a surface treatment 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 substrate 102 may for example be a textile material and may be supplied 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 section 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 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 various sections
of the system 100 to guide the material through the system.
The treatment section (or process chamber) 120 may generally comprise three regions (or
areas, or zones):
- optionally, a pre-treatment (or precursor) region 122,
- a treatment (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) atmospheric pressure (AP) plasma, the elements of which are
generally well known, some of which 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 atmospheric pressure (AP) plasma 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 (e1) and 214 (e2) are shown, one of which may be considered to
be a cathode, the other of which may be considered to be an anode. These two electrodes e1
and e2 may be disposed generally parallel with one another, extending parallel to the y axis,
and spaced apart from one another in the x direction. For example, the electrodes e1 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 material, and spaced apart from one another nominally, a
distance sufficient to allow for clearance of the thickness of the material processed. The
electrodes e1 and e2 may be disposed approximately 1 mm above the top surface 102a of the
substrate 102 being treated.
The electrodes e1 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 e1 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 treatment 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, approximately parallel to and between the
electrodes e1 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 e1 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 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 being generated by the
two electrodes e1 and e2. More particularly, the 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 laser beam 132 may make an angle of “a”
which is approximately less than 1 - 10 degrees 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 (“a” = 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 e1 and e2 or the substrate
102, or both.
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 region) with the substrate (material) being treated. In addition to
interacting with the first energy source, 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 sustained 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 e1 and e2, and in
the substrate 102 is disposed between the two electrodes e1 and e2. In both cases,
the plasma created by the electrodes e1 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 e1 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 e1 and e2, a row of plasma jets (not shown) delivering a
plasma may be provided to create the desired plasma above the surface 102a of the substrate
102.
shows that in the pre-treatment region (area) 122, a row of spray heads (nozzles) 322
covering the full width of the material to be treated, or other suitable means, may be used to
dispense precursor materials 323 in solid, liquid or gaseous phase onto the substrate 102 to
enable the processing of/for specific properties 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
treatment (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 treated (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 treatment region (124)
FIGs. 4A - 4G illustrate various embodiments of elements in the treatment region 124.
illustrates an embodiment 400A wherein:
- A first (“top”) roller 412 is operative to function as an electrode e1, 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 function as an electrode e2, and may
have a diameter of approximately 15cm, and a length (into the page) of 2 meters. 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 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 (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 adjacent 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 12 cm,
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 between 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 between the
rollers 416 and 414.
- A second (“left”) nip or feed roller 418 (n2) is disposed adjacent a bottom-left (as
viewed) quadrant of the 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 12 cm,
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 between 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 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 and containing the plasma. The overall cavity 440 may comprise a first
(“right”) portion 440a in the space between the top, right and bottom rollers 412, 416, 414 and
a second (“left”) portion 440b in the space between 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 necessary. However, end caps or plates (not
shown) may be disposed 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 instead 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 through), 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 precursor 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 precursor 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 plasma.
shows an arrangement 400E incorporating a row of HV plasma nozzles (jets) 430,
rather than the cylindrical electrodes e1 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 provide 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 pre-treatment region 122. A
shield (not shown) such as 420 (refer to ) may be incorporated to contain the hybrid
plasma.
This arrangement enables treatment of metallic or other conductive substrates.
illustrates an embodiment 400F a first (“top”) roller 412 operative to function as an
electrode e1 (or anode), a second (“bottom”) roller 414 operative to function as an electrode
e2 (or cathode), and two nip rollers 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, although they will still help contain the plasma, they may not function as feed
rollers, and separate feed rollers (not shown) may need to be provided .
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 a reactive metallic plasma which may readily couple with the
substrate surface radicals to create nano-layer coatings with metallic composition on the
substrate material. The metallic material (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 nano-scale layers.
The metallic material coating the rollers 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 material, 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 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.)
illustrates an embodiment 400G using two flat sheet, plate electrodes 452 and 454,
rather than rollers (412, 414), spaced apart from one 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 region is indicated by the circle 440a, the laser beam is indicated 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 of the 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 material being treated, precursor materials 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 silanes (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 further penetrate the thickness of porous substrates. shows that suction
means, such as platen (bed) 324 over which the substrate 102 passes, in the treatment area
124, may be provided with a plurality of holes and connected in a suitable manner to suction
means (not shown) to create the desired effect. 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 function.
It should be understood that the process is dry and has a low environmental 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 materials with at least two energy sources,
wherein the two energy sources comprise (i) an AP plasma produced by various 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
invention that two or more lasers may be used.
Some exemplary parameters for generating the plasma in the treatment region are 1 - 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 described. 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 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 material. In this manner, both surfaces 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) material. In some cases, both top and
bottom surfaces as well as the core of the 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 suitable 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 microwave and laser, or microwave and
electromagnetically generated 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 of process steps may be performed, such as:
step 1 - (optional) precursor application,
step 2 - exposure to hybrid energy,
step 3 - (optional) precursor or finishing 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 introduce 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%
Reactive Gas O2 … 20%
Flow rate 15 liter/min Pressure: slightly above 1 bar
Power 2 KW
Treatment 2 - Dyeability
Precursor
Either no precursor or other precusor catalysts
Laser
Frequency 250Hz
Power 380 mJ
Plasma
Carrier Gas Argon … 80%
Reactive Gas O2 or N2 … 20%
Flow rate 15 liter/min Pressure: slightly above 1 bar
Power 2 KW
Treatment 3 - Hydrophobicity
Precursor octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble,
hydrogen methyl polysiloxane mixed with polydimethylsiloxane with polyglycolether (water
soluble) or combination of the 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 relevant additives - these are essentially 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
Treatment 4 - Fire retardancy
Precursor
Copolymers and Terpolymers based on siloxane/silane and polyborosiloxane with key
inorganic compounds, essentially transition oxides of titanium, 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
soluble) mixed with polydimethylsiloxane with polyglycolether (water soluble) or
combination 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 phosphate
- 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 (fumed,
gel or amorphous), Al2O3, 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 laser). 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 CO2 or N2 … 2-20%
Flow rate 10-20 liter/min Pressure: slightly above 1 bar
Power 0.5 – 1 KW
Treatment 5 - Anti Microbial
Precursor
siloxane/silane blends as per hydrophobicity platform, with the addition of
octadecyldimethyl (3triethoxysilpropyl) ammonium chloride.
octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble)mixed with
polydimethylsiloxane with polyglycolether (water soluble) or combination of above with
polydimethylsiloxanewith additives of:
- octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride),
- Chitosan
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 10-20 liter/min Pressure: slightly above 1 bar
Power 0.5 - 1 KW
Some Additional Embodiments and Enhancements
Some additional embodiments, variations of the techniques and applications for the “MLSE”
(Multiplexed Laser Surface Enhancement) system described hereinabove will now be
described, some of which have may have been discussed only briefly.
Processing non-rolled fabrics
The system described above shows treating fabrics running roll-to-roll. The techniques
disclosed herein may also be used for “yard goods”, including polymeric and composite films.
As mentioned above, rigid materials such as flat sheets of glass (such as for touch screens)
may be treated by the techniques disclosed herein. Three-dimensional (3D) components may
also be treated with the system.
The system may be modified to run non-rolled fabrics, such as pieces of fabric that are not
rolled, but supplied loose, allowing “short run” fabrics such as expensive or high performance
materials (including materials inherently not well-suited to roll format). As described in
greater detail hereinbelow, these pieces of fabric (substrates being treated) may be disposed
on a carrier membrane, as described below.
illustrates a MLSE system 500 using (by way of example) a configuration such as in
where the left and right rollers 416 and 418 are moved slightly outward from the
(nip) rollers 412 and 414, thereby opening up the cavity 440 to allow for thicker and /or stiffer
substrates to be processed through the system. The material being treated, in this case a
plurality of exemplary fabric substrate pieces 504 on a continuous carrier membrane 502 may
be driven through the reaction zone (energy milieu) of the system by the outside feeding and
take up rollers 416 and 418 (“n1” and “n2”). The fabric pieces 504 on the carrier membrane
502 may be stretched and tensioned prior to passing through the MLSE process such as by
first feeding the carrier/substrates through a traditional “twitcher” system 520.
Processing loose fibers, fragile membranes, individual fibers
shows that substrates 500 comprising fragile and loose structures and membrane
substrates (such as carded wool) 504 can be processed (transported for treatment) through the
MLSE system using a backing membrane (carrier) 502 of natural or manmade fabrics to
support the loose structure(s) 504 which may be held in place on the backing membrane 502
by (i) the natural affinity of two materials (502, 504), or (ii) electrical discharge fixing or (iii)
suitable bonding media (tacky or temporary adhesive).
shows that loose fibers 506, such as individual fibers or clumps of individual fibers
(e.g. raw wool) can be processed through the MLSE system using a backing membrane
(carrier) 502 of natural or manmade fabrics to support the loose structure(s) 514 which may
be held in place on the backing membrane 502 by (i) the natural affinity of two materials
(502, 504), or (ii) electrical discharge fixing or (iii) suitable bonding media (tacky or
temporary adhesive).
shows that the MLSE process can be adapted to process individual or multiple
strands 508 of fibers or yarns. The equipment may run either (i) reel-to-reel, with the MLSE
process chamber 510 treating single or multiple strands; or (ii) may use pre-prepared single
rolls (bobbins) B of multiple strands which are wound off and onto individual drums D.
Grooved guide rollers (not shown) may be to guide the strands through the system. individual
bobbins or drums. As the strands of individual fibers are passing through the system, the
MLSE process parameters may be maintained constant, or may be varied.
Precursor Application
Precursors or accelerants converted during the MLSE process can be pre-applied to the carrier
or fabric material, and presented to the MLSE system either wet or dry. This process may be
referred to as “doping”. These precursors or accelerants may be applied to the carrier or
fabric material as either (i) a spray, (ii) through roller deposition, (iii) through electrostatic
discharge or (iv) a bath through which the carrier or fabric material is passed. Carrier or
fabric material being treated can be soaked, then allowed to dry (partially or completely), then
passed through the MLSE system. This may be applicable to loose fibers, fragile membranes,
individual fibers.
The precursor or accelerants (“dopants”) may be in the form of suspensions or solutions (for
example sol-gel materials). For example octamethylcyclotetrasiloxane/polydimethylsilane
blend (water soluble) and/or other silane or siloxane family of materials with additives of
calcium metaborate and/or boron solutions, silicon oxide and titanium iospropoxide applied
to fabrics and dried prior to MLSE treatment to effect fire retardancy. Other suitable
precursors may be used to provide functionalities such as hydrophilicity, hydrophobicilty or
antimicrobial protection.
Doped Carrier Membrane
Where loose fibers or fragile substrates are being processed, the carrier membrane may be
doped with a precursor or accelerant. During the treatment process, the carrier may lose only
a portion (such as 10%) of its doping, and can thus be reused a number of times before re-
doping the carrier. Carriers with different dopants can be prepared in advance (and “off
line”), and brought into service on an as-needed basis.
The elements within the precursor may react directly with the treated substrate or may react in
the process chamber with the other environmental elements to effect the chemical and
material synthesis at the surface of the substrate material.
Three treatment examples are now discussed, with respect to FIGs. 6A, B, C. In each
example, precursor material (“dopant”) 604 is resident on (has previously been applied to) the
carrier membrane 602 (compare 502) which is supporting pieces of fabric substrate 606 (such
as fabric material 504, 506) as they are transported through the process milieu, such as an
atmospheric plasma 610 created in a treatment region (process chamber, reaction chamber,
compare 120). The substrate pieces 606 on the doped carrier 602 may together be considered
to be an overall substrate 600 that may be fed through the treatment region (124).
In , the line 612 indicates that precursor (or accelerant) elements 604 may react in the
process chamber (treatment region) 610 to become incorporated with (into or onto) the
substrate 606. In , the line 614 indicates that precursor elements 604 may react
directly with the substrate 606. In , the line 616 indicates that process chamber
elements (gases, chemistry in the plasma, as discussed above) may react directly with the
substrate 606. In each example, different process parameters may be employed to selectively
achieve the desired results, and different sequences and combinations of the results may also
readily be obtained (different sequences and combinations of the process parameters may be
employed on a given substrate being treated).
Electrostatic deposition
Electrostatic deposition may be used to dope fabrics or yard goods materials before they enter
the MLSE process chamber. For example oxide powders, natural or synthetic fibers may be
applied to the surface of the substrate material. For example, oriented fibers or pre-doped
fibers may be applied to the substrate surface. This process (not shown) may proceed in a
manner similar to conventional “flocking” (the process of depositing many small fiber
particles, called “flock”, onto a surface) wherein the "flock" is given a negative charge whilst
the substrate is earthed (grounded).
Topographical Changes
The MLSE process can be used to change the topographical structure of individual fibers or
fibers or yarns within a woven or knitted fabric. These changes may affect/modify the
physical properties of the fibers, including but not limited to strength, wear resistance, surface
area etc. Generally, these topographical changes may be done independently of the
aforementioned chemical changes (such as with precursor material), but can certainly be done
in conjunction with those other surface treatment regimes.
The “topographical” changes to the substrate, which may also be considered to be “surface
treatments”, may include, but are not limited to:
- Re-melting or selective ablation may be used to smooth out surface imperfections
from extrusion or forming processes
- Inducing controlled surface roughness to increase friction of the surface
Unique structures, topography or texture can be created on the surface of the fiber,
reconfiguring the substrate to produce such structures as nano brushes created on the surface
of a polypropylene fiber. The topographically modified structures and fibers may be less
smooth, may exhibit linear structures, and may have increased surface area which may be
useful (for example) in filters such as for trapping microbes. A variety of applications for
topographically modified fabrics, treated by the techniques disclosed herein, are possible.
Application And Creation Of Metal And Ceramic Oxides
Using solgel materials in a range of formats, treatments with a range of compositions such as
metal or ceramic oxides are produced on or in the surface of the fiber substrate, either in
individual fibers or fibers in a woven or knitted fabric. This also includes the use of rare
earths to create “smart” functionality such as supermagnetism, electrical conductivity, sensing
capabilities, etc. For example, titanium oxide may be created in the surface of polyethylene
fibers using the MLSE system for self cleaning and antibacterial and durability properties.
Multifunctionality
The MLSE System can be used to create multifunctionality within a monolithic fiber, yarn,
knitted fabric, woven fabric, non woven materials or yard material. Some examples are:
- (Different Treatments on Different Sides) The process parameters of the MLSE
system can be altered to affect the depth of processing. The characteristic changes
effected can be controlled to be either throughout the fabric structure or to a controlled
depth. Thus, processing the fabric on two passes, with alternate process parameters on
either side allows components to be produced that have different properties on both
sides. For example, non-woven materials may be produced that exhibit
hydrophobicity on one face and hydrophilicity on the other, for use in such
applications as incontinence wear, engineering filters and medical bandages.
- (Single Precursor, multiple processing) A single precursor applied to the substrate can
be treated (processed) multiple times to effect different performance characteristics.
This may be achieved by passing the material being treated multiple (several) times
through the energy milieu (treatment region) with different MLSE process settings or
by using multiple energy sources simultaneously which react with different elements
within the substrate material.
- (Multiple Pass treatments) Multifunctionality can be achieved by running the substrate
through the MLSE process multiple times, each time using different precursors or
different process parameters. At each pass the reactions effected may be substantially
solely dependant on the new substrate applied or may be a composite reaction of the
new precursor with the chemistries effected at previous processing passes.
Laser Configuration
As discussed above, the laser beam may be shaped to provide a rectangular beam of
consistent power density across the entire treatment area. Some further variations and
enhancements are now discussed.
- (Laser Beam shaping) For specific applications and process milieu, the process can be
seen to work with different shaped beams, including but not limited to round, oval or
thin line profiles. Further, the option to provide a laser grating of different powers or
intensities working in unison across the treatment area may provide different process
results.
- (Multiple laser beam sources) The MLSE process can be configured with a device to
provide the laser energy into the process through an overlapping series (array) of
small, individual beams acting perpendicular to either the material or the process
chamber. This array can be created by either a series of individual fiber lasers or a
single beam with beam-splitting and a mirror arrangement. The array may be
incorporated into a fixed bank interacting with a block or plate plasma, or can be
incorporated into an assembly in which a fixed roller replaces one of the nip rollers in
the cylindrical electrode (e1, e2) configurations such as shown above.
- (Laser Wavelengths) The MLSE process can achieve different process parameters by
using different wavelength lasers, such as 172 nanometers to 10.6 microns, which will
include the use of different types of laser sources or lasers with tunable wavelengths
e.g. CO2, NdYag, Diode or Fiber lasers.
FIGs. 7A, 7B show a system 700 comprising a block plasma generator 702, a bank (such as a
plurality of laser beams 704 impinging on the plasma 706 and the material (substrate) 710
being treated. Multiple lasers may be used to generate the multiple beams, some individual
lasers may be used to generate several of the beams.
(compare ) shows a material substrate passing through roller electrodes e1,
e2),with a bank of lasers generating beams impinging on the plasma and the material
(substrate) being treated. These techniques are suitable for simple material substrates, or
pieces of fabric substrate on carrier membranes, as discussed above (FIGs. 5A, 5B).
Microencapsulation
Microencapsulation is the technology whereby chemical compounds are locked into
microcapsules, whereby the capsule structure is designed to degrade under certain
environmental conditions to release the stored chemical compounds. The chemical
compounds can be such things as drugs and medications or dye colorants. The method of
degradation may be time, heat, reaction with certain chemistries or electrical discharge. The
microcapsules may be bonded to a fabric structure. The current technology uses a heat setting
process in water over extended times to affix the microcapsules to the fabric weave. Thus, the
capsule structure needs to be resilient enough to withstand the affixing method.
The MLSE system disclosed herein can be used to created covalent bonding of microcapsules
to a substrate surface dry, either using the environmental gases or other suitable precursors,
substantially instantaneously, with minimal heat dispersed into the capsule structures. This
may allow for a new generation of super-sensitive microencapsulation technologies.
Atomic Layer Deposition
The process parameters of the MLSE system can be modified to produce a membrane
structure over the substrate which is an atomic layer deposition. For example carbon or silicon
based structures.
While the invention has been described with respect to a limited number of embodiments,
these should not be construed as limitations on the scope of the invention, 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, based on the disclosure set forth herein, and as may be claimed.
Claims (16)
1. A method for treating a textile material comprising: creating a high voltage alternating current atmospheric pressure plasma in a process chamber having a treatment region between two spaced-apart electrodes, wherein the two electrodes are first and second rollers disposed substantially parallel to each other with a gap therebetween, to allow the material to be fed between the rollers; directing a laser beam into the plasma, approximately parallel to and between the electrodes, wherein the laser beam interacts with the plasma, resulting in a hybrid plasma, and the laser beam also acts directly upon the material being treated; feeding the material being treated through the treatment region; and disposing the material being treated on a carrier membrane which is driven through the process chamber.
2. The method of claim 1, further comprising: feeding the material being treated to the process chamber through a twitcher system.
3. The method of claim 1, wherein the material being treated comprises: strands of fibers or yarns.
4. The method of claim 1, wherein the material being treated comprises: pieces of fabric material disposed on the carrier membrane.
5. The method of claim 4, further comprising: prior to feeding the fabric material through the process chamber, applying precursors or accelerants to the carrier membrane as either (i) a spray, (ii) through roller deposition, (iii) through electrostatic discharge or (iv) a bath through which the substrate is passed.
6. The method of claim 5, wherein treatment comprises one or more of: reacting the precursors or accelerants in the treatment region, to become incorporated with (into or onto) the fabric material; reacting the precursors or accelerants directly with the fabric material; and reacting gases and chemistry in the plasma with the fabric material.
7. The method of claim 6, wherein, for each of the treatments, different process parameters are employed to selectively achieve desired results.
8. The method of claim 7, wherein different sequences and combinations of the process parameters are employed on a given material being treated.
9. The method of claim 1, further comprising: using electrostatic deposition to dope fabrics or yard goods materials with dopants before they enter the process chamber.
10. The method of claim 9, wherein the dopants comprise oxide powders or natural or synthetic fibers applied to the surface of the material being treated.
11. The method of claim 10, further comprising: applying oriented fibers or pre-doped fibers to the surface of the material being treated.
12. The method of claim 1, further comprising changing the topographical structure of materials which comprise individual fibers or fibers or yarns within a woven or knitted fabric.
13. The method of claim 1, further comprising performing different treatments on each side of a material being treated.
14. The method of claim 1, further comprising: passing the material being treated several times through the treatment region.
15. The method of claim 1, further comprising: using a bank of laser beams impinging on the plasma.
16. The method of claim 1, further comprising: passing the material being treated several times through the treatment region, at least some of the times using different precursors or different process parameters.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/536,257 | 2012-06-28 | ||
US13/536,257 US9309619B2 (en) | 2011-06-28 | 2012-06-28 | Method and apparatus for surface treatment of materials utilizing multiple combined energy sources |
PCT/US2012/071596 WO2014003822A1 (en) | 2012-06-28 | 2012-12-25 | Treating materials with combined energy sources |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ703898A NZ703898A (en) | 2016-08-26 |
NZ703898B2 true NZ703898B2 (en) | 2016-11-29 |
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