WO2020016853A1 - Thermal substrate with high-resistance magnification and positive temperature coefficient - Google Patents

Thermal substrate with high-resistance magnification and positive temperature coefficient Download PDF

Info

Publication number
WO2020016853A1
WO2020016853A1 PCT/IB2019/056207 IB2019056207W WO2020016853A1 WO 2020016853 A1 WO2020016853 A1 WO 2020016853A1 IB 2019056207 W IB2019056207 W IB 2019056207W WO 2020016853 A1 WO2020016853 A1 WO 2020016853A1
Authority
WO
WIPO (PCT)
Prior art keywords
hrm
ptc
substrate
thermal substrate
ptc ink
Prior art date
Application number
PCT/IB2019/056207
Other languages
French (fr)
Other versions
WO2020016853A4 (en
Inventor
Shuyong XIAO
Richard C. Abbott
Original Assignee
LMS Consulting Group
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/041,076 external-priority patent/US10822512B2/en
Application filed by LMS Consulting Group filed Critical LMS Consulting Group
Publication of WO2020016853A1 publication Critical patent/WO2020016853A1/en
Publication of WO2020016853A4 publication Critical patent/WO2020016853A4/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/027Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06573Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
    • H01C17/06586Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/021Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient formed as one or more layers or coatings
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/146Conductive polymers, e.g. polyethylene, thermoplastics
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/20Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/20Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H05B3/342Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs heaters used in textiles
    • H05B3/347Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs heaters used in textiles woven fabrics
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013Heaters using resistive films or coatings
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/014Heaters using resistive wires or cables not provided for in H05B3/54
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017Manufacturing methods or apparatus for heaters
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/02Heaters using heating elements having a positive temperature coefficient

Definitions

  • the present disclosure relates to the field of PTC inks. It relates to applications that use PTC inks exhibiting switching characteristics, high resistance magnification and the delayed onset of NTC behavior in a temperature range relevant to a particular application.
  • PTC positive temperature coefficient
  • PTCR positive temperature coefficient of resistivity
  • Polymers can be made electrically conductive by dispersing suitable amounts of conductive particles such as carbon black or fine metal particles.
  • a sub-class of electrically conductive polymers can be made to exhibit PTC behavior.
  • Polymeric compositions exhibiting PTC behavior and devices incorporating the same have been used in many applications, especially in the electronics industries.
  • a common use in an electronic circuit is limitation of current which is controlled by the temperature of a PTC element forming part of the circuit.
  • An increasing use of PTC materials is for constant temperature heaters.
  • NTC Negative Temperature Coefficient
  • transition temperature region between the low resistance state and the high resistance state where only partial current flows.
  • the transition region varies in width proportional to ambient temperature and the overall conditions for heat transfer. Therefore, the operational characteristics of the heater are determined by many design factors involving its physical environment. This affects the heater's power dissipation, the time-to- switch and the heater's hold current.
  • PTC inks One application for PTC inks is electrically heated fabrics. Electrically heated fabrics are used commonly in clothing for outdoor activities, medical devices and some industrial applications.
  • the term fabric as used herein refers to a woven material comprising threads or yarns or a non-woven material such as thermoplastic polyurethane when used as part of a garment.
  • heated fabrics utilizes heating elements of nickel-chromium or other resistive alloy in foil or wire form with a battery as a portable energy source.
  • Another class uses polymer films with electrically conductive polymers deposited on a film as described in EiS Pat. No. 9,161,393 B2.
  • Pat. No. CN 104,476,890 B describes printing directly on the fabric using screen printing.
  • the heating elements placed adjacent to or attached to the fabric, typically provide non-uniform heat and develop constant power in the element.
  • the metal interconnects are subject to bending and cracking thereby causing heater failure.
  • conductive polymers that are not PTC require controls and when PTC inks are used, they are subject to NTC failure or burn out together with poor self-regulation due to their small resistance multiplication.
  • Fabrics with heating elements woven like threads into the fabric constitute yet another class. Wires have been woven into the fabric as described in Pat. No. US 1,703,005 A. In Pat. No. GB 2,092,868 A, a metallized woven fabric is described, its purpose being to solve the problem of stretching. In most cases described, a simple voltage regulator adjusts temperature level with no feedback control. Also, the woven wires are problematic for making good electrical connections. They are subject to damage because their small size is determined by the electrical resistance necessary to generate low power and not the robustness of the fabric.
  • Pat. No. US 7,151,062 B2 describes a woven fabric with yarns coated with conductive polymers including PTC ink comprising coated spheres.
  • the PTC ink described is subject to the deficiencies of common PTC inks as described above.
  • US‘062 also claims wire conductors to serve as interconnects cross-woven to the conductive yarns.
  • a thermal substrate comprising a substrate and a high- resistance magnification (HRM) PTC ink and a substrate, wherein the HRM PTC ink that has a positive temperature coefficient (PTC) and a resistance magnification of at least 15 in a temperature range of at least 20 degrees Celsius above a switching temperature of the HRM PTC ink.
  • HRM high- resistance magnification
  • the resistance magnification of the HRM PTC ink may be at least 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180 or 200.
  • the temperature range may be 25 degrees Celsius, 30 degrees Celsius, 35 degrees Celsius or 40 degrees Celsius above the switching temperature.
  • the switching temperature of the HRM PTC ink may be between 0 and 160 degrees Celsius.
  • the HRM PTC ink may be a double resin ink that comprises: a first resin that provides a first PTC effect in a first temperature range; and a second resin that provides a second PTC effect in a second temperature range, wherein the second temperature range is higher than the first temperature range.
  • the double-resin HRM PTC ink may comprise about 10-30 wt % conductive particles; about 5-15 wt % of a first polymer resin; about 5-15 wt % of a second polymer resin; about 40-80 wt % of an organic solvent; and about 0-5 wt % other additives.
  • the conductive particles can be one of, or a mixture of: a metallic powder, a metal oxide, carbon black and graphite.
  • the first polymer resin may be a kind of crystalline or semi crystalline polymer, such as polyurethane, nylon, and polyester.
  • the second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
  • the selection of the solvent is based on its proper boiling point and the solubility of polymer resins, since the polymer resins are completely dissolved in the organic solvent prior to blending with other components. Any organic, inert liquid may be used as the solvent for the so long as the polymer is fully solubilized.
  • the solvent may be selected from MEK, N-methyl pyrolidone (NMP), toluene, xylene, and the like.
  • the other additives include a dispersing/wetting additive and a rheology additive.
  • the HRM PTC ink may comprise about 5-15 wt% of a thermally active polymer resin- 1 having a melting point of 30-70° C and providing a first temperature coefficient characteristic in the first temperature range below 70 0 C; about 5-15 wt% thermally active polymer resin-2 having a melting point of 70-140° C and providing a second positive temperature coefficient characteristic in the second temperature range above 70° C; about 10-30 wt% conductive particles; about 40-80 wt% organic solvent having a boing point higher than 100° C, the organic solvent being capable of dissolve both the polymer resin- 1 and polymer resin-2, and about 0-5 wt% additives.
  • the additives may comprise dispersing additives, wetting additives and rheological additives, with the additives having enhanced dispersing/wetting and rheology properties.
  • the first polymer resin may be a kind of crystalline or semi-crystalline polymer, such as polyurethane, nylon, and polyester.
  • the second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
  • the thermal substrate may be a fabric, a mesh or a film.
  • the HRM PTC ink may be deposited onto the substrate.
  • deposition method include screen printing, use of a thick film dispenser or a 3-D printer.
  • the substrate is a fabric or mesh
  • deposition of the HRM PTC ink may provide a printed circuit with resistors in parallel.
  • the thermal substrate may further comprise electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer.
  • the HRM PTC ink may be deposited on at least one insulating thread, yam or filament that is incorporated into a fabric or mesh.
  • An insulator can seal the HRM PTC ink.
  • the HRM PTC ink may be deposited on at least one conducting thread, yarn or filament that is incorporated into a fabric or mesh, with the HRM PTC ink sealed on an outer surface thereof with a conductor.
  • An insulating layer may be applied to the conductor.
  • the substrate may be a film.
  • the film may be a polymer selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), aluminum and steel (for meshes), glass composite, molded plastic, high-density polyethylene (HDPE) and styrene ethylene butylene styrene (SEBS).
  • the thermal substrate may comprise electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer.
  • An optional layer of a second film may be laminated onto the HRM PTC ink.
  • FIG. 1 shows the relationship of the PTC ratio R. T /R.25 versus temperature T of a typical PTC composition.
  • FIG. 2 shows the relative resistance magnification of a high-resistance magnification (HRM) PTC ink that exhibits an upper resistance magnification greater than 200 above a temperature of 70 Celsius.
  • HRM high-resistance magnification
  • FIG. 3 illustrates an embodiment of a printed circuit that comprises multiple resistors that regulate temperatures independently over each small area covered by each individual resistor.
  • FIG. 4A illustrates a cross-section of an embodiment of a PTC coating on an insulating yarn or filament.
  • FIG. 4B is a schematic of an embodiment of a mesh or fabric that incorporates an insulating yam or filament constructed as shown in FIG. 4A.
  • FIG. 4C illustrates a cross-section of an embodiment of a PTC coating on a conductive yarn or filament.
  • FIG. 4D is a schematic of an embodiment of a mesh or fabric that incorporates a conductive yam or filament constructed as shown in FIG. 4C.
  • FIGS. 5 A and 5B are each a schematic cross section of a PTC ink and interconnects deposited on a film (FIG. 5A) and subsequently laminated (FIG. 5B).
  • FIGS. 5C-5F are each a schematic cross section of a laminated HRM PTC thermal substrate positioned in thermal communication with a fabric or mesh.
  • FIG. 1 shows the relationship of the PTC ratio R1/R25 versus temperature T of a typical PTC ink composition.
  • the PTC ratio R T /R 2 5 also known as a“resistance magnification” or“resistivity magnification”
  • the PTC ratio R T /R25 IS defined as the ratio between a resistance Rr at temperature T and the resistance R25 at temperature 25° C.
  • the lower resistance at the onset of NTC leads to excessive current flow and the heating element is overpowered. Therefore, the NTC temperature region is a potential safety-risk temperature region.
  • FIG. 2 shows the relative resistance magnification of a high-resistance magnification (HRM) PTC ink suitable for applications in the present disclosure.
  • the HRM PTC ink exhibits the following properties: its switching temperature is at about 40° C; its resistance magnification (or PTC ratio R T/ TG S ) rises to about 200 within 30° C of the switching temperature; and it exhibits only PTC behavior 30° C beyond the switching temperature. That is, within a span of 30° C above the switching temperature, the current flowing through the HRM PTC ink is reduced by a factor of 200, thereby providing a self-regulating mechanism by which the power consumption is reduced by 200.
  • HRM PTC ink exhibits the following properties: its switching temperature is at about 40° C; its resistance magnification (or PTC ratio R T/ TG S ) rises to about 200 within 30° C of the switching temperature; and it exhibits only PTC behavior 30° C beyond the switching temperature. That is, within a span of 30° C above the switching temperature,
  • the HRM PTC ink has an upper resistance magnification greater than 200 above a temperature of 70° C. Furthermore, no NTC effect is observable 30° C above the switching temperature, implying use of the HRM PTC ink is safe within this temperature range.
  • the NTC effect is well above the switching temperature as compared to the NTC effect depicted in FIG. 1.
  • hysteresis effects are absent, transition regions are short and resistance recovery times are short.
  • the slope of the curve for the HRM PTC ink in Fig. 2 is steeper than that depicted in FIG. 1, which allows more tightly controlled temperature regulation.
  • the HRM PTC ink of FIG. 2 may be used in applications where a PTC effect, along with a high resistance magnification (i.e. power consumption reduction) are required between about 40° C and 70° C.
  • the high resistance magnification can be greater than 50, or greater than 100, or greater than 150, in the temperature range of interest.
  • HRM PTC ink with a) a switching temperature; b) PTC effect; and c) high resistance magnification in the required temperature range.
  • An example of an HRM PTC ink is disclosed in US Pat. Pub. No. 20170327707, incorporated herein by reference. However, as discussed above, any HRM PTC ink that exhibits substantially similar characteristics may be used. The requisite HRM PTC ink exhibits a switching temperature, high resistance magnification and a PTC effect over the temperature range required for the application.
  • the HRM PTC ink may comprise a first resin that provides a first PTC effect in a first temperature range and a second resin that provides a second PTC effect in a second temperature range, wherein the second temperature range is higher than the first temperature range.
  • the double-resin HRM PTC ink may comprise about 10-30 wt % conductive particles; about 5-15 wt % of a first polymer resin; about 5-15 wt % of a second polymer resin; about 40-80 wt % of an organic solvent; and about 0-5 wt % other additives.
  • the conductive particles can be one of, or a mixture of: a metallic powder, a metal oxide, carbon black and graphite.
  • the first polymer resin may be a kind of crystalline or semi crystalline polymer, such as polyurethane, nylon, and polyester.
  • the second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
  • the selection of the solvent is based on its proper boiling point and the solubility of polymer resins, since the polymer resins are completely dissolved in the organic solvent prior to blending with other components.
  • Any organic, inert liquid may be used as the solvent for the so long as the polymer is fully solubilized.
  • the solvent may be selected from MEK, N-methyl pyrolidone (NMP), toluene, xylene, and the like.
  • the other additives include a dispersing/wetting additive and a rheology additive.
  • the HRM PTC ink may comprise about 5-15 wt% of a thermally active polymer resin- 1 having a melting point of 30-70° C and providing a first temperature coefficient characteristic in the first temperature range below 70 0 C; about 5-15 wt% thermally active polymer resin-2 having a melting point of 70-140° C and providing a second positive temperature coefficient characteristic in the second temperature range above 70° C; about 10-30 wt% conductive particles; about 40-80 wt% organic solvent having a boing point higher than 100° C, the organic solvent being capable of dissolve both the polymer resin- 1 and polymer resin-2, and about 0-5 wt% additives.
  • the additives may comprise dispersing additives, wetting additives and rheological additives, with the additives having enhanced dispersing/wetting and rheology properties.
  • the first polymer resin may be a kind of crystalline or semi-crystalline polymer, such as polyurethane, nylon, and polyester.
  • the second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
  • the HRM PTC ink can provide the elimination of NTC and therefore avoid catastrophic failure.
  • the high resistivity of the HRM PTC ink in a temperature window of 20° C to 40° C above the switch temperature can provide precise temperature self-regulation with rapid time-to- temperature.
  • Non-limiting examples of a substrate include a fabric, a mesh and a film.
  • the present disclosure describes applications of the HRM PTC ink described above that extends or eliminates the onset of the NTC effect, offers magnification factors greater than 15, 25, 50, 100, 150 or 200, and switches in the range of 0°- 160° C. Such applications are therefore safer, more reliable and dissipate minimal power at the switch temperature. Moreover, the wide switch temperature range of HRM PTC inks offers greater design flexibility and the steep temperature-resistance transition enables tighter temperature control.
  • Thermal substrates that use HRM PTC ink may be created using various materials - depending on the specific application. For example, for outdoor wear, a nylon fabric may be used. For an industrial application that requires a higher operating temperature, a woven glass fiber mesh may be used. Similarly, various substrates may be used depending on the parameters of the application. For example, for clothing where low- weight and flexibility are required, thermoplastic polyurethane (TPU), polyester or a natural fabric such as cotton or a cotton blend is appropriate.
  • TPU thermoplastic polyurethane
  • polyester polyester
  • a natural fabric such as cotton or a cotton blend is appropriate.
  • a thermal substrate may be made by deposition of a HRM PTC ink onto a fabric or mesh.
  • the HRM PTC ink may be deposited on the substrate by various techniques. For example, screen printing onto a substrate may be used successfully because of the favorable dispersion of the HRM PTC ink. Other suitable techniques include gravure or rotogravure (e.g. “doctor blade”) methods.
  • the HRM PTC ink may also be dispensed over simple or complex surfaces using nozzles mounted on programmable robots or embedded in components by 3-D printing. Other methods of depositing a HRM PTC ink with substantial accuracy are known in the art.
  • interconnects e.g. contacts and bus lines
  • other metals e.g. metal foils or wires
  • metal alloys or electrically conductive materials such as, but not limited to, aluminum, copper, nickel and alloys thereof, or highly conductivity electronic polymers
  • interconnects can be designed for minimal length to lessen the possibility of cracking.
  • An HRM PTC ink is methodically deposited on a substrate such that the resulting circuit pattern provides for optimum power delivered by the resulting thermal substrate.
  • the switch temperature is determined by the composition of the HRM PTC ink
  • the power delivered by the thermal substrate is determined by the HRM PTC ink’s circuit pattern.
  • FIG. 3 depicts a printed circuit that comprises multiple deposits of printed HRM PTC ink.
  • Each deposit of ink 380 acts as a resistor that regulates temperatures independently over a small area covered by the individual resistor 380.
  • Each resistor 380 in a column is powered by line voltage busses 390 and interconnects 391.
  • the printed circuit arises from deposition of the HRM PTC ink and conductive interconnects onto the substrate, as described above.
  • the power, P is determined by arranging the printed resistors in parallel in a column on the substrate, as shown in FIG. 3.
  • the power dissipated by a column, P coi is:
  • the resistors may have a length of from about 0.2 cm to about 10 cm.
  • the temperature at each resistor is independently regulated. This circuit pattern allows independent temperature control of small areas, controlled power delivery and temperature uniformity, or non-uniformity if desired, over the surface of the substrate regardless of the local thermal load.
  • the gap between discrete resistors may also be reduced to zero to form a contiguous line of resistors with identical behavior of the heater, i.e. local self-regulation in response to local thermal load conditions. In all cases, the resistivity of the HRM PTC ink may be adjusted appropriately.
  • the HRM PTC ink may be deposited on a thread, yarn or mesh element for weaving into a fabric or mesh to create a thermal fabric or mesh.
  • FIG. 4A illustrates a cross-section of an HRM PTC coating 420 on an insulating thread, yarn or filament 410.
  • the HRM PTC ink is deposited as a coating 420 on the insulating thread, yarn or filament 410 and preferably sealed for electrical isolation on the outer surface with an insulating polymer 430. Coating and sealing may be done by dipping, extrusion or vapor deposition. Conduction of current is therefore along the length of the thread, yarn or filament. In this configuration, the HRM PTC ink is formulated for low resistivity, while multiple coated threads, yarns or filaments may be connected in parallel.
  • the HRM PTC ink 472 can be deposited on a conductive thread, yam or filament 471 (e.g. such as a copper wire) and coated with another electrically conductive layer 473 such as copper or silver. As above, there can be an optional insulating layer 474 around the conductive layer 473. In this case, the HRM PTC ink may be formulated for high resistivity and electrical current flows radially inward from the outer conductive layer 473 to the conductive thread 471.
  • FIG. 4C illustrates an example of how the coated threads 460 may be woven into the weft of a fabric or mesh to form a thermal substrate using an insulator as a thread, yam or filament.
  • Wires 450 and 451 carry supply voltage and are woven into the warp.
  • Contact with the heater threads can be made by coating with pressure-sensitive adhesive and subsequently simultaneously applying heat and pressure, pulse welding, swaging, sealing with an overcoat or other means known in the art.
  • the remaining threads 470 in the warp are standard fabric or mesh materials, e.g. polyester.
  • FIG. 4D is a schematic of a mesh or fabric that incorporates a conductive yarn or filament constructed as shown in FIG. 4C.
  • One wire carrying supply voltage 480 makes contact with the outer conductor layer of the heater threads 490, which constitute the weft; the other wire 481 makes contact with the inner conductor of the coated threads.
  • the remaining threads 495 are the customary fabric material.
  • the inner conductors are exposed by stripping the HRM PTC ink from the threads with solvent or mechanical means.
  • a thermal substrate 505 may be made by depositing the HRM PTC ink 510 and conductive interconnects 511 onto a polymer film 520, as shown in FIG. 5A.
  • the printed elements may be subsequently encapsulated by optionally laminating a second film 530 of the same composition (as that of film 520), resulting in a laminated thermal substrate 535, as shown in FIG. 5B.
  • Lamination may be achieved by using a pressure and temperature adhesive.
  • Suitable substrate and encapsulation materials include, but are not limited to: polyester, polyimide, polypropylene, rubber, silicone, thermoplastic polyurethane, laminates, ethylene-vinyl acetate (EVA) adhesive film, acrylate adhesive film and silicon adhesive film, fabric, silicone, and polyethylene terephthalate (PET). Additionally, the fabric or mesh heated by the thermal substrate 505 may have other layers of materials bonded to it such as, but not limited to: adhesive films, thermal barriers, reflective films, high or low emissivity films, absorptive films, alkaline resistant films, ground planes or EMI/RFI protective layers.
  • the laminated thermal substrate 535 can be positioned in thermal communication with a fabric or mesh 560 in order to heat the fabric or mesh 560, as shown in FIG.5C.
  • the laminated thermal substrate 535 may be merely positioned close to the fabric or mesh 560 to be in contact therewith. While laminated thermal substrate 535 (of FIG. 5B) is shown, thermal substrate 505 (of FIG. 5 A) may be used in place of the laminated thermal substrate 535.
  • the laminated thermal substrate 535 may be attached to the fabric or mesh 560 by a fastener 570 (such as, but not limited to: a rivet, snap, clasp or stud), as shown in FIG.
  • a fastener 570 such as, but not limited to: a rivet, snap, clasp or stud
  • thermo substrate 535 (of FIG. 5B) is shown in in FIG. 5C, the thermal substrate 505 (of FIG. 5A) may be used in place of the laminated thermal substrate 535.
  • the laminated thermal substrate 535 may not need to be proximate to the fabric or mesh 560. Then, an air gap 580 may be configured, as shown in FIG. 5E, between the laminated thermal substrate 535 and the fabric or mesh 560. While laminated thermal substrate 535 (of FIG. 5B) is shown, the thermal substrate 505 (of FIG. 5A) may be used in place of the laminated thermal substrate 535.
  • FIG. 5F illustrated a configuration where a laminated thermal substrate 535 is fastened to a mesh or fabric 560, and placed near a layer of material 590, with an air gap 580.
  • a heated jacket can have a fabric lining that has an HRM PTC film attached thereto, along with a waterproof fabric that forms an outer layer of the jacket.
  • the fabric or mesh heated by the thermal film may have a sensor positioned proximate to it or laminated in it, Furthermore, it may use a feedback loop to adjust its temperature based on the sensor.
  • the HRM PTC ink itself may be used as its own temperature sensor since it manifests such a strong and repeatable relationship between resistance and temperature.
  • an auxiliary circuit may be configured to measure real-time heater resistance for an accurate temperature integrated over the entire thermal film.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

A thermal substrate that comprises a high-resistance magnification (HRM) positive- temperature coefficient (PTC) ink and a substrate, wherein the HRM PTC ink has a positive temperature coefficient (PTC) and a resistance magnification of at least 15 in a temperature range of at least 20 degrees Celsius above a switching temperature of the HRM PTC ink.

Description

THERMAL SUBSTRATE WITH HIGH-RESISTANCE MAGNIFICATION AND POSITIVE TEMPERATURE COEFFICIENT
TECHNICAL FIELD
[0001] The present disclosure relates to the field of PTC inks. It relates to applications that use PTC inks exhibiting switching characteristics, high resistance magnification and the delayed onset of NTC behavior in a temperature range relevant to a particular application.
BACKGROUND
[0002] The terms positive temperature coefficient (PTC) materials and positive temperature coefficient of resistivity (PTCR) materials, as used herein, refer to materials that increase resistivity nonlinearly when their temperature is raised. Reference may be made, for example, to U.S. Pat. Nos. 4,628, 187, 5, 181,006, 5,344,591, and 5,714,096, and Japanese Patent Publication Nos. 2008293672, 2009151976, and 2009199794. The temperature where the resistance increases nonlinearly, thereby reducing current, is referred to herein as the switch temperature.
[0003] Polymers can be made electrically conductive by dispersing suitable amounts of conductive particles such as carbon black or fine metal particles. A sub-class of electrically conductive polymers can be made to exhibit PTC behavior. Polymeric compositions exhibiting PTC behavior and devices incorporating the same have been used in many applications, especially in the electronics industries. A common use in an electronic circuit is limitation of current which is controlled by the temperature of a PTC element forming part of the circuit. An increasing use of PTC materials is for constant temperature heaters.
[0004] However, carbon-based polymeric PTC materials suffer from several important operational technical problems. For example, most PTC compositions exhibit Negative Temperature Coefficient (NTC) characteristics of resistivity immediately after the PTC characteristics. This change from PTC behavior to a strong NTC behavior is often undesirable and may cause self-burning in some cases. The lower resistance at the onset of NTC leads to excessive current flow and the resistor, or heater, is overpowered. Therefore, the NTC temperature region is a potential safety-risk temperature region. Various efforts have been made to reduce the NTC effect as described in U.S. Pat. Nos. 8,496,854 and 5,227,946 and European Pat. EP 0311142. However, the NTC effect is only reduced and not eliminated.
[0005] Another problem with current polymeric PTC materials is a low resistance magnification at the switch temperature, typically ranging from 5-15. This results in some power dissipation even at maximum resistance which results in poor temperature regulation.
[0006] Another problem is the transition temperature region between the low resistance state and the high resistance state where only partial current flows. The transition region varies in width proportional to ambient temperature and the overall conditions for heat transfer. Therefore, the operational characteristics of the heater are determined by many design factors involving its physical environment. This affects the heater's power dissipation, the time-to- switch and the heater's hold current.
[0007] Still another problem is that many PTC materials exhibit resistance hysteresis when switched. This is observed as a partial resistance increase over the starting resistance even hours after the switch event. In time, the original resistance is approached but it may be days, months or years. Fortunately, the resistance is not cumulative over subsequent switch events so strategies can be taken to account for this phenomenon.
[0008] Yet another problem is the PTC materiaTs resistance recovery time after a reset event. The time is usually one to two minutes but can be longer depending on the heat transfer environment of the heater and its material design.
[0009] One application for PTC inks is electrically heated fabrics. Electrically heated fabrics are used commonly in clothing for outdoor activities, medical devices and some industrial applications. The term fabric as used herein refers to a woven material comprising threads or yarns or a non-woven material such as thermoplastic polyurethane when used as part of a garment. One class of heated fabrics utilizes heating elements of nickel-chromium or other resistive alloy in foil or wire form with a battery as a portable energy source. Another class uses polymer films with electrically conductive polymers deposited on a film as described in EiS Pat. No. 9,161,393 B2. In yet another class, Pat. No. CN 104,476,890 B describes printing directly on the fabric using screen printing.
[0010] In all cases but the last, the heating elements, placed adjacent to or attached to the fabric, typically provide non-uniform heat and develop constant power in the element. In the last case, the metal interconnects are subject to bending and cracking thereby causing heater failure. In all cases, conductive polymers that are not PTC require controls and when PTC inks are used, they are subject to NTC failure or burn out together with poor self-regulation due to their small resistance multiplication.
[0011] Fabrics with heating elements woven like threads into the fabric constitute yet another class. Wires have been woven into the fabric as described in Pat. No. US 1,703,005 A. In Pat. No. GB 2,092,868 A, a metallized woven fabric is described, its purpose being to solve the problem of stretching. In most cases described, a simple voltage regulator adjusts temperature level with no feedback control. Also, the woven wires are problematic for making good electrical connections. They are subject to damage because their small size is determined by the electrical resistance necessary to generate low power and not the robustness of the fabric.
[0012] Pat. No. US 7,151,062 B2 describes a woven fabric with yarns coated with conductive polymers including PTC ink comprising coated spheres. The PTC ink described is subject to the deficiencies of common PTC inks as described above. US‘062 also claims wire conductors to serve as interconnects cross-woven to the conductive yarns.
SUMMARY
[0013] In one aspect, there is disclosed a thermal substrate comprising a substrate and a high- resistance magnification (HRM) PTC ink and a substrate, wherein the HRM PTC ink that has a positive temperature coefficient (PTC) and a resistance magnification of at least 15 in a temperature range of at least 20 degrees Celsius above a switching temperature of the HRM PTC ink.
[0014] The resistance magnification of the HRM PTC ink may be at least 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180 or 200. In addition, the temperature range may be 25 degrees Celsius, 30 degrees Celsius, 35 degrees Celsius or 40 degrees Celsius above the switching temperature. Furthermore, the switching temperature of the HRM PTC ink may be between 0 and 160 degrees Celsius.
[0015] As an example, the HRM PTC ink may be a double resin ink that comprises: a first resin that provides a first PTC effect in a first temperature range; and a second resin that provides a second PTC effect in a second temperature range, wherein the second temperature range is higher than the first temperature range. [0016] As an example, the double-resin HRM PTC ink may comprise about 10-30 wt % conductive particles; about 5-15 wt % of a first polymer resin; about 5-15 wt % of a second polymer resin; about 40-80 wt % of an organic solvent; and about 0-5 wt % other additives. The conductive particles can be one of, or a mixture of: a metallic powder, a metal oxide, carbon black and graphite. The first polymer resin may be a kind of crystalline or semi crystalline polymer, such as polyurethane, nylon, and polyester. The second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin. The selection of the solvent is based on its proper boiling point and the solubility of polymer resins, since the polymer resins are completely dissolved in the organic solvent prior to blending with other components. Any organic, inert liquid may be used as the solvent for the so long as the polymer is fully solubilized. As examples, the solvent may be selected from MEK, N-methyl pyrolidone (NMP), toluene, xylene, and the like. The other additives include a dispersing/wetting additive and a rheology additive.
[0017] As an example of the double resin composition, the HRM PTC ink may comprise about 5-15 wt% of a thermally active polymer resin- 1 having a melting point of 30-70° C and providing a first temperature coefficient characteristic in the first temperature range below 70 0 C; about 5-15 wt% thermally active polymer resin-2 having a melting point of 70-140° C and providing a second positive temperature coefficient characteristic in the second temperature range above 70° C; about 10-30 wt% conductive particles; about 40-80 wt% organic solvent having a boing point higher than 100° C, the organic solvent being capable of dissolve both the polymer resin- 1 and polymer resin-2, and about 0-5 wt% additives. The additives may comprise dispersing additives, wetting additives and rheological additives, with the additives having enhanced dispersing/wetting and rheology properties. The first polymer resin may be a kind of crystalline or semi-crystalline polymer, such as polyurethane, nylon, and polyester. The second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
[0018] The thermal substrate may be a fabric, a mesh or a film.
[0019] Furthermore, the HRM PTC ink may be deposited onto the substrate. Non-limiting examples of deposition method include screen printing, use of a thick film dispenser or a 3-D printer.
[0020] Where the substrate is a fabric or mesh, deposition of the HRM PTC ink may provide a printed circuit with resistors in parallel. In this case, the thermal substrate may further comprise electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer.
[0021] In other embodiments of the thermal substrate, the HRM PTC ink may be deposited on at least one insulating thread, yam or filament that is incorporated into a fabric or mesh. An insulator can seal the HRM PTC ink.
[0022] In other embodiments of the thermal substrate, the HRM PTC ink may be deposited on at least one conducting thread, yarn or filament that is incorporated into a fabric or mesh, with the HRM PTC ink sealed on an outer surface thereof with a conductor. An insulating layer may be applied to the conductor.
[0023] In other embodiments, the substrate may be a film. The film may be a polymer selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), aluminum and steel (for meshes), glass composite, molded plastic, high-density polyethylene (HDPE) and styrene ethylene butylene styrene (SEBS). As with the other embodiments, the thermal substrate may comprise electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer. An optional layer of a second film may be laminated onto the HRM PTC ink.
[0024] Additional features and advantages are realized through the techniques of the present invention. Other embodiments and aspects of the invention are described in detail herein and are considered a part of the claimed invention.
[0025] The recitation herein of desirable embodiments is not meant to imply or suggest that any or all of these embodiments are present as essential features, either individually or collectively, in the most general embodiment of the present invention or in any of its more specific embodiments.
BRIEF DESCRIPTION OF DRAWINGS
[0026] The foregoing and other advantages of the disclosure will become apparent upon reading the following detailed description and upon reference to the drawings.
[0027] FIG. 1 shows the relationship of the PTC ratio R.T/R.25 versus temperature T of a typical PTC composition. [0028] FIG. 2 shows the relative resistance magnification of a high-resistance magnification (HRM) PTC ink that exhibits an upper resistance magnification greater than 200 above a temperature of 70 Celsius.
[0029] FIG. 3 illustrates an embodiment of a printed circuit that comprises multiple resistors that regulate temperatures independently over each small area covered by each individual resistor.
[0030] FIG. 4A illustrates a cross-section of an embodiment of a PTC coating on an insulating yarn or filament.
[0031] FIG. 4B is a schematic of an embodiment of a mesh or fabric that incorporates an insulating yam or filament constructed as shown in FIG. 4A.
[0032] FIG. 4C illustrates a cross-section of an embodiment of a PTC coating on a conductive yarn or filament.
[0033] FIG. 4D is a schematic of an embodiment of a mesh or fabric that incorporates a conductive yam or filament constructed as shown in FIG. 4C.
[0034] FIGS. 5 A and 5B are each a schematic cross section of a PTC ink and interconnects deposited on a film (FIG. 5A) and subsequently laminated (FIG. 5B).
[0035] FIGS. 5C-5F are each a schematic cross section of a laminated HRM PTC thermal substrate positioned in thermal communication with a fabric or mesh.
[0036] While the present disclosure is susceptible to various modifications and alternative forms, specific embodiments or implementations have been shown by way of example in the drawings and will be described in detail herein. It should be understood, however, that the disclosure is not intended to be limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of an invention as defined by the appended claims.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0037] FIG. 1 shows the relationship of the PTC ratio R1/R25 versus temperature T of a typical PTC ink composition. When the temperature T is in excess of 70° C, the PTC ratio RT/R25 (also known as a“resistance magnification” or“resistivity magnification”) begins to decline. The PTC ratio RT/R25 IS defined as the ratio between a resistance Rr at temperature T and the resistance R25 at temperature 25° C. The lower resistance at the onset of NTC leads to excessive current flow and the heating element is overpowered. Therefore, the NTC temperature region is a potential safety-risk temperature region.
[0038] FIG. 2 shows the relative resistance magnification of a high-resistance magnification (HRM) PTC ink suitable for applications in the present disclosure. The HRM PTC ink exhibits the following properties: its switching temperature is at about 40° C; its resistance magnification (or PTC ratio RT/TGS) rises to about 200 within 30° C of the switching temperature; and it exhibits only PTC behavior 30° C beyond the switching temperature. That is, within a span of 30° C above the switching temperature, the current flowing through the HRM PTC ink is reduced by a factor of 200, thereby providing a self-regulating mechanism by which the power consumption is reduced by 200. In fact, further investigation reveals that the HRM PTC ink has an upper resistance magnification greater than 200 above a temperature of 70° C. Furthermore, no NTC effect is observable 30° C above the switching temperature, implying use of the HRM PTC ink is safe within this temperature range.
[0039] For example, common commercially available PTC inks typically manifest a resistance multiplication of 10-15, as shown in FIG. 1. On the other hand, the resistance magnification of an HRM PTC ink reaches 200 as shown in Fig. 2.
[0040] Moreover, the NTC effect is well above the switching temperature as compared to the NTC effect depicted in FIG. 1. In addition, hysteresis effects are absent, transition regions are short and resistance recovery times are short. Finally, the slope of the curve for the HRM PTC ink in Fig. 2 is steeper than that depicted in FIG. 1, which allows more tightly controlled temperature regulation.
[0041] These properties imply that the HRM PTC ink of FIG. 2 may be used in applications where a PTC effect, along with a high resistance magnification (i.e. power consumption reduction) are required between about 40° C and 70° C. The high resistance magnification can be greater than 50, or greater than 100, or greater than 150, in the temperature range of interest.
[0042] It follows that applications that require a PTC effect and high magnification resistance in a different temperature range can use an HRM PTC ink with a) a switching temperature; b) PTC effect; and c) high resistance magnification in the required temperature range. [0043] An example of an HRM PTC ink is disclosed in US Pat. Pub. No. 20170327707, incorporated herein by reference. However, as discussed above, any HRM PTC ink that exhibits substantially similar characteristics may be used. The requisite HRM PTC ink exhibits a switching temperature, high resistance magnification and a PTC effect over the temperature range required for the application.
[0044] For example, the HRM PTC ink may comprise a first resin that provides a first PTC effect in a first temperature range and a second resin that provides a second PTC effect in a second temperature range, wherein the second temperature range is higher than the first temperature range.
[0045] As an example, the double-resin HRM PTC ink may comprise about 10-30 wt % conductive particles; about 5-15 wt % of a first polymer resin; about 5-15 wt % of a second polymer resin; about 40-80 wt % of an organic solvent; and about 0-5 wt % other additives. The conductive particles can be one of, or a mixture of: a metallic powder, a metal oxide, carbon black and graphite. The first polymer resin may be a kind of crystalline or semi crystalline polymer, such as polyurethane, nylon, and polyester. The second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin. The selection of the solvent is based on its proper boiling point and the solubility of polymer resins, since the polymer resins are completely dissolved in the organic solvent prior to blending with other components. Any organic, inert liquid may be used as the solvent for the so long as the polymer is fully solubilized. As examples, the solvent may be selected from MEK, N-methyl pyrolidone (NMP), toluene, xylene, and the like. The other additives include a dispersing/wetting additive and a rheology additive.
[0046] As an example of the double resin composition, the HRM PTC ink may comprise about 5-15 wt% of a thermally active polymer resin- 1 having a melting point of 30-70° C and providing a first temperature coefficient characteristic in the first temperature range below 70 0 C; about 5-15 wt% thermally active polymer resin-2 having a melting point of 70-140° C and providing a second positive temperature coefficient characteristic in the second temperature range above 70° C; about 10-30 wt% conductive particles; about 40-80 wt% organic solvent having a boing point higher than 100° C, the organic solvent being capable of dissolve both the polymer resin- 1 and polymer resin-2, and about 0-5 wt% additives. The additives may comprise dispersing additives, wetting additives and rheological additives, with the additives having enhanced dispersing/wetting and rheology properties. The first polymer resin may be a kind of crystalline or semi-crystalline polymer, such as polyurethane, nylon, and polyester. The second polymer resin may be a kind of non-crystalline polymer, such as acrylic resin.
Thermal Substrate
[0047] In a thermal substrate comprising a substrate and an HRM PTC ink, the HRM PTC ink can provide the elimination of NTC and therefore avoid catastrophic failure. Moreover, the high resistivity of the HRM PTC ink in a temperature window of 20° C to 40° C above the switch temperature can provide precise temperature self-regulation with rapid time-to- temperature.
Non-limiting examples of a substrate include a fabric, a mesh and a film.
[0048] The present disclosure describes applications of the HRM PTC ink described above that extends or eliminates the onset of the NTC effect, offers magnification factors greater than 15, 25, 50, 100, 150 or 200, and switches in the range of 0°- 160° C. Such applications are therefore safer, more reliable and dissipate minimal power at the switch temperature. Moreover, the wide switch temperature range of HRM PTC inks offers greater design flexibility and the steep temperature-resistance transition enables tighter temperature control.
[0049] Thermal substrates that use HRM PTC ink may be created using various materials - depending on the specific application. For example, for outdoor wear, a nylon fabric may be used. For an industrial application that requires a higher operating temperature, a woven glass fiber mesh may be used. Similarly, various substrates may be used depending on the parameters of the application. For example, for clothing where low- weight and flexibility are required, thermoplastic polyurethane (TPU), polyester or a natural fabric such as cotton or a cotton blend is appropriate.
[0050] In general, all-natural fibers, many polymer films and, in the case of meshes, metal wires are amenable to heating with a HRM PTC ink.
First embodiment of a thermal substrate
[0051] In some embodiments, a thermal substrate may be made by deposition of a HRM PTC ink onto a fabric or mesh.
[0052] The HRM PTC ink may be deposited on the substrate by various techniques. For example, screen printing onto a substrate may be used successfully because of the favorable dispersion of the HRM PTC ink. Other suitable techniques include gravure or rotogravure (e.g. “doctor blade”) methods. The HRM PTC ink may also be dispensed over simple or complex surfaces using nozzles mounted on programmable robots or embedded in components by 3-D printing. Other methods of depositing a HRM PTC ink with substantial accuracy are known in the art.
[0053] Once the HRM PTC ink has been deposited on a fabric or mesh, silver or other conductive paste may be deposited on the substrate to create electrical interconnects (e.g. contacts and bus lines) for use in heater applications. In some embodiments, other metals (e.g. metal foils or wires), metal alloys or electrically conductive materials such as, but not limited to, aluminum, copper, nickel and alloys thereof, or highly conductivity electronic polymers may be deposited on the substrate as a paste or ink to create interconnects In all cases, interconnects can be designed for minimal length to lessen the possibility of cracking.
[0054] An HRM PTC ink is methodically deposited on a substrate such that the resulting circuit pattern provides for optimum power delivered by the resulting thermal substrate. For any given heating application, whereas the switch temperature is determined by the composition of the HRM PTC ink, the power delivered by the thermal substrate is determined by the HRM PTC ink’s circuit pattern.
[0055] FIG. 3 depicts a printed circuit that comprises multiple deposits of printed HRM PTC ink. Each deposit of ink 380 acts as a resistor that regulates temperatures independently over a small area covered by the individual resistor 380. Each resistor 380 in a column is powered by line voltage busses 390 and interconnects 391. The printed circuit arises from deposition of the HRM PTC ink and conductive interconnects onto the substrate, as described above.
[0056] Since the HRM PTC resistor 380 material typically has high sheet resistance, the power, P, is determined by arranging the printed resistors in parallel in a column on the substrate, as shown in FIG. 3. The power dissipated by a column, Pcoi, is:
P col V2/Rcol , where V is the applied voltage and Rcoiis the total resistance of the column. If the number of resistors in parallel within a column is ncoi and the resistance of individual resistor 380 is R, the resistance of the column, Red, is: Rcoi R/ncoi.
For a total of N columns (as depicted in FIG. 3), the total power dissipated by the sheet, P, is P = ncoi NV2/R.
The resistors may have a length of from about 0.2 cm to about 10 cm. The temperature at each resistor is independently regulated. This circuit pattern allows independent temperature control of small areas, controlled power delivery and temperature uniformity, or non-uniformity if desired, over the surface of the substrate regardless of the local thermal load. The gap between discrete resistors may also be reduced to zero to form a contiguous line of resistors with identical behavior of the heater, i.e. local self-regulation in response to local thermal load conditions. In all cases, the resistivity of the HRM PTC ink may be adjusted appropriately.
Second Embodiment of a thermal substrate
[0057] In other embodiments, the HRM PTC ink may be deposited on a thread, yarn or mesh element for weaving into a fabric or mesh to create a thermal fabric or mesh.
[0058] FIG. 4A illustrates a cross-section of an HRM PTC coating 420 on an insulating thread, yarn or filament 410. The HRM PTC ink is deposited as a coating 420 on the insulating thread, yarn or filament 410 and preferably sealed for electrical isolation on the outer surface with an insulating polymer 430. Coating and sealing may be done by dipping, extrusion or vapor deposition. Conduction of current is therefore along the length of the thread, yarn or filament. In this configuration, the HRM PTC ink is formulated for low resistivity, while multiple coated threads, yarns or filaments may be connected in parallel.
[0059] In another embodiment shown in FIG.4B, the HRM PTC ink 472 can be deposited on a conductive thread, yam or filament 471 (e.g. such as a copper wire) and coated with another electrically conductive layer 473 such as copper or silver. As above, there can be an optional insulating layer 474 around the conductive layer 473. In this case, the HRM PTC ink may be formulated for high resistivity and electrical current flows radially inward from the outer conductive layer 473 to the conductive thread 471.
[0060] FIG. 4C illustrates an example of how the coated threads 460 may be woven into the weft of a fabric or mesh to form a thermal substrate using an insulator as a thread, yam or filament. Wires 450 and 451 carry supply voltage and are woven into the warp. Contact with the heater threads can be made by coating with pressure-sensitive adhesive and subsequently simultaneously applying heat and pressure, pulse welding, swaging, sealing with an overcoat or other means known in the art. The remaining threads 470 in the warp are standard fabric or mesh materials, e.g. polyester.
[0061] FIG. 4D is a schematic of a mesh or fabric that incorporates a conductive yarn or filament constructed as shown in FIG. 4C. One wire carrying supply voltage 480 makes contact with the outer conductor layer of the heater threads 490, which constitute the weft; the other wire 481 makes contact with the inner conductor of the coated threads. The remaining threads 495 are the customary fabric material. The inner conductors are exposed by stripping the HRM PTC ink from the threads with solvent or mechanical means.
Third Embodiment of a thermal substrate
[0062] In yet another embodiment a thermal substrate 505 may be made by depositing the HRM PTC ink 510 and conductive interconnects 511 onto a polymer film 520, as shown in FIG. 5A. The printed elements may be subsequently encapsulated by optionally laminating a second film 530 of the same composition (as that of film 520), resulting in a laminated thermal substrate 535, as shown in FIG. 5B. Lamination may be achieved by using a pressure and temperature adhesive. Suitable substrate and encapsulation materials include, but are not limited to: polyester, polyimide, polypropylene, rubber, silicone, thermoplastic polyurethane, laminates, ethylene-vinyl acetate (EVA) adhesive film, acrylate adhesive film and silicon adhesive film, fabric, silicone, and polyethylene terephthalate (PET). Additionally, the fabric or mesh heated by the thermal substrate 505 may have other layers of materials bonded to it such as, but not limited to: adhesive films, thermal barriers, reflective films, high or low emissivity films, absorptive films, alkaline resistant films, ground planes or EMI/RFI protective layers.
[0063] If the primary heat transfer mechanism is conduction, the laminated thermal substrate 535 can be positioned in thermal communication with a fabric or mesh 560 in order to heat the fabric or mesh 560, as shown in FIG.5C. In the embodiment shown, the laminated thermal substrate 535 may be merely positioned close to the fabric or mesh 560 to be in contact therewith. While laminated thermal substrate 535 (of FIG. 5B) is shown, thermal substrate 505 (of FIG. 5 A) may be used in place of the laminated thermal substrate 535. [0064] Alternatively, the laminated thermal substrate 535 may be attached to the fabric or mesh 560 by a fastener 570 (such as, but not limited to: a rivet, snap, clasp or stud), as shown in FIG. 5D, or by various other means such as adhesives, sewing or removable clips. While laminated thermal substrate 535 (of FIG. 5B) is shown in in FIG. 5C, the thermal substrate 505 (of FIG. 5A) may be used in place of the laminated thermal substrate 535.
[0065] If the primary mode of heat transfer is infrared radiation or convection, the laminated thermal substrate 535 may not need to be proximate to the fabric or mesh 560. Then, an air gap 580 may be configured, as shown in FIG. 5E, between the laminated thermal substrate 535 and the fabric or mesh 560. While laminated thermal substrate 535 (of FIG. 5B) is shown, the thermal substrate 505 (of FIG. 5A) may be used in place of the laminated thermal substrate 535.
[0066] Whether the laminated thermal substrate 535 (or thermal substrate 505) is adjacent to the mesh or fabric 560 (as in FIG. 5C), fastened to the mesh or fabric 560 (as in FIG. 5D), or separated from the mesh or fabric 560 by an air gap 580 (as in FIG. 5E), an optional layer of material may be used for thermal insulation, water proofing, etc. FIG. 5F illustrated a configuration where a laminated thermal substrate 535 is fastened to a mesh or fabric 560, and placed near a layer of material 590, with an air gap 580. For example, in an embodiment, a heated jacket can have a fabric lining that has an HRM PTC film attached thereto, along with a waterproof fabric that forms an outer layer of the jacket.
[0067] In various applications, the fabric or mesh heated by the thermal film may have a sensor positioned proximate to it or laminated in it, Furthermore, it may use a feedback loop to adjust its temperature based on the sensor. In other applications, the HRM PTC ink itself may be used as its own temperature sensor since it manifests such a strong and repeatable relationship between resistance and temperature. In such an application, an auxiliary circuit may be configured to measure real-time heater resistance for an accurate temperature integrated over the entire thermal film.
[0068] While particular implementations and applications of the present disclosure have been illustrated and described, it is to be understood that the present disclosure is not limited to the precise construction disclosed herein and that various modifications, changes, and variations can be apparent from the foregoing descriptions without departing from the spirit and scope of an invention as defined in the appended claims.

Claims

1. A thermal substrate comprising an HRM PTC ink and a substrate, wherein the HRM PTC ink has a positive temperature coefficient (PTC) and a resistance magnification of at least 15 in a temperature range of at least 20 degrees Celsius above a switching temperature of the HRM PTC ink.
2. The thermal substrate of claim 1, wherein the resistance magnification is at least 50.
3. The thermal substrate of claim 2, wherein the temperature range is 30 degrees Celsius above the switching temperature.
4. The thermal substrate of claim 1, wherein the switching temperature is between 0 and 160 degrees Celsius.
5. The thermal substrate of claim 1, wherein the substrate is a fabric, a mesh or a film.
6. The thermal fabric of claim 1, wherein the HRM PTC ink comprises a first resin that provides a first PTC effect in a first temperature range and a second resin that provides a second PTC effect in a second temperature range, wherein the second temperature range is higher than the first temperature range.
7. The thermal substrate of claim 6, wherein the HRM PTC ink comprises:
a) 5-15 wt% of a thermally active first polymer resin having a melting point of 30-70° C and providing a first temperature coefficient characteristic in the first temperature range below 70° C,
b) 5-15 wt% of a thermally active second polymer resin having a melting point of 70-140 0 C and providing a second positive temperature coefficient characteristic in the second temperature range above 700 C,
c) 10-30 wt% conductive particles,
d) 40-80 wt% organic solvent having a boing point higher than 100 0 C, said organic solvent being capable of dissolve both the polymer resin- 1 and polymer resin-2, and e) 0-5 wt% additives, said additives comprising: dispersing additives, wetting additives and rheological additives, said additives having enhanced dispersing/wetting and rheology properties.
8. The thermal substrate of claim 7, wherein the first polymer resin comprises a crystalline or semi-crystalline polymer; and the second polymer resin comprises a non-crystalline polymer.
9. The thermal substrate of claim 1, further comprising electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer.
10. The thermal substrate of claim 9 wherein the HRM PTC ink is deposited onto the substrate.
11. The thermal substrate of claim 10 wherein the HRM PTC ink is deposited onto the substrate by screen printing, a thick film dispenser or a 3-D printer.
12. The thermal substrate of claim 10, wherein deposition of the HRM PTC ink provides a printed circuit with resistors in parallel.
13. The thermal substrate of claim 10 wherein the HRM PTC ink is deposited on at least one insulating thread, yarn or filament that is incorporated into a fabric or mesh.
14. The thermal substrate of claim 13, wherein an insulator seals the HRM PTC ink.
15. The thermal substrate of claim 10, wherein the HRM PTC ink is deposited on at least one conducting thread, yarn or filament that is incorporated into a fabric or mesh, and the HRM PTC ink is sealed on an outer surface thereof with a conductor.
16. The thermal substrate of claim 15, wherein an insulating layer is applied to the conductor.
17. The thermal substrate of claim 1, wherein the substrate is a film.
18. The thermal substrate of claim 17, wherein the film is a polymer selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), aluminum and steel (for meshes), glass composite, molded plastic, high-density polyethylene (HDPE) and styrene ethylene butylene styrene (SEBS).
19. The thermal substrate of claim 18, further comprising electrical interconnects that comprise at least one of a metal paste, a metal foil, a metal alloy, aluminum, copper, nickel and a high-conductivity electronic polymer.
20. The thermal substrate of claim 19, wherein a layer of a second film is laminated onto the HRM PTC ink.
PCT/IB2019/056207 2018-07-20 2019-07-19 Thermal substrate with high-resistance magnification and positive temperature coefficient WO2020016853A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16/041,076 US10822512B2 (en) 2016-02-24 2018-07-20 Thermal substrate with high-resistance magnification and positive temperature coefficient
US16/041,076 2018-07-20

Publications (2)

Publication Number Publication Date
WO2020016853A1 true WO2020016853A1 (en) 2020-01-23
WO2020016853A4 WO2020016853A4 (en) 2020-04-02

Family

ID=67998529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2019/056207 WO2020016853A1 (en) 2018-07-20 2019-07-19 Thermal substrate with high-resistance magnification and positive temperature coefficient

Country Status (1)

Country Link
WO (1) WO2020016853A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3822599A1 (en) * 2019-11-17 2021-05-19 Littelfuse, Inc. Thermal sensing wire and techniques for thermal sensing

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1703005A (en) 1928-01-05 1929-02-19 Frank W Hewitt Electric heating pad and fabric
GB2092868A (en) 1981-02-10 1982-08-18 Mb Metals Ltd Electrically heated fabric articles
US4628187A (en) 1984-03-02 1986-12-09 Tokyo Cosmos Electric Co., Ltd. Planar resistance heating element
EP0311142A2 (en) 1981-04-02 1989-04-12 Raychem Corporation Radiation cross-linking of ptc conductive polymers
US5181006A (en) 1988-09-20 1993-01-19 Raychem Corporation Method of making an electrical device comprising a conductive polymer composition
US5227946A (en) 1981-04-02 1993-07-13 Raychem Corporation Electrical device comprising a PTC conductive polymer
US5344591A (en) 1990-11-08 1994-09-06 Smuckler Jack H Self-regulating laminar heating device and method of forming same
US5714096A (en) 1995-03-10 1998-02-03 E. I. Du Pont De Nemours And Company Positive temperature coefficient composition
US7151062B2 (en) 2000-10-27 2006-12-19 Milliken & Company Thermal textile
JP2008293672A (en) 2007-05-22 2008-12-04 Panasonic Corp Resistor composition, and surface heat generating body using this
JP2009151976A (en) 2007-12-19 2009-07-09 Panasonic Corp Polymer heating element
JP2009199794A (en) 2008-02-20 2009-09-03 Panasonic Corp Planar heating element
US8496854B2 (en) 2009-10-30 2013-07-30 Sabic Innovative Plastics Ip B.V. Positive temperature coefficient materials with reduced negative temperature coefficient effect
CN104476890A (en) 2014-10-24 2015-04-01 徐若谷 Heating cloth and manufacturing method thereof
US9161393B2 (en) 2006-10-04 2015-10-13 T+Ink, Inc. Heated textiles and methods of making the same
US20150361287A1 (en) * 2014-06-12 2015-12-17 1-Material Inc Electrically conductive PTC screen printable ink with double switching temperatures and method of making the same
US20170158898A1 (en) * 2014-06-12 2017-06-08 LMS Consulting Group Electrically conductive ptc ink with double switching temperatures and applications thereof in flexible double-switching heaters
WO2017147480A1 (en) * 2016-02-24 2017-08-31 LMS Consulting Group An electrically conductive ptc ink with double switching temperatures and applications thereof in flexible double-switching heaters
US20170327707A1 (en) 2014-06-12 2017-11-16 1-Material Inc Electrically Conductive PTC Screen Printable Ink with Double Switching Temperatures and Method of Making the Same

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1703005A (en) 1928-01-05 1929-02-19 Frank W Hewitt Electric heating pad and fabric
GB2092868A (en) 1981-02-10 1982-08-18 Mb Metals Ltd Electrically heated fabric articles
EP0311142A2 (en) 1981-04-02 1989-04-12 Raychem Corporation Radiation cross-linking of ptc conductive polymers
US5227946A (en) 1981-04-02 1993-07-13 Raychem Corporation Electrical device comprising a PTC conductive polymer
US4628187A (en) 1984-03-02 1986-12-09 Tokyo Cosmos Electric Co., Ltd. Planar resistance heating element
US5181006A (en) 1988-09-20 1993-01-19 Raychem Corporation Method of making an electrical device comprising a conductive polymer composition
US5344591A (en) 1990-11-08 1994-09-06 Smuckler Jack H Self-regulating laminar heating device and method of forming same
US5714096A (en) 1995-03-10 1998-02-03 E. I. Du Pont De Nemours And Company Positive temperature coefficient composition
US7151062B2 (en) 2000-10-27 2006-12-19 Milliken & Company Thermal textile
US9161393B2 (en) 2006-10-04 2015-10-13 T+Ink, Inc. Heated textiles and methods of making the same
JP2008293672A (en) 2007-05-22 2008-12-04 Panasonic Corp Resistor composition, and surface heat generating body using this
JP2009151976A (en) 2007-12-19 2009-07-09 Panasonic Corp Polymer heating element
JP2009199794A (en) 2008-02-20 2009-09-03 Panasonic Corp Planar heating element
US8496854B2 (en) 2009-10-30 2013-07-30 Sabic Innovative Plastics Ip B.V. Positive temperature coefficient materials with reduced negative temperature coefficient effect
US20150361287A1 (en) * 2014-06-12 2015-12-17 1-Material Inc Electrically conductive PTC screen printable ink with double switching temperatures and method of making the same
US20170158898A1 (en) * 2014-06-12 2017-06-08 LMS Consulting Group Electrically conductive ptc ink with double switching temperatures and applications thereof in flexible double-switching heaters
US20170327707A1 (en) 2014-06-12 2017-11-16 1-Material Inc Electrically Conductive PTC Screen Printable Ink with Double Switching Temperatures and Method of Making the Same
CN104476890A (en) 2014-10-24 2015-04-01 徐若谷 Heating cloth and manufacturing method thereof
WO2017147480A1 (en) * 2016-02-24 2017-08-31 LMS Consulting Group An electrically conductive ptc ink with double switching temperatures and applications thereof in flexible double-switching heaters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3822599A1 (en) * 2019-11-17 2021-05-19 Littelfuse, Inc. Thermal sensing wire and techniques for thermal sensing
US11614369B2 (en) 2019-11-17 2023-03-28 Littelfuse, Inc. Thermal sensing wire and techniques for thermal sensing

Also Published As

Publication number Publication date
WO2020016853A4 (en) 2020-04-02

Similar Documents

Publication Publication Date Title
US11136467B2 (en) Thermal substrate with high-resistance magnification and positive temperature coefficient
US20240101851A1 (en) Thermal substrate with high-resistance magnification and positive temperature coefficient ink
CA1062755A (en) Layered self-regulating heating article
US4330703A (en) Layered self-regulating heating article
US4654511A (en) Layered self-regulating heating article
US4543474A (en) Layered self-regulating heating article
EP0340361B1 (en) Electrical device comprising a PTC-resistive polymer element
US5422462A (en) Electric heating sheet
WO1990003713A1 (en) Flexible heater comprising a conductive polymer
CA2977983C (en) Ptc heater with autonomous control
WO1989004532A1 (en) Apparatus for displaying information
US5677662A (en) Heat-sensitive resistive compound and method for producing it and using it
WO2020016853A1 (en) Thermal substrate with high-resistance magnification and positive temperature coefficient
AU579881B2 (en) Electric blankets
SE515262C2 (en) Device for current limiting and protection against short-circuit currents in an electrical system
EP3873170A1 (en) Pptc heater and material having stable power and self-limiting behavior
TW201842515A (en) Hybrid device structures including negative temperature coefficient/positive temperature coefficient device
US20200305237A1 (en) Self-limiting sheet heater and structures made therewith
KR20220137080A (en) PPTC heaters and materials with stable power and self-limiting behavior
KR200433719Y1 (en) Planar Heating Panel
JP2011003328A (en) Polymer heating element
EP4235724A2 (en) Thermal protection device to withstand high voltage
KR101421692B1 (en) Carbon-based electrodes for heating pads
KR200448475Y1 (en) Heater using paste composition
JP3828238B2 (en) Current limiter

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19772857

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 16/06/2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19772857

Country of ref document: EP

Kind code of ref document: A1