WO2022021195A1 - 一种低成本可拉伸穿戴式电转中红外发射器及其制备方法 - Google Patents

一种低成本可拉伸穿戴式电转中红外发射器及其制备方法 Download PDF

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WO2022021195A1
WO2022021195A1 PCT/CN2020/105742 CN2020105742W WO2022021195A1 WO 2022021195 A1 WO2022021195 A1 WO 2022021195A1 CN 2020105742 W CN2020105742 W CN 2020105742W WO 2022021195 A1 WO2022021195 A1 WO 2022021195A1
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infrared
electro
layer
insulating layer
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刘焕明
王志强
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Foshan Hl Science & Technology Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption

Definitions

  • the invention relates to a wearable product, in particular to a low-cost stretchable wearable electro-to-mid-infrared emitter (SEME) and a preparation method thereof.
  • SEME electro-to-mid-infrared emitter
  • Infrared light waves refer to electromagnetic radiation whose energy quantum is smaller than that of red light. Infrared light waves are important because the energy quanta in infrared light waves match the vibrational energy levels of molecules, which has led to the development of molecular infrared spectroscopy for identifying and track molecules. Furthermore, infrared radiation is a major component of the spectral radiation emitted by all warm objects, especially all biological objects. Therefore, infrared light waves are closely related to human beings.
  • a black body An ideal radiation emitter (called a black body) emits according to the above electromagnetic wave spectral distribution without any self-absorption in the entire radiation spectrum, and its emissivity is also set as a reference standard of 100% emissivity.
  • blackbodies are professionally produced and calibrated and are widely used as emissivity standards.
  • Figure 1 shows the electromagnetic wave emission spectrum of a black body when the temperature is 310K (37°C, human body temperature).
  • the electromagnetic wave emission spectrum of the human body is also very close to the electromagnetic wave emission spectrum of a standard black body.
  • the total spectral intensity of electromagnetic wave radiation below 3 ⁇ m wavelength is only 0.02% of its entire spectrum, and the total spectral intensity above 50 ⁇ m is only 2%, so 98% of the total radiation is located in the wavelength range of 3-50 ⁇ m . Because the human body cannot be exposed to temperatures above 320K and below 290K for long periods of time, the blackbody spectra at these two temperatures are also included in Figure 1.
  • the electromagnetic wave radiation spectrum of healthy human body is characterized by: (1) the effective spectrum is mainly in the electromagnetic wave radiation spectrum region of 3 ⁇ m-50 ⁇ m; (2) "extremely hot” and “extremely cold” human body
  • the peak shape of the electromagnetic radiation spectrum is similar, and the peak position only moves slightly from 9.0 ⁇ m to 10.0 ⁇ m, but the radiation intensity is very different.
  • Figure 1 it can also be judged that in the "extremely hot” state, the human body emits more electromagnetic wave quanta of 3 ⁇ m-50 ⁇ m to reduce excess energy, while in the "extremely cold” state, the human body emits less electromagnetic wave quanta of 3 ⁇ m-50 ⁇ m to reduce energy radiation.
  • the shape of the electromagnetic wave radiation spectrum of the surrounding objects that help the human body "restore to a healthy state” should preferably match the shape of the electromagnetic wave radiation spectrum in Figure 1, so that the human body can capture and absorb the electromagnetic wave quantum radiation of the surrounding objects according to its own spectral characteristics.
  • the present invention corrects the scientific corruption in the wearable electric heating and hyperthermia industry according to this quantum physics principle and elucidates the aesthetic and functional design, preparation method, benchmark test/validation of low-cost stretchable wearable electro-to-mid-infrared emitter (SEME) and application.
  • references 6-15 are examples of published industry literature, and they employ the following extremely different wavelength spans of electromagnetic radiation from narrow to broad: "5-12 ⁇ m” [6], “3-14 ⁇ m” [9], “3-15 ⁇ m” [13], “4-16 ⁇ m” [11, 12, 14], “5-20 ⁇ m” [15], “4-20 ⁇ m” [8] and "5.6-25 ⁇ m” [ 10].
  • the spectral bands used in this industry must be standardized and standardized.
  • wavelength range of 3-50 ⁇ m is clearly defined as mid-infrared, of which 0.78 ⁇ m-3 ⁇ m is near-infrared, and 50 ⁇ m-1000 ⁇ m is far-infrared.
  • many commercial products [19] and most of the references [5-13] arbitrarily use the term "far infrared" to describe radiation in the 3-50 ⁇ m wavelength range.
  • Infrared radiation Optical radiation with wavelengths longer than visible light, ranging from 780nm to 1mm.
  • IR-A 780nm to 1400nm, or 0.78 ⁇ m to 1.4 ⁇ m
  • IR-B 1.4 ⁇ m to 3.0 ⁇ m
  • IR-C 3 ⁇ m to 1mm.
  • the infrared spectrum is also divided into “near”, “mid” and “far” infrared.
  • the partition boundaries vary by application area (eg, meteorology, photochemistry, optical design, thermophysics, etc.).
  • the present invention By adopting the ISO20473 standard to correct mistakes in the industry and correctly refer to the spectral band of 3-50 ⁇ m as mid-infrared, the present invention also requires all those who research, manufacture and sell mid-infrared products to review the mid-infrared performance of these products. Quantitative description.
  • the present invention advocates the use of a universal reference blackbody to calibrate the spectral radiant intensity and emissivity of mid-infrared radiation emitters, which should be a function of the emitter's radiation wavelength at a particular temperature.
  • the temperature of the object is 25 °C-50 °C, which is similar to the human body temperature, 98% of the electromagnetic wave radiation intensity of the object is emitted in the mid-infrared spectral band of 3-50 ⁇ m, so all such objects can be classified as medium Infrared transmitter, which is in line with ISO20473 standard.
  • the wavelength of the mid-infrared emitter should be calibrated by emissivity as a function of the emitter wavelength at a specific temperature, using a blackbody with standard emissivity as a reference. In the absence of explicit specification, emissivity refers to the average emissivity in a specific spectral band calibrated with a black body.
  • radiation intensity as a function of radiation wavelength can be accurately measured using a high-end infrared spectrometer that can cover the mid-infrared band from 3-50 ⁇ m.
  • radiation intensity as a function of radiation wavelength can also be readily measured with ordinary infrared spectrometers, which typically cover the spectral range of 0.78 ⁇ m-25 ⁇ m. Therefore, the emissivity in the partial spectral band of 3-25 ⁇ m in the mid-infrared range of 3-50 ⁇ m can be easily measured by this method.
  • the present invention employs and advocates this measurement method to determine the radiative spectral characteristics and emissivity characteristics of all mid-infrared emitters. This standardized approach overcomes the unprofessional nature of spectroscopic specifications in the design, preparation and application of infrared radiation products relevant to the human body.
  • the present invention reveals key design parameters in SEME.
  • SEME standard heat transfer temperature
  • the working surface temperature of the transmitter will not cause human skin burns, which is known to be 46.5°C. While this is well below the typical sauna temperature of about 80°C, the present invention sets 46°C as the upper limit for the surface temperature of the SEME facing and contacting the wearer for safety reasons. In short, an ideal SEME should be designed to provide comfort to the wearer with its maximum operating temperature limited to 46°C.
  • Such an ideal SEME should include a high emissivity facet facing the wearer, where the infrared emissivity is close to that of a black body. If such a surface temperature is maintained at 46°C, the total mid-infrared radiation intensity is 59 mW/cm 2 according to Planck's law.
  • the ideal SEME should also include a non-emissive face facing away from the wearer, where the infrared emissivity is close to zero to minimize wasted radiation and lost energy. Therefore, the ideal SEME should be a structure with top and bottom opposite functions. Under these conditions, the transmitter can easily operate from a safe and convenient USB power source or a small battery with 5V current less than 2A.
  • the innovative SEME of the present invention overcomes deficiencies in the industry and enhances its professionalism. Specifically, many commercial electric heating products with heating and physiotherapeutic effects [19] and many related publications in the scientific literature [2-16] have made a common mistake of misrepresenting their Electromagnetic wave radiation in the temperature range is attributed to far-infrared radiation rather than mid-infrared radiation. Furthermore, they either ignore the precise specification of the radiation wavelength span, or specify an arbitrary radiation wavelength span that covers only a small fraction of the mid-infrared.
  • the innovative SEME of the present invention unquestionably covers 98% of its total radiation in the mid-infrared spectral band specified by ISO20473 from 3-50 ⁇ m, and its radiation and emission were tested and clarified using an infrared spectrometer The rate characteristics cover the spectral band of 3-25 ⁇ m and use a reference black body as the spectral reference.
  • the design and manufacture of the innovative SEMEs of the present invention are scientifically defined and professional.
  • This radiant emissivity meter is equipped with an internal blackbody emitter with a temperature of 100°C that irradiates the test sample and detects and measures the emissivity of the test sample through the temperature change of the blackbody-like radiation absorber .
  • This radiant emissivity meter covers an emissivity range of 0.05%-98% with a spectral range of 2.5-40 ⁇ m. Since Planck's law states that at 100°C, a blackbody emits only 0.14% of its total radiation in 2.5-3 ⁇ m, the actual starting measurement wavelength of this emissivity meter is about 3-40 ⁇ m.
  • this emissivity meter design is effective for quickly measuring mid-infrared emissivity, this design only provides average emissivity over the entire mid-infrared spectral range without wavelength-specific emissivity information. This deficiency can only be overcome by using an infrared spectrometer equipped with a black body.
  • the core function of the SEME of the present invention is to deliver mid-infrared radiation to the wearer. Since SEMEs must also be aesthetically pleasing to the wearer, SEMEs are often decorated in a visible color. In this case, a layman, or even a scientist/engineer with routine skills in the industry, may mistakenly equate the visible light emissivity with the mid-infrared emissivity, since humans can only see visible colors and not the mid-infrared Light. So one might feel that a SEME reference decorated in black doesn't emit visible light, so it doesn't emit mid-infrared light either. Likewise, a layman might also feel that SEMEs with different visible colors must have large differences in mid-infrared emission.
  • the present invention once again corrects this confusion by upholding scientific rigor and evidence-based norms.
  • the present invention prepared and tested a special black polyester abrasion-resistant cloth, wherein the infrared wavelength dispersive emissivity is shown in Fig. 2a.
  • the mid-infrared emission spectral curve of this black polyester is very close to the mid-infrared emission spectral curve of the reference black body, and the total emissivity is 96% in the measured spectral range of 3-33 ⁇ m, which is very close to 100%.
  • the floor is heated by absorbing radiation from the heater and absorbing thermal energy from the heater through normal thermal conduction, which then emits mid-infrared radiation according to the mid-infrared emission spectral characteristics of the floor surface material, in contrast to the heating element or the body under the floor skin.
  • the mid-infrared emission spectral characteristics of the floor surface are often very different, and even the mid-infrared emissivity of the floor surface material is close to 0, and the heat release mainly depends on heating air and hot air convection rather than mid-infrared radiation.
  • mid-infrared radiation from any wearable electro-to-mid-infrared emitter is determined by the optical properties of its top surface material, rather than by the electrothermal heating elements inside the heater.
  • all wearable electro-to-mid-infrared devices that use graphene as the electric heating element and the most common wearable fabric, colored cotton as the topmost wrapping layer, have the mid-infrared characteristics of colored cotton, but not Mid-infrared signatures of graphene. Since cotton is known to have mid-infrared emissivity in the range of 68%-88% [22-23], cotton without surface engineering to increase mid-infrared emissivity is not ideal for producing wearable electro-to-mid-infrared products choose. Likewise, all physiotherapy products with embedded "high-emissivity jewelry" appear to mislead buyers, as the actual mid-infrared radiation of such products is determined by the properties of the outermost material, not the embedded material.
  • the common wearable electric-to-mid-infrared transmitters can neither provide a wearer-facing top surface with a mid-infrared emissivity close to 100% to ensure the mid-infrared benefits of the product, nor can they provide a mid-infrared emission that faces away from the wearer.
  • the present invention comprehensively addresses all these deficiencies in the industry, clarifies the scientific definition of mid-infrared emission and absorption, and proposes an optimal overall design and a low-cost production method for a stretchable wearable electro-to-mid-infrared transmitter.
  • the present invention also explains that the electro-transfer mid-infrared transmitter is characterized by efficiently transmitting mid-infrared radiation to the wearer, so that the wearer can absorb mid-infrared to generate warmth and mid-infrared curative effect.
  • the functional principle and practical application of this product are subversive. There are the principles, applications and practical benefits of the generation and transmission of heat energy of wearable electric heaters in the industry.
  • PCHsu, AYSong, PBCatrysse, C. Liu, YCPeng, J. Xie, SHFan, and Y. Cui "Radiative human body cooling by nanoporous polyethylene textile", Science 353(2016)1019 -1023;PCHsu,C.Liu,AYSong,Z.Zhang,YCPeng,J.Xie,K.Liu,CLWu,PBCatrysse,LLCai,S.Zhai,A.Majumdar,SHFan,and Y .Cui, "A dual-mode textile for human body radiative heating and cooling", Sci.Adv.3(2017)#1700895.
  • Amazon.com lists 157 commercial far-infrared heat-pad products. These products typically give no specific radiation intensity distribution in the ISO20473 far-infrared spectral span of 50-1000 ⁇ m, and give no specific radiation intensity distribution in the ISO20473 mid-infrared spectral span of 3-50 ⁇ m.
  • the present invention relates to a design and preparation method of a novel SEME for physiotherapy or personal thermal management, which meets the market demand for safe, effective and comfortable physiotherapy and low-cost personal thermal management, high-performance SEME. Furthermore, the present invention follows a normative approach that emphasizes scientific clarity and evidence-based in designing new SEMEs. More specifically, the present invention discloses the following unusual SEME design rules that conform to this approach:
  • the mid-infrared emitting element of SEME is a block electro-transfer mid-infrared emitting film, including low-cost nano-carbon polymer composite film, the square resistance of the film is less than 50 ⁇ / ⁇ and the mid-infrared emissivity is close to 100%, when the film is powered by a low-voltage power supply ( When powered by a 5V-USB compatible small rechargeable battery pack), more than 90% of the entire film area emits mid-infrared radiation uniformly.
  • the electro-transfer mid-infrared emitting film has flexible stretchability, and its thickness does not exceed 100 ⁇ m, which makes the emitter light in weight and soft and thin.
  • the low-cost nanocarbons in the electro-transfer mid-infrared emissive film originate from coal or coke [PCT/CN2018/104910], so although the composite film contains graphene, carbon nanotubes, carbon nanofibers and other conductive nanocarbons, its price Inexpensive, the production cost is much lower than conductive films containing graphene, carbon nanotubes, or any expensive nanocarbon derived from graphite.
  • the electro-transfer mid-infrared emitting film is completely wrapped by a layer of electrically insulating polymer coating to ensure safe operation of SEME, preventing any leakage, and the polymer is low cost and stretchable.
  • the encapsulated mid-infrared emitting film is perforated so that the SEME has sufficient breathability to ensure its wearing comfort.
  • the breathable mid-infrared emitting film is coated with a second layer of electrically insulating polymer to prevent leakage of electricity from the hole wall of the breathable mid-infrared emitting film.
  • the design of the second polymer coating meets the color appearance and hydrophilic feel commonly required for all wearable products.
  • the uppermost surface of the second polymer coating must also be designed to have a mid-infrared emissivity close to 100%, which allows the SEME to efficiently convert electrical energy into what the wearer receives. of mid-infrared radiation.
  • the electrically insulating cladding of the electro-to-mid-infrared transmitter is also designed to have an asymmetric structure related to thermal conductivity, especially since the electro-to-mid-infrared transmitter faces The thermal conductivity of the wearer side is high and the thermal conductivity of the opposite side is low. This asymmetry is easily achieved by inserting porous polymer layers. For a polymer foam layer with a thickness of 300 ⁇ m and a thermal conductivity of 0.01 W/(m ⁇ °C), the temperature of the cover layer drops to 15°C when the heater is powered at a typical power density of 0.05W/cm 2 .
  • the temperature of the wearer-facing surface of the mid-infrared emitter can be kept at 46°C, while the surface temperature on the opposite side is 31°C.
  • the combination of asymmetry in thermal conductivity and asymmetry in mid-infrared emissivity is a novel approach to reduce SEME energy loss.
  • a comfortable and wearable electro-to-mid-infrared transmitter characterized as follows: breathability is achieved by strategically passing through the transmitter by designing appropriate pores to ensure skin comfort; stretchability is adapted to the wearer's body movement through elastic engineering, such as Arms/legs flex; surface hydrophilic, ensuring skin compatibility through advanced surface engineering.
  • the maximum working temperature of the SEME designed using the electro-transfer mid-infrared emitting film is 60°C.
  • Planck's law [1] when an electro-transduced mid-infrared emitting film with near-unit emissivity is at 60 °C, it emits mid-infrared with a power density of about 68 mW/cm 2 .
  • the upper surface temperature of the SEME facing the wearer is 46°C, and the maximum surface temperature of the opposite side is 31°C.
  • the wearer-facing top surface of the SEME has a much stronger mid-infrared ray intensity than the opposite surface. At 46°C and a mid-infrared emissivity of 95%, the mid-infrared radiation is 56 mW/cm 2 . In the mid-infrared physiotherapy industry, most known treatments use mid-infrared radiation power densities of no more than 30 mW/cm 2 and treatment times of 30 minutes. Therefore, the SEME of the present invention has an extremely high mid-infrared radiation capability for therapeutic applications and can be down-regulated and corrected in its actual therapeutic operation.
  • the power consumption of the SEME is less than 14W in the suspended state when it is not worn.
  • the wearer's body is at a body temperature close to 37°C, and its power consumption will be much lower than 14W.
  • the wearer emits mid-infrared radiation at a power density close to 50mW/ cm2 , a portion of which is reflected back, in addition to SEME's electro-transitioned mid-infrared emission radiation to the wearer. Therefore, the actual electrical power consumption of the SEME of the present invention is lower than 5 W/200 cm 2 .
  • the mid-infrared physiotherapy time can be limited to less than 30 minutes. Therefore, the energy consumption per physiotherapy treatment can easily be set to less than 2.5 W ⁇ hr. If a small USB battery is used, the power supply weight can be less than 50g.
  • the present invention illustrates a low-cost stretchable wearable electro-to-mid-infrared transmitter through embodiments, the transmitter includes a top surface covering layer, a first insulating layer, and an electro-to-mid-infrared emitting film layer that are stacked in sequence , the second insulating layer and the bottom cover layer, each layer can be stretched and breathable;
  • the emitter includes a first surface and a second surface disposed opposite to each other in a stacking direction, the top cover layer is adjacent to the first surface, the bottom cover layer is adjacent to the second surface, and the first surface faces
  • the mid-infrared emissivity of the first surface is greater than or equal to 90%, and the mid-infrared emissivity of the second surface is less than or equal to 10%;
  • the hydrophilic contact angle of the top cover layer is less than 90°
  • the electro-transfer mid-infrared emitting film layer comprises a low-cost coal-based nano-carbon polymer composite material, and the mid-infrared emissivity of the electro-transfer mid-infrared emitting film layer is greater than or equal to 90%;
  • the first insulating layer and the second insulating layer cover the whole of the electro-transfer mid-infrared emitting film layer;
  • the transmitter also includes a temperature sensor and a power management component.
  • the mid-infrared spectral wavelength range is 3-50 ⁇ m band.
  • the mid-infrared emissivity of the first surface is greater than or equal to 95%.
  • one or more layers of the top cover layer, the first insulating layer, the electro-transition mid-infrared emitting film layer, the second insulating layer and the bottom cover layer have a single-layer or multi-layer structure.
  • the average mid-infrared emissivity of the electro-transfer mid-infrared emitting film layer is ⁇ 95%.
  • the sheet resistance of the electro-transfer mid-infrared emitting film layer is less than or equal to 100 ⁇ / ⁇ , the thickness is less than or equal to 200 ⁇ m, and the elastic tensile strain is not less than 10%.
  • the nanocarbons in the composite material include one or more of graphene, carbon nanotubes, and carbon nanofibers.
  • the nanocarbon in the composite material includes one or several multi-morphological conductive nanocarbons obtained from coal or coke, including graphene, carbon nanotubes, and carbon nanofibers.
  • the polymer in the composite material includes thermoplastic polyurethane, thermoplastic polystyrene, thermoplastic polyester, carbon-based rubber, silicon-based rubber, polypropylene, polyethylene, polyvinyl alcohol, parylene One or more of the phthalamides.
  • the thickness of the top cover layer is less than or equal to 100 ⁇ m.
  • the structural material of the top cover layer includes one or more of polyester, thermoplastic polyester, thermoplastic polyurethane, carbon-based rubber, and silicon-based rubber; the dyeing material of the top cover layer Including lead-free and chrome-free pigments, aluminum particles, coated aluminum particles, titanium dioxide particles, coated titanium dioxide particles, nanocarbon black, perylene red, quinone phthalocyanine, bismuth yellow, indigo, phthalocyanine blue, cobalt blue, copper phthalocyanine One or more of green, iron oxide orange, iron oxide brown, and lead-free yellow 83.
  • the materials of the first insulating layer and the second insulating layer include one or more of polypropylene, polyethylene, polyester, thermoplastic polyester, carbon-based rubber, and silicon-based rubber, and the thickness is ⁇ 500 ⁇ m.
  • the material of the bottom cover layer includes one or more of zirconium-containing metal-rich oxycarbonitride, zirconium, aluminum, copper, zirconium alloy, aluminum alloy, copper alloy, chromium alloy, and stainless steel ;
  • the thickness of the bottom cover layer is less than or equal to 100 nm.
  • the present invention also provides a wearable product, the wearable product comprising any one of the above-mentioned stretchable wearable electro-transfer mid-infrared transmitters.
  • the wearable article includes one or more of clothing, clothing accessories, bedding, and physical therapy devices.
  • the present invention also provides a method for preparing any of the above-mentioned stretchable wearable electro-transfer mid-infrared transmitters, the method comprising:
  • a first insulating layer and a second insulating layer are respectively stacked on the upper and lower sides of the electro-transfer mid-infrared emitting film layer to obtain a stacked structure of the first insulating layer, the electro-transfer mid-infrared emitting film layer and the second insulating layer in sequence , wherein the electro-transfer mid-infrared emitting film layer is wrapped by a first insulating layer and a second insulating layer, and a plurality of ventilation holes extending along the stacking direction are formed in the stacked structure to obtain a ventilation structure;
  • a top surface covering layer is formed on the side of the air-permeable structure close to the first insulating layer, and a bottom surface covering layer is formed on the side of the air-permeable structure close to the second insulating layer.
  • Figure 1 shows the distribution of infrared radiation energy density of a standard black body at different temperatures.
  • Figure 2 shows the distribution of infrared radiation energy density of different materials.
  • FIG. 3 is a front view of the stretchable wearable electro-transfer mid-infrared transmitter of the present invention.
  • FIG. 4 is a top view of the stretchable wearable electro-rotation mid-infrared transmitter of the present invention.
  • FIG. 5 is the ventilation path in the stretchable wearable electro-transducer mid-infrared transmitter of the present invention.
  • FIG. 6 is a schematic diagram of the preparation method of the stretchable wearable electro-transducer mid-infrared transmitter of the present invention.
  • Figure 7-1 shows the design of the strip-shaped stretchable wearable electro-transition mid-infrared emitter of the present invention, wherein strips of pre-packaged mid-infrared emitting film are laminated on the perforated constituent layers. (Cross-sectional view of the air hole)
  • Figure 7-2 is the design of the strip-shaped stretchable wearable electro-transition mid-infrared emitter of the present invention, wherein the strips of pre-packaged mid-infrared emitting film are laminated on the perforated constituent layers. (Cross-sectional view without air holes)
  • FIG. 8 is the design of the strip-shaped stretchable wearable electro-transfer mid-infrared emitter of the present invention, wherein the mid-infrared emitting film stripes are produced by printing.
  • FIG. 9 is a comparison of measurement characteristics between SEME and market competitors under the same power.
  • the present invention discloses the basic structure of a stretchable wearable electro-to-mid-infrared emitter (SEME), including the following multilayers starting from the front side of the SEME, as shown in FIG. 3, the emitter includes The top surface covering layer 31, the first insulating layer 32, the electro-transfer mid-infrared emitting film layer 33, the second insulating layer 34 and the bottom surface covering layer 35 are stacked in sequence;
  • SEME stretchable wearable electro-to-mid-infrared emitter
  • the emitter includes a first surface (top surface) and a second surface (bottom surface) oppositely disposed along the stacking direction, the top cover layer 31 is close to the first surface, and the bottom cover layer 35 is close to the first surface.
  • the second surface wherein, the mid-infrared emissivity of the first surface is greater than or equal to 90%, and the mid-infrared emissivity of the second surface is less than or equal to 10%.
  • the top cover layer 31, the first insulating layer 32, the electro-transfer mid-infrared emitting film layer 33, the second insulating layer 34 and the bottom cover layer 35 may respectively have the following characteristics:
  • the top cover layer 31 is a hydrophilic, breathable, beautiful and wearable encapsulation layer, wherein the infrared emissivity is greater than or equal to 90%; preferably, the average mid-infrared emissivity of the top cover layer is greater than or equal to 95 %, more preferably the average mid-infrared emissivity of the top cover layer is close to 100%;
  • the first insulating layer 32 is an electrically insulating, mid-infrared transparent, breathable and flexibly stretchable layer
  • the electro-transfer mid-infrared emissive film layer 33 is an electro-transfer mid-infrared emissive film with coal-based nanocarbon as a filler and a mid-infrared emissivity close to 100% that can be stretched flexibly, breathable, and highly conductive;
  • the second insulating layer 34 is an electrically insulating, mid-infrared transparent, thermally insulating, breathable and flexible stretchable layer;
  • Bottom cover layer 35 is a durable ultra-thin metal/alloy decorative layer with an infrared emissivity close to 0 (preferably, average mid-infrared emissivity ⁇ 5%).
  • temperature sensors 36 and power management components 37 including control circuits and power supplies are also added to produce a functional and operable SEME.
  • each of the five basic functional layers 31-35 in FIG. 3 includes a single-layer or multi-layer structure to optimize the functional performance of each basic functional layer.
  • the material of the top cover layer 31 includes one or more of polyester, thermoplastic polyester, thermoplastic polyurethane, carbon-based rubber, and silicon-based rubber; preferably Yes, the material of the top cover layer also includes lead-free and chromium-free pigments, aluminum particles, coated aluminum particles, titanium dioxide particles, coated titanium dioxide particles, nano carbon black, perylene red, quinonephthalein yellow, bismuth yellow, One or more of indigo blue, phthalocyanine blue, cobalt blue, copper phthalocyanine green, iron oxide orange, iron oxide brown, and lead-free yellow 83; the thickness of the top cover layer is ⁇ 100 ⁇ m, and the hydrophilic contact angle is less than or equal to 100 ⁇ m.
  • mid-infrared emissivity ⁇ 90% preferably, the average mid-infrared emissivity of the top cover layer is ⁇ 95%, more preferably, the average mid-infrared emissivity of the top cover layer is close to 100% .
  • the top cover layer 31 is a hydrophilic, breathable, beautiful and stretchable wearable layer with a mid-infrared emissivity close to 100%. More specifically, the material of the top cover layer 31 includes a The polyester has a mid-infrared emissivity close to 100%, and the mid-infrared emissivity of general polyester is not close to 100%. The present invention ensures the output of the polyester by monitoring the infrared spectrum of the raw materials and intermediate products from the process of preparing the polyester. Esters have mid-infrared emissivity close to 100%. Evidence for the production of this mid-infrared emissivity approaching 100% is shown in Figure 2.
  • the high emissivity layer is colored white, black, red, green, blue, yellow, and combinations thereof, and maintains mid-infrared emissivity near 100%.
  • Figure 2 shows evidence that special polyesters with various colors produce near 100% mid-infrared emissivity. Colored polyesters are the most widely used wearable polymers in the apparel industry and are therefore the preferred materials for producing the SEMEs of the present invention.
  • the material of the top cover 31 can be any wearable polymer having a color as long as it has a mid-infrared emissivity close to 100% and is as low cost as polyester.
  • the materials of the first insulating layer 32 and the second insulating layer 34 include one of polypropylene, polyethylene, polyester, thermoplastic polyester, carbon-based rubber, and silicon-based rubber or several, with a thickness of ⁇ 500 ⁇ m.
  • the materials of the first insulating layer 32 and the second insulating layer 34 include polyethylene.
  • polyethylene can be designed to be the polymer with the best mid-infrared transparency, and the polyethylene has low cost, suitable heat insulation and flexible stretchability, and is suitable for the SEME disclosed in the present invention. structure.
  • the polyethylene layer is surface modified to become more hydrophilic.
  • the second insulating layer 34 also includes polyethylene foam to optimize the insulating properties of this layer.
  • the material of the first insulating layer 32 and the second insulating layer 34 includes polypropylene.
  • Polypropylene outperforms polyethylene in certain aspects of polymer properties including thermal, chemical and optical properties. Like polyethylene, polypropylene is also very cheap. Therefore, polypropylene is also suitable for the structure of SEME disclosed in this invention.
  • the polypropylene layer is surface modified to become more hydrophilic.
  • the second insulating layer 34 also includes polypropylene foam to optimize the insulating properties of this layer.
  • the materials of the first insulating layer 32 and the second insulating layer 34 may further include thermoplastic polyurethane, thermoplastic polyester, carbon-based rubber, silicone-based rubber, polypropylene, polyethylene and the like. combination.
  • the sheet resistance of the electro-transfer mid-infrared emission film layer 33 is less than or equal to 100 ⁇ / ⁇ , the thickness is less than or equal to 200 ⁇ m, the mid-infrared emissivity is greater than or equal to 90%, and the elastic tensile strain is not less than 10%; preferably, the electro-transfer mid-infrared emission The mid-infrared emissivity of the film layer is ⁇ 95%.
  • the electrotransduced mid-infrared emitting film layer 33 includes a nanocarbon polymer composite material, wherein the nanocarbon in the composite material includes one or more of graphene, carbon nanotubes, and carbon nanofibers.
  • the nanocarbon in the composite material includes one or several multi-morphological conductive nanocarbons obtained from coal or coke, including graphene, carbon nanotubes, and carbon nanofibers.
  • the polymer in the composite material includes one or more of thermoplastic polyurethane, thermoplastic polystyrene, thermoplastic polyester, carbon-based rubber, silicon-based rubber, polypropylene, and polyethylene.
  • the nanocarbon is composed of coal-based nanocarbon with resistivity lower than 1 ⁇ -cm, and its production cost is at least 50 times lower than that of graphene.
  • the carbon black is further graphitized to a resistivity below 1 ⁇ -cm and used to make the SEME of the present invention.
  • the electro-transfer mid-infrared emitting film layer 33 includes a plurality of ventilation holes extending along the stacking direction, and the holes are formed by mechanical drilling, arc machining, laser cutting, selective area etching and melt-blown cloth molding. formed in one or more ways.
  • the bottom cover layer 35 may be a durable ultra-thin metal/alloy decorative layer with a mid-infrared emissivity close to 0 (eg, average mid-infrared emissivity ⁇ 5%), which includes metal-rich oxycarbonitride compound ZrAlvNxCyOz, where 0 ⁇ v ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1.
  • This metal-like coating can be produced by ordinary sputtering equipment at low cost and is a durable coating with a shiny platinum-like appearance.
  • the infrared emissivity is close to 0.
  • an ultra-thin aluminum base coat is prepared to enhance the adhesion of the durable coating.
  • the bottom cover layer 35 comprises one or more of zirconium-containing metal-rich oxycarbonitride, zirconium, aluminum, copper, zirconium alloy, aluminum alloy, copper alloy, chromium alloy, stainless steel kind.
  • an ultra-thin aluminum basecoat or titanium basecoat is prepared on one or both sides of the bottom cover layer 35 to enhance the adhesion of the durable coating.
  • the electro-transduced mid-infrared emitting film layer 33 comprises flexible parallel strips 411, 412, . . . It is connected with the breathable spacers 421, 422... 42n, and its stretchability and breathability are mainly realized by designing the spacers.
  • breathable pathways through multiple layers of the SEME of the present invention are achieved through pore engineering. In some embodiments, this ventilation path is designed through perforations. In some embodiments, the ventilation paths are evenly distributed throughout the SEME, as shown in the right panel of FIG. 5 . In some embodiments, the breathable pathway is strategically located in the selective area, and the breathable area is strategically located in the SEME. In some embodiments, the breathable paths are strategically located in the spacer strips between strips of electroporated mid-infrared emitting film, as shown in the left panel of FIG. 5 .
  • strip 611 of electro-transfer mid-infrared emitting film is first sandwiched by two thin electrically insulating laminate layers 612 and 613 . These wrapped strips of mid-infrared emitting film are then spaced in parallel and laminated into a flexible stretchable and breathable mid-infrared emitting film.
  • Figures 7-1 and 7-2 show that the resulting mid-infrared emitting film 73 is surrounded by the constituent layers 71, 72, 74, 75 of the multilayer SEME design. Therein, the vent holes or stretchable vent membranes run through all the constituent layers 71-75 of the entire launcher.
  • strips 83 of mid-infrared emitting film are printed onto the constituent layers 81 of the prefabricated constituent layers.
  • the resulting printed layer 83 is laminated to obtain a layer having the constituent layer 81 .
  • All constituent layers 81 include elastic stretch polymers, copolymers, hybrid polymers, and combinations thereof.
  • perforations are formed in the spaced domains between each pair of printed stripes to form ventilation paths.
  • the present invention also provides a method for preparing the above-mentioned stretchable wearable electro-transfer mid-infrared transmitter, the method comprising:
  • a first insulating layer and a second insulating layer are respectively stacked on the upper and lower sides of the electro-transfer mid-infrared emitting film layer to obtain a stacked structure of the first insulating layer, the electro-transfer mid-infrared emitting film layer and the second insulating layer in sequence , wherein the electro-transfer mid-infrared emitting film layer is wrapped by a first insulating layer and a second insulating layer, and a plurality of ventilation holes extending along the stacking direction are formed in the stacked structure to obtain a ventilation structure;
  • a top surface covering layer is formed on the side of the air-permeable structure close to the first insulating layer, and a bottom surface covering layer is formed on the side of the air-permeable structure close to the second insulating layer.
  • a high performance SEME is produced.
  • a stretchable and flexible mid-infrared emitting film was prepared by dispersing thermoplastic polyurethane in cyclohexanone and dispersing conductive coal-based nanocarbons in thermoplastic polyurethane solution using a standard slurry film-forming process.
  • the resulting thin film had a square resistance of 26 ⁇ 2 ⁇ / ⁇ and a thickness of 80 ⁇ 2 ⁇ m, and a mid-infrared emitting film with a resistance of 6 ⁇ and a size of 156 cm 2 was prepared.
  • the applied voltage is 5V
  • the current through the mid-infrared emitting film is 0.83A
  • the rated power and power per unit area are 4.2W and 0.027W/cm 2 , respectively.
  • the mid-infrared emitting film is sandwiched by two thin layers of polypropylene, and the wrapped mid-infrared emitting film is perforated for breathability.
  • the breathable mid-infrared emissive film was then coated with a thin solution of polyester with a white dye to electrically insulate the sidewalls of the perforations, and the topmost surface of the encapsulated mid-infrared emissive film was engineered so that It has a mid-infrared emissivity close to 100%. Polyester is also used because of its hydrophilic properties and comfortable abrasion resistance.
  • the bottom surface of the mid-infrared emitter is coated with an ultra-thin layer containing zirconium, nitrogen, carbon and oxygen to create a durable surface with near-zero mid-infrared emissivity.
  • the synthesized SEME is stretchable and breathable, and has a hydrophilic surface in contact with the wearer.
  • the temperature of the surface in contact with the wearer was raised to 46°C, and the power was adjusted to maintain the desired temperature.
  • the surface temperature is 46°C
  • the infrared emissivity of the mid-infrared radiation on the top surface of the SEME facing the wearer is 96%
  • the mid-infrared emissivity of the metal coating surface is 96% with the reference black body as the calibration benchmark. 5%.
  • the power density of mid-infrared radiation to the human body is about 55 mW/cm 2 .
  • this mid-infrared radiation is much higher than that of common infrared therapy lamps on the market.
  • this infrared light is specified to have an emission spectral range of 3-25 ⁇ m, a peak spectral sensitivity of 5 ⁇ m, and a recommended power density of less than 30 mW/cm 2 .
  • the temperature of a black body with a peak emission spectrum of 5 ⁇ m is about 300°C; therefore, the heat source of this infrared lamp operates at temperatures above 300°C.
  • the SEME in this example emits mid-infrared with a spectral peak of 9 ⁇ m and an operating temperature close to 46°C.
  • SEME works safer, where the infrared signal is better matched to the body's emission/absorption characteristics.
  • FIG. 9 is a comparison of the measurement characteristics between the SEME of the present embodiment and the competitive product in the market under the same power. It can be seen from FIG. 9 that the temperature of the side facing the wearer of the SEME of the present invention reaches 46°C, and the mid-infrared emissivity reaches 98%, while the temperature of the side facing away from the wearer or the decorative surface is maintained at a lower 31°C, The mid-infrared emissivity is as low as 10%, that is, the power loss is very low.
  • the temperature on the front of the competing products is 38°C, and the mid-infrared emissivity is only 93%, which means that the heating power to the wearer is relatively low; while the mid-infrared emissivity on the back is as high as 93%, which has a very high power loss. .
  • a high performance SEME is produced.
  • the production process is the same as in Example 1, except that the white polyester is replaced by the black polyester.
  • the mid-infrared emissivity of the SEME mid-infrared radiation at a surface temperature of 46 °C is 97%, and the mid-infrared emissivity of the metal coating surface is 5%.
  • the power density of mid-infrared radiation to the human body is about 56 mW/cm 2 .
  • a high performance SEME was fabricated.
  • the production process is the same as in Example 1, except that the white polyester is replaced by the red polyester.
  • the mid-infrared emissivity of SEME's mid-infrared radiation is 92% when the surface temperature is 46°C with the reference black body as the calibration reference. Under this operating condition, the power density of mid-infrared radiation to the human body is about 53 mW/cm 2 .
  • a high performance SEME was fabricated.
  • the production process is the same as in Example 1, except that in the production process, the polyester is replaced by green polyester.
  • the mid-infrared radiation of SEME when the surface temperature is 46 °C, the mid-infrared radiation of SEME, the mid-infrared emissivity is 91%. Under this operating condition, the power density of mid-infrared radiation to the wearer is about 52 mW/cm 2 .
  • a test SEME was produced.
  • the production process was the same as Example 1, except that the SEME surface opposite the wearer was not covered by the glossy metal rich overlay. Therefore, this surface is also highly radiative.
  • the power rating to maintain the same operating temperature of 46°C is about 1.6 times that of the SEME in Example 1. Obviously, the design of the top-bottom opposite functional structure reduces energy consumption.
  • a test SEME was produced.
  • the production process is the same as that of Example 1, except that the electro-transfer mid-infrared emitting film is replaced by a slender zig-zag electric heating wire with the same resistance.
  • the mid-infrared radiation from this electrothermal wire heater was captured with an infrared camera, and the surface temperature on the front of the wearer was 46°C.
  • Mid-infrared imaging confirmed that the surface temperature and mid-infrared radiation were not uniform.

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Abstract

一种低成本可拉伸穿戴式电转中红外发射器及其制备方法，发射器包括面向穿戴者依次层叠设置的顶面覆盖层（31）、第一绝缘层（32）、电转中红外发射膜层（33）、第二绝缘层（34）及底面覆盖层（35），且每层都可拉伸和透气；顶面覆盖层（31）和底面覆盖层（35）的中红外发射率分别是≥90％和≤10％，顶面覆盖层（31）的亲水接触角小于90°，电转中红外发射膜层（33）以低成本煤基纳米碳聚合物复合材料制备。这些可量化属性的结合，使电转中红外发射器具有穿戴舒适性和电转中红外单向穿戴者发射的低能耗与高功效性。

Description

一种低成本可拉伸穿戴式电转中红外发射器及其制备方法 技术领域
本发明涉及一种可穿戴式产品，尤其涉及一种低成本可拉伸穿戴式电转中红外发射器(SEME)及其制备方法。
背景技术
近年来，可穿戴电转红外发射器已经被生产并在市场上销售。然而，这些产品在辐射光谱波长和强度方面缺乏科学和定量的规范。因此本发明首先阐明此领域中相关科学原理和工程技术的背景。
红外光波是指能量量子小于红光能量的电磁波辐射。红外光波很重要，因为红外光波中的能量量子与分子的振动能级相匹配，这导致了分子红外光谱学的发展，用于在化学工程，医学，食品工程和环境工程的各个领域中识别和跟踪分子。此外，红外辐射是所有温暖物体发出的光谱辐射的主要成分，特别是所有生物物体发出的主要光谱辐射。因此，红外光波与人类息息相关。
在宏观上物体的温暖状态和冷热变化都以温度来量化，而微观上物体的温暖状态和变化则其实应循量子物理学的电磁波量子发射特性来量化，普朗克定律用以下简单方程式——(1)设置了电磁波量子辐射强度(I)、辐射波长(λ)、和温度(T)——的函数关系的定量描述[1]：
Figure PCTCN2020105742-appb-000001
理想的辐射发射器(称为黑体)根据上述电磁波光谱分布发射，在整个辐射光谱中没有任何自吸收，其发射率也被设置为发射率100％的参考标准。如今，黑体已经过专业生产和校准，并广泛用作发射率标准。例如，图1所示为温度为310K(37℃、人体温度)时黑体的电磁波发射光谱，而实际上人体的电磁波发射光谱也很贴近标准黑体的电磁波发射光谱。它的特征在于：在3μm波长以下的电磁波辐射的总光谱强度仅为其整个光谱的0.02％，50μm以上的总光谱强度仅为2％，则总辐射的98％位于3-50μm的波长范围内。因为人体不能长期暴露在高于320K和低于290K的温度下，因此图1中还包括了这两个温度下的黑体光谱。比较320K，310K和290K的黑体光谱可见健康人体的电磁波辐射光谱特征在于：(1)有效光谱主要在3μm-50μm的电磁波辐射光谱区域；(2)“极热”与“极冷”的人体的电磁波辐射光谱峰形状相近，峰位只从9.0μm微移到10.0μm，但辐射强度差异很大。分析图1也可判断“极热”状态下，人体较多发射3μm-50μm的电磁波量子以降减多余能量，而在“极冷”状态下，人体减少发射3μm-50μm的电磁波量子以降低能量辐射消耗，并通过吸收周边温暖物体发射出的3μm-50μm的电磁波量子来保持310K的“健康”微观电磁波辐射光谱状态。理所当然，周边帮助人体“恢复健康状态”的物体的电磁波辐射光谱形状最好与图1的电磁波辐射光谱形状匹配，才有利于人体按自身人体光谱特征来捕捉和吸收外界周边物体的电磁波量子辐射。本发明按此量子物理原理纠正可穿戴电热和热疗行业里的科学讹误和阐述低成本可拉伸穿戴式电转中红外发射器(SEME)的兼顾美学和功能设计、制备方法、基准测试/验证和应用。
3μm-50μm辐射对人类健康的重要性确实已经得到了充分的证实和评估[2-5]。科学实验证明这波段的辐照可提高人体血液循环和免疫力[6-9]，增强伤口愈合能力[10]，减轻疼痛[11-12]，减轻抑郁压力[13]，改善睡眠质量[14]，并延缓记忆力衰退[15]。将3μm-50μm辐射的这些知识与个人热管理的新兴领域协同整合[16-17]，出现了新的科学研究领域并制造出新的产品。但是，当前实践中采用的电磁波辐射的波长跨度具有一定的随意性，这种随意性阻碍了这一新兴行业的发展和市场的可持续接受能力。例如，参考文献6-15是已发表的行业文献典范，而它们采用了以下从窄到宽的相异极大的电磁波辐射波长跨度：“5-12μ m”[6]，“3-14μm”[9]，“3-15μm”[13]，“4-16μm”[11,12,14]，“5-20μm”[15]，“4-20μm”[8]和“5.6-25μm”[10]。显然，此行业采用的光谱带必须要进行规范和标准化。
尽管波长跨度为3-50μm的电磁波辐射具有如此重要的意义，并促成了众多堪称典范的论文与专利，但令人惊讶的是，甚至波长跨度的命名也被写成相当随意的形式。根据国际光谱标准ISO20473，将3-50μm的波长范围明确定义为中红外，其中0.78μm-3μm为近红外，50μm-1000μm为远红外。但是，许多商业产品[19]和参考文献[5-13]中的大多数文献都随意使用了“远红外”一词来描述3-50μm波长范围内的辐射。其中一些文献错误地引用了国际照明委员会(International Commission on Illumination)对红外辐射的定义，以证明他们随意使用“远红外”来描述波长在3-50μm范围内的辐射是合理的。为明确起见，国际照明委员会网站(WWW.CIE.CO.AT)公开公布的确切定义辑录如下:
红外辐射：波长比可见光更长的光辐射，波长为780nm至1mm。
注1：对于红外辐射，通常分为780nm至1mm的范围：IR-A：780nm至1400nm，或0.78μm至1.4μm；IR-B:1.4μm至3.0μm；IR-C：3μm至1mm。
注2：无法定义“可见”和“红外”之间的精确边界，因为波长大于780nm的视觉感受是由于波长较长的非常明亮的光源引起的。
注3：在某些应用中，红外光谱也分为“近”，“中”和“远”红外。但是，分区边界随应用领域不同(例如，气象学，光化学，光学设计，热物理等)而变化。
以上说明了一个结论，即国际照明委员会仅承认某些光谱应用将红外分区为“近”，“中”和“远”红外，但未对应如何设置这些分区提出意见。相比之下，ISO20473[18]将0.78-1.4μm的IR-A波段和1.4-3.0μm的IR-B波段明确组合为0.78-3.0μm的“近红外”波段，并将宽范围的IR-C3.0-1000.0μm波段分拆，其中“中红外”波段为3.0-50.0μm，“远红外”波段为50.0-1000.0μm。简而言之，本发明提倡严格执行将3-50μm的光谱带标记为中红外，以符合ISO20473的要求。
通过采用ISO20473标准来纠正行业中的错误，并正确地将3-50μm的光谱带称为中红外，本发明还要求所有对中红外产品研究、制造和销售的人员对这些产品的中红外性能进行定量说明。特别地，本发明提倡使用通用的基准黑体来校准中红外辐射发射器的光谱辐射强度和发射率，该光谱辐射强度和发射率在特定温度下应是发射器的辐射波长的函数。当物体的温度是在人体温相近的25℃-50℃时，物体电磁波辐射强度的98％是在3-50μm的中红外光谱带中发射的，因此，所有此类物体都可以归类为中红外发射器，这才符合ISO20473标准。此外，应以具有标准发射率的黑体为基准，将中红外发射器的波长通过发射率作为特定温度下发射器波长的函数进行校准。在没有明确规定的情况下，发射率是指用黑体校准的特定光谱带中的平均发射率。在实践中，可以使用高端红外光谱仪准确测量作为辐射波长的函数的辐射强度，该高端红外光谱仪可以覆盖3-50μm的中红外波段。另外，也可以用通常覆盖0.78μm-25μm的光谱范围的普通红外光谱仪容易地测量作为辐射波长的函数的辐射强度。因此，通过这种方法可以容易地测量在3-50μm的中红外范围内的3-25μm的部分光谱带中的发射率。尽管此测量方法仅覆盖3-25μm的光谱带，而不覆盖3-50μm的整个中红外范围，但因为黑体的温度范围在25-50℃时在3-25μm的光谱带中发射出的总辐射强度是整个3-50μm中红外带的85％，所以所测得的发射率数据已很好地表示了被测对象的发射率特性。因此，本发明采用并提倡这种测量方法来确定所有中红外发射器的辐射光谱特性和发射率特性。这种标准化的做法克服了在设计、制备和应用与人体相关红外辐射产品于光谱规格方面的不专业性。
基于这些方法上的考虑，本发明揭示了SEME中的关键设计参数。在利用中红外有益人体健康这一特性设计应用与人类有关的中红外辐射的产品时，必须考虑发射器的工作表温不会导致人体皮肤灼伤，已知该温度为46.5℃。尽管这远低于典型的约80℃的桑拿温度， 但出于安全考虑，本发明将46℃设置为SEME面向并接触穿戴者的表面温度的上限。简而言之，一个理想的SEME应该被设计成在其最高工作温度被限制在46℃的条件下来为穿戴者提供舒适感。这种理想的SEME应该包括一个面向穿戴者的高发射率面，其中红外发射率接近黑体。如果将此类表面温度保持在46℃，则根据普朗克定律，其总中红外辐射强度为59mW/cm 2。此外，理想的SEME还应包括一个背向穿戴者的非发射性面，其中红外发射率接近0，以最大程度地减少辐射的浪费和能量的损失。因此，理想的SEME应为具有顶底相反功能的结构。在这些条件下，发射器可以很容易地使用安全方便的USB电源或5V电流小于2A的小电池工作。迄今为止，既没有涉及这种SEME的相关设计出现，也没有涉及具有顶底相反功能结构的SEME任何相关产品出现，从而向穿戴者发出接近59mW/cm 2的辐射，并且发射器的反向面应几乎不会发射中红外辐射。由于文献中报道的中红外辐射的治疗效果已经被实验跟踪并经过彻底验证，而典型的中红外辐射强度不高于30mW/cm 2，辐射时间通常为30分钟。因此本发明创新设计的SEME可以在远低于其理想的59mW/cm 2辐射强度情况下轻松达到治疗效果。这意味着，使用远低于10W的电源，运行时间小于30分钟，就可以实现实验中验证过的中红外辐射对人体的治疗效果。因此，由于SEME的应用简单、方便、且便宜，因此本发明创新的SEME具有很大的实际影响力和应用前景。
基于强调科学的清晰度和以证据为基础的规范，本发明创新的SEME克服了行业中的缺陷，提高了它的专业性。具体而言，许多用具有加温和理疗效果的商业电热产品[19]以及科学文献中的许多相关出版物[2-16]都犯了一个普遍的错误，他们错误地将其与人体有关的温度范围内的电磁波辐射归结为远红外辐射而非中红外辐射。此外，他们不是忽略了辐射波长跨度的精确规定，就是指定了仅覆盖中红外的一小部分的任意辐射波长跨度。相比之下，本发明的创新型SEME毫无疑问地在3-50μm的ISO20473规定的中红外光谱带中覆盖了其总辐射的98％，并且使用红外光谱仪测试并弄清了其辐射和发射率特性覆盖3-25μm的光谱带，并以基准黑体作为光谱参考。简而言之，本发明创新的SEMEs的设计和制造在科学上是明确且专业的。
由于本发明SEME的创新关键在于其定义明确的辐射区间和发射率区间，特别是其顶底相反功能的发射结构，因此有必要对中红外发射率的检测和优化进行阐述。用于检测中红外辐射率的主要工具有两个：(a)通过简单的辐射发射率测量仪测得的非波长色散发射率，以及(b)通过装有黑体的红外光谱仪测得的波长色散发射率。一篇最近出版的文献[20]描述，校准并验证了一种工业用辐射发射率测量仪。该辐射发射率测量仪配备有一个内部黑体发射器，该内部黑体发射器的温度为100℃，可辐照测试样品，并通过类黑体辐射吸收器的温度变化来检测和计量测试样品的发射率。该辐射发射率测量仪覆盖了0.05％-98％的发射率范围，光谱范围为2.5-40μm。由于普朗克定律规定，在100℃时，黑体在2.5-3μm中仅发射其总辐射的0.14％，因此该发射率测量仪的实际开始测量波长约为3-40μm。虽然，这种发射率测量仪设计对于快速测量中红外发射率是有效的，但是，该设计仅提供了整个中红外光谱范围的平均发射率，而没有特定波长发射率的信息。这种缺陷只能通过使用配备有黑体的红外光谱仪来克服。
本发明SEME的核心功能是向穿戴者传递中红外辐射。由于SEME还必须在美学上使穿戴者感到愉悦，因此通常以可见的颜色装饰SEME。在这种情况下，外行，甚至是具有行业常规技能的科学家/工程师，都可能错误地将可见光发射率等同于中红外发射率，因为人类只能看到可见的颜色，而看不到中红外光。因此，人们可能会觉得用黑色装饰的SEME参考不会发出可见光，所以也不会发出中红外光。同样，外行人也可能会觉得具有不同可见颜色的SEME在中红外发射方面一定存在很大差异。本发明再次通过坚持对科学严谨的态度和基于证据的规范来纠正这种混乱。例如，在本发明的一个实施例中，本发明制备与测试了一种特殊的黑色聚酯耐磨布，其中红外波长色散发射率如图2a所示。这种黑色聚酯 的中红外发射光谱曲线与基准黑体的中红外发射光谱曲线非常接近，在3-33μm的测量光谱范围内，总发射率为96％，非常接近100％。一个不懂中红外科学的外行人也可能会认为，将黑色染料换成白色染料会大大改变降中红外发射率；但实际上，本发明的另一个实施例证实：通过选择合适的白色染料可以保留近乎完美的中红外发射光谱和保持高发射率于95％，如图2b所示。相比之下，参考文献[21]报导了该研究组制备的白色聚乙烯箔片的中红外发射光谱比黑色聚乙烯箔片和标准黑体的中红外发射光谱差，特别是在3-7μm的谱带，白色箔片的发射率只有黑体的83％。由此可见，本发明阐述以通过研究定量的中红外波长色散发射率来设计和生产SEME的方法是严谨和新颖的。
为了设计和验证SEME在将电能转换为中红外发射能并将相关的中红外传递给穿戴者方面的性能，对沿从辐射源到穿戴者的路径中的辐射吸收进行彻底的光谱分析非常重要。业界缺乏此类分析。例如，石墨烯地板加热器被积极地推向市场，声称石墨烯辐射红外容易被人体吸收。实际上，石墨烯地板加热器的加热元件中包含石墨烯，但实际加热元件上覆盖一层对中红外辐射不透明的木质或陶瓷地板。因此，加热元件产生的中红外辐射不会透过地板材料。取而代之的是，地板通过吸收来自加热器的辐射并通过正常的热传导从加热器吸收热能来加热，再根据地板表面材料的中红外发射光谱特征发出中红外辐射，与加热元件或地板表皮下的主体的中红外发射光谱特征往往差异极大，甚至地板表面材料的中红外发射率接近0，热的释放主靠加热空气和热空气对流而并非中红外辐射。类似地，来自任何可穿戴电转中红外发射器的中红外辐射由其顶部表面材料的光学性质决定，而不是由加热器内部的电热加热元件决定。例如，所有以石墨烯为电热元件、以最常见的可穿戴面料——彩棉作为最顶层的包裹层的可穿戴式电转中红外器，其辐射都具有彩棉的中红外特征，而不具有石墨烯的中红外特征。由于已知棉花的中红外发射率范围为68％-88％[22-23]，因此未经表面工程处理以提高其中红外发射率的棉花对于生产可穿戴电转中红外产品而言并不是理想的选择。同样，所有嵌入“高发射性珠宝”的理疗产品都有误导买家之嫌，因为此类产品的实际中红外辐射是由最外层材料的性质决定的，而不是由嵌入材料决定的。此外，普遍的可穿戴式电转中红外发射器既不能够提供中红外发射率接近100％的面向穿戴者的顶面来保障产品中红外效益，也不能够提供背向穿戴者的、中红外发射率接近零的背面品的节能效益。最近，尽管参考文献[24]报导了一种具顶底红外发射率相反的功能薄膜结构，该薄膜也可作为电转中红外发射器使用，但加热顶面采用了低发射率的纳米铜，而反方向的底面却采用了高发射率材料去散热。显然，这种顶底相反功能结构设计与本发明的设计是背道而驰的。
相关文献报导在理疗方面[2-15，19]、个人热管理方面[16-19；US7642489；US10457424；US2018/0320067]和军事应用方面[US7313909]介绍了这些应用所需的发射和操作红外辐射的设备,都犯波段范围和辐射率不符中红外规范毛病,发射器工作时发射表面温度高于46℃有导致人体皮肤灼伤危险的毛病；其中有采用传统的红外发射器[US8975604；US9249492],具有体积大和笨重的缺点,不符合可拉伸和可穿戴的市场需求。
本发明全面地解决了行业中的所有这些缺陷，阐明了中红外发射和吸收的科学定义，并且提出了可拉伸穿戴式的电转中红外发射器的最优整体设计和低成本的生产方式。本发明又阐释了电转中红外发射器的特征在于高效传送中红外辐射给射穿戴者，达到让穿戴者吸收中红外而产生暖意和中红外疗效，这款产品功能原理与实际应用颠覆性现有行业中可穿戴电热器的产生与传送热能原理、应用和实际效益。
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发明内容
本发明涉及一种用于理疗或个人热管理的新型SEME的设计和制备方法,满足市场对安全、有效、舒适的理疗和低成本个人热管理、高性能的SEME的需求。此外，本发明遵循在设计新的SEME过程中强调科学清晰和基于证据的规范方法。更具体地说，本发明揭示了符合这种方法的以下不寻常的SEME设计守则：
1.SEME的中红外发射元件是块电转中红外发射膜，包括低成本的纳米碳聚合物复合膜，薄膜的方阻＜50Ω/□和中红外发射率接近100％，当薄膜由低压电源(如5V-USB电源 兼容的小型可充电电池组)供电时，超过90％的整个薄膜区域均匀地发出中红外辐射。
2.电转中红外发射膜具有灵活的拉伸性，其厚度不超过100μm，使得发射器的重量轻且柔软轻薄。
3.电转中红外发射膜里的低成本纳米碳源于煤或焦炭[PCT/CN2018/104910]，因此尽管复合膜含有石墨烯、碳纳米管、碳纳米纤维和其他导电纳米碳，但它价格低廉，生产成本远低于含有石墨烯的导电膜，纳米碳管，或任何昂贵的源于石墨中的纳米碳。
4.电转中红外发射膜由一层电绝缘聚合物涂层完全包裹，以确保SEME的安全运行，防止任何漏电，并且该聚合物成本低且可拉伸。
5.封装的中红外发射膜开有孔，以使SEME具有足够的透气性，以确保其穿着舒适性。
6.透气中红外发射膜涂有第二层电绝缘聚合物，以防止透气中红外发射膜的孔壁漏电。最重要的是，第二层聚合物涂层的设计满足了所有可穿戴产品通常所需的彩色外观和亲水触感。此外，为了获得有效的SEME，第二层聚合物涂层的最上面的表面也必须将其设计成中红外发射率接近100％，这便使得SEME能将电能高效地转换为穿戴者所接收到的中红外辐射。
7.将背对穿戴者的外表面的中红外发射率设计接近于0，以使辐射的浪费和能量的损失最小化。满足此设计要求的一种实用方法是在前表面涂覆一层闪亮的金属涂层，该涂层通常具有接近0的中红外发射率。低成本在高分子膜上涂超薄铝由于其生产简单、成本低廉等优点，在工业包装中得到了广泛的应用。在一些实施例中，为防磨蚀保护添加了具有漂亮的铂外观和接近0发射率[US7264668]的超薄锆铝超耐磨化合物顶层。本发明的超薄设计保留了SEME的灵活性和耐磨性。
8.除了设计顶底相反功能结构以尽量减少任何能量损失外，电转中红外发射器的电绝缘包层还设计成具有与热导率有关的不对称结构，特别是由于电转中红外发射器面向穿戴者一面的热导率高而反向面的热导率低。这种不对称性很容易通过插入多孔聚合物层来实现。对于厚度为300μm、导热系数为0.01W/(m·℃)的聚合物泡沫层，当加热器以0.05W/cm 2的典型功率密度供电时，覆盖层的温度降为15℃。在这种情况下，出于安全考虑，中红外发射器面向穿戴者的表面温度可以保持在46℃，而相对面的表面温度在31℃。在SEME结构中，热导率的不对称性和中红外发射率的不对称性相结合是减小SEME能量损失的一种新方法。
9.舒适可穿戴的电转中红外发射器，其特征如下：透气性是通过设计适当的气孔策略性地穿过发射器确保皮肤舒适；可拉伸性通过弹性工程迎合穿戴者的身体运动，如手臂/腿部弯曲；表面亲水性，通过先进的表面工程确保皮肤相容性。
10.根据这些设计考虑，在本发明的优选实施例中，使用电转中红外发射膜设计的SEME最高工作温度为60℃。根据普朗克定律[1]，当具有接近单位发射率的电转中红外发射膜处于60℃时，它以约68mW/cm 2的功率密度发射中红外。当红外反射器就位时，几乎所有的辐射都会照射到穿戴者身上。SEME面向穿戴者的表面温度上限为46℃，相对面的最高表面温度上限为31℃。SEME面向穿戴者的顶面表面的中红外射线强度比反向面表面的强得多。在46℃和95％的中红外发射率下，中红外辐射为56mW/cm 2。在中红外理疗行业中，大多数已知的治疗方法使用的中红外辐射功率密度不超过30mW/cm 2，治疗时间为30分钟。因此，本发明的SEME在治疗应用具有极高的中红外辐射能力，并且可以在其实际治疗操作中向下调节和校正。由于普通可穿戴加热器的加热器面积不超过200cm 2，因此，在本实施例中，如在不被穿戴的悬空状态下，SEME的功耗小于14W。然而，在SEME的实际使用中，穿戴者的身体处于接近37℃的体温下，它的功耗会远低于14W。在这种情况下，穿戴者以接近50mW/cm 2的功率密度发射中红外，其中一部分被反射回来，除此之外还有SEME的对穿戴者的电转中红外发射辐射。因此，本发明的SEME的实际电功率消耗低于5W/200cm 2。由于对穿戴者的中红外辐射进行了全面的设计和优化，中红外理疗时间可以限 制在30分钟以内。因此，每次理疗处理的能量消耗可以很容易地设置为小于2.5W·hr。如果使用小型USB电池，电源重量可以小于50g。
有鉴于此，本发明通过实施例阐明一种低成本可拉伸穿戴式电转中红外发射器，所述发射器包括依次层叠设置的顶面覆盖层、第一绝缘层、电转中红外发射膜层、第二绝缘层及底面覆盖层，每层都可拉伸和透气；
所述发射器包括沿层叠方向相对设置的第一表面和第二表面，所述顶面覆盖层靠近所述第一表面，所述底面覆盖层靠近所述第二表面，所述第一表面面向穿戴者，所述第一表面的中红外发射率≥90％，所述第二表面的中红外发射率≤10％；
所述顶面覆盖层的亲水接触角小于90°；
所述电转中红外发射膜层包括低成本煤基纳米碳聚合物复合材料，所述电转中红外发射膜层的中红外发射率≥90％；
所述第一绝缘层和第二绝缘层包覆整个所述电转中红外发射膜层；
所述发射器还包括温度传感器和电力管理组件。
可选的是，所述中红外的光谱波长范围为3-50μm波段。
可选的是，所述第一表面的中红外发射率≥95％。
可选的是，所述顶面覆盖层、第一绝缘层、电转中红外发射膜层、第二绝缘层及底面覆盖层中的其中一层或多层为单层或多层结构。
可选的是，所述电转中红外发射膜层的平均中红外发射率≥95％。
可选的是，所述电转中红外发射膜层的薄层电阻≤100Ω/□，厚度≤200μm，弹性拉伸应变不少于10％。
可选的是，所述复合材料中的纳米碳包括石墨烯、碳纳米管、碳纳米纤维中的其中一种或几种。
可选的是，所述复合材料中的纳米碳包括从煤或焦炭中获得的包括石墨烯、碳纳米管、碳纳米纤维中的其中一种或几种多形貌导电纳米碳。
可选的是，所述复合材料中的聚合物包括热塑性聚氨酯、热塑性聚苯乙烯、热塑性聚酯、碳基橡胶、硅基橡胶、聚丙烯、聚乙烯、聚乙烯醇、聚对亚苯基对苯二甲酰胺中的其中一种或多种。
可选的是，所述顶面覆盖层的厚度≤100μm。
可选的是，所述顶面覆盖层的的结构材料包括聚酯、热塑性聚酯、热塑性聚氨酯、碳基橡胶、硅基橡胶其中的一种或多种；所述顶面覆盖层的染色材料包括无铅和无铬颜料、铝颗粒、涂层铝颗粒、二氧化钛颗粒、涂层二氧化钛颗粒、纳米碳黑、苝红、醌酞黄，铋黄、靛蓝、酞菁蓝、钴蓝、铜酞菁绿、氧化铁橙、氧化铁棕、无铅黄83其中的一种或多种。
可选的是，所述第一绝缘层和第二绝缘层的材料包括聚丙烯、聚乙烯、聚酯、热塑性聚酯、碳基橡胶、硅基橡胶中的其中一种或几种，厚度≤500μm。
可选的是，所述底面覆盖层的材料包括含锆的富金属氧碳氮化物、锆、铝、铜、锆合金、铝合金、铜合金、铬合金、不锈钢中的其中一种或几种；所述底面覆盖层的厚度≤100nm。
本发明还提供一种可穿戴式制品，所述可穿戴式制品包括上述任一种的可拉伸穿戴式电转中红外发射器。
可选的是，所述可穿戴式制品包括服装、服装配饰、床上用品、理疗装置中的其中一种或几种。
本发明还提供一种用于制备上述任一种可拉伸穿戴式电转中红外发射器的方法，所述方法包括：
(1)采用纳米碳聚合物复合材料制备电转中红外发射膜层：将所述复合材料中的聚合物分散在有机溶剂中形成第一混合液，再将所述复合材料中的纳米碳分散在上述第一混合溶液中形成第二混合液；采用标准液浆成膜工艺制备了所述电转中红外发射膜层；
(2)在所述电转中红外发射膜层的上下两面分别叠置第一绝缘层和第二绝缘层以得到依次为第一绝缘层、电转中红外发射膜层和第二绝缘层的层叠结构，其中，所述电转中红外发射膜层被第一绝缘层和第二绝缘层包裹，在所述层叠结构中形成多个沿层叠方向延伸的透气孔以得到透气结构；
(3)在所述透气结构靠近所述第一绝缘层的一侧形成顶面覆盖层，并在所述透气结构靠近所述第二绝缘层的一侧形成底面覆盖层。
附图说明
通过参考附图会更加清楚的理解本发明的特征和优点，附图是示意性的而不应理解为对本发明进行任何限制，在附图中：
图1为不同温度下标准黑体的红外辐射能量密度分布图。
图2为不同材料的红外辐射能量密度分布图。
图3为本发明的可拉伸穿戴式电转中红外发射器的主视图。
图4为本发明的可拉伸穿戴式电转中红外发射器的顶视图。
图5为本发明的可拉伸穿戴式电转中红外发射器中的透气路径。
图6为本发明的可拉伸穿戴式电转中红外发射器的制备方法示意图。
图7-1为本发明的条状可拉伸穿戴式电转中红外发射器设计，其中预封装的中红外发射膜条纹层压在穿孔的组成层上。(有气孔处截面图)
图7-2为本发明的条状可拉伸穿戴式电转中红外发射器设计，其中预封装的中红外发射膜条纹层压在穿孔的组成层上。(无气孔处截面图)
图8为本发明的条状可拉伸穿戴式电转中红外发射器设计，其中通过印刷产生中红外发射膜条纹。
图9为相同功率下本发明的实施例一SEME与市场竞品的测量特性对比
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在下面的部分中，给出并解释了一些实施例，以进一步说明本发明的技术细节。参照附图2-8可以更好地理解本发明的许多方面。图中的组成部分不一定按比例绘制，而是将重点放在清楚地说明本次展示的SEME原理上。
在一些实施例中，本发明揭示了一种可拉伸穿戴式电转中红外发射器(SEME)的基本结构，包括从SEME正面开始的以下多层，如图3所示，所述发射器包括依次层叠设置的顶面覆盖层31、第一绝缘层32、电转中红外发射膜层33、第二绝缘层34及底面覆盖层35；
所述发射器包括沿层叠方向相对设置的第一表面(顶表面)和第二表面(底表面)，所述顶面覆盖层31靠近所述第一表面，所述底面覆盖层35靠近所述第二表面；其中，所述第一表面的中红外发射率≥90％，所述第二表面的中红外发射率≤10％。
在一些具体的实施例中，顶面覆盖层31、第一绝缘层32、电转中红外发射膜层33、第二绝缘层34及底面覆盖层35可以分别具有如下特点：
(a)顶面覆盖层31为亲水，透气，美观和可拉伸穿戴的封装层，其中红外发射率≥90％；优选的是，所述顶面覆盖层的平均中红外发射率≥95％，更优选的是所述顶面覆盖层的平均中红外发射率接近100％；
(b)第一绝缘层32为电绝缘，中红外透明，透气且可灵活拉伸的层；
(c)电转中红外发射膜层33为以煤基纳米碳为填充剂且中红外发射率接近100％的可灵活拉伸，透气，高导电性的电转中红外发射膜；
(d)第二绝缘层34为电绝缘，中红外透明，热绝缘，透气和可灵活拉伸的层；
(e)底面覆盖层35为耐用的超薄金属/合金装饰层，其中红外发射率接近0(优选的是，平均中红外发射率≤5％)。
最后，还增加了温度传感器36和包括控制电路和电源在内的电力管理组件37，以生产功能性和可操作的SEME。
在本发明的一些实施例中，图3中的5个基本功能层31-35中的每一个都包含单层或多层结构，以优化每一个基本功能层的功能性能。
在本发明的一些实施例中，如图3所示，顶面覆盖层31的材料包括聚酯、热塑性聚酯、热塑性聚氨酯、碳基橡胶、硅基橡胶其中的一种或多种；优选的是，所述顶面覆盖层的材料还包括包括无铅和无铬颜料、铝颗粒、涂层铝颗粒、二氧化钛颗粒、涂层二氧化钛颗粒、纳米碳黑、苝红、醌酞黄，铋黄、靛蓝、酞菁蓝、钴蓝、铜酞菁绿、氧化铁橙、氧化铁棕、无铅黄83其中的一种或多种；所述顶面覆盖层的厚度≤100μm，亲水接触角小于90°，中红外发射率≥90％；优选的是，所述顶面覆盖层的平均中红外发射率≥95％，更优选的是所述顶面覆盖层的平均中红外发射率接近100％。
在一个具体的实施例中，顶面覆盖层31为具有中红外发射率接近100％的亲水、透气、美观和可拉伸穿戴层，更具体地，顶面覆盖层31的材料包括一种具有中红外发射率接近100％的聚酯,一般聚酯的中红外发射率并不接近100％,本发明通过从制备聚酯过程中对原材料与中间产物的红外光谱监控,保障产出的聚酯具有接近100％的中红外发射率。产生这种中红外发射率接近100％的证据如图2所示。在本发明的一些实施例中，该高发射率层着色为白色、黑色、红色、绿色、蓝色、黄色及其组合，并保持中红外发射率接近100％。图2显示了具有各种颜色的特殊聚酯产生接近于100％的中红外发射率的证据。有色聚酯是服装工业中使用最广泛的可穿戴聚合物，因此是生产本发明中SEME的优选材料。
在本发明的一些实施例中，顶面覆盖层31的材料可以是具有颜色的任何可穿着的聚合物，只要它的中红外发射率接近于100％，并且与聚酯一样成本较低。
在本发明的一些实施例中，所述第一绝缘层32和第二绝缘层34的材料包括聚丙烯、聚乙烯、聚酯、热塑性聚酯、碳基橡胶、硅基橡胶中的其中一种或几种，厚度≤500μm。
在一个具体的实施例中，所述第一绝缘层32和第二绝缘层34的材料包含聚乙烯。本发明揭示了聚乙烯可被设计成中红外透明效果最好的聚合物，并且聚乙烯成本较低，具有适当的隔热性和灵活可拉伸特性，适用于本发明中所揭示的SEME的结构。在一些实施方案中，聚乙烯层被表面改性以变得更具亲水性。在一些实施例中，第二绝缘层34还包括聚乙烯泡沫用以优化该层的隔热性能。
在本发明的一些实施例中，所述第一绝缘层32和第二绝缘层34的材料包括聚丙烯。在聚合物性能(包括热，化学和光学性能)的某些方面，聚丙烯的性能优于聚乙烯。像聚乙烯一样，聚丙烯也非常便宜。因此，聚丙烯也适用于本发明中揭示的SEME的结构。在一些实施方案中，聚丙烯层被表面改性以变得更具亲水性。在一些实施例中，第二绝缘层34还包括聚丙烯泡沫以优化该层的隔热性能。
在本发明的一些实施例中，所述第一绝缘层32和第二绝缘层34的材料还可以包括热塑性聚氨酯，热塑性聚酯，碳基橡胶，硅酮基橡胶，聚丙烯，聚乙烯及其组合。
所述电转中红外发射膜层33的薄层电阻≤100Ω/□，厚度≤200μm，中红外发射率≥90％，弹性拉伸应变不少于10％；优选的是，所述电转中红外发射膜层的中红外发射率≥95％。
所述电转中红外发射膜层33包括纳米碳聚合物复合材料，其中，所述复合材料中的纳米碳包括石墨烯、碳纳米管、碳纳米纤维中的其中一种或几种。所述复合材料中的纳米碳包括从煤或焦炭中获得的包括石墨烯、碳纳米管、碳纳米纤维中的其中一种或几种多形貌导电纳米碳。所述复合材料中的聚合物包括热塑性聚氨酯、热塑性聚苯乙烯、热塑性聚酯、 碳基橡胶、硅基橡胶、聚丙烯、聚乙烯中的其中一种或多种。其中，所述纳米碳由电阻率低于1Ω-cm的煤基纳米碳组成，其生产成本至少比石墨烯低50倍。在一些实施例中，炭黑被进一步石墨化至电阻率低于1Ω-cm，并用于制造本发明中的SEME。在一些实施例中，所述电转中红外发射膜层33包括多个沿层叠方向延伸的透气孔，孔是采用机械打孔、电弧加工、激光切割、选择性区域蚀刻及熔喷布成型其中的一种或几种方式形成的。
在本发明的一些实施例中，底面覆盖层35可以是具有中红外发射率接近0(例如平均中红外发射率≤5％)的耐用超薄金属/合金装饰层，其中包含富金属氧碳氮化物ZrAlvNxCyOz，其中，0<v<1,0<x<1,0<y<1,0<z<1。这种类似金属的涂层可以由普通的溅射设备制造，成本低廉，是一种耐用的涂层，具有闪亮的铂类外观。其中红外发射率接近于0。在一些实施例中，制备超薄铝底涂层以增强耐用涂层的附着力。
在本发明的一些实施例中，底面覆盖层35包含含锆的富金属氧碳氮化物、锆、铝、铜、锆合金、铝合金、铜合金、铬合金、不锈钢中的其中一种或多种。在一些实施例中，在底面覆盖层35的一面或两面制备超薄铝底涂层或钛底涂层以增强耐用涂层的附着力。
在一些实施例中，如图4所示，电转中红外发射膜层33包括电转中红外发射膜的柔性平行条带411、412……41n，这些条带通过灵活可拉伸的、电绝缘的和透气的间隔条421、422……42n连接在一起，其拉伸性和透气性主要通过设计间隔条来实现。
在一些实施例中，通过孔工程实现了通过本发明的SEME的多层的透气路径。在一些实施例中，这种透气路径是通过穿孔设计的。在一些实施例中，透气路径在整个SEME上均匀地分布，如图5右图所示。在一些实施例中，透气路径策略性地位于选择性区域中，并且透气区域策略性地位于SEME中。在一些实施例中，透气路径策略性地位于电转中红外发射膜条之间的间隔条中，如图5左图所示。
在一些实施例中，如图6所示，电转中红外发射膜条带611首先被两个薄的电绝缘层压层612和613夹在中间。然后这些包裹的中红外发射膜条带平行间隔并且层压成可灵活拉伸和透气中红外发射膜。
图7-1和图7-2显示所得中红外发射膜73被多层SEME设计的组成层71、72、74、75包围。其中，透气孔或可拉伸透气隔膜贯穿整个发射器的所有组成层71-75。
在一些实施例中，如图8所示，将中红外发射膜条83印刷到预制构成层的构成层81上。层压该所得的印刷层83得到具有构成层81的层。所有组成层81包括弹性拉伸聚合物、共聚物、混合聚合物及其组合。最后，在每对印刷条纹之间的间隔域中穿孔形成透气路径。
本发明还提供用于制备上述可拉伸穿戴式电转中红外发射器的方法，所述方法包括：
(1)采用纳米碳聚合物复合材料制备电转中红外发射膜层：将所述复合材料中的聚合物分散在有机溶剂中形成第一混合液，再将所述复合材料中的纳米碳分散在上述第一混合溶液中形成第二混合液；采用标准液浆成膜工艺制备了所述电转中红外发射膜层；
(2)在所述电转中红外发射膜层的上下两面分别叠置第一绝缘层和第二绝缘层以得到依次为第一绝缘层、电转中红外发射膜层和第二绝缘层的层叠结构，其中，所述电转中红外发射膜层被第一绝缘层和第二绝缘层包裹，在所述层叠结构中形成多个沿层叠方向延伸的透气孔以得到透气结构；
(3)在所述透气结构靠近所述第一绝缘层的一侧形成顶面覆盖层，并在所述透气结构靠近所述第二绝缘层的一侧形成底面覆盖层。
实施例
下面详细阐述一些具体的实施例。需要说明的是，以下内容只是在本发明原则的适用情况的例证或说明。在不背离现有原则和范围的前提下，我们可以做很多修改，用其他成分、方法和系统进行代替。因此，尽管在上文中已详细描述了本发明，但是下面的示例提供了目前被认为是最可行方案的进一步细节。
实施例1
具有顶底相反功能结构的SEME的生产和性能验证，其穿戴者正面朝前，视觉外观为白色，中红外发射率接近100％，其相反的面中红外发射率接近0。
在本发明的优选实施例1中，制造了高性能的SEME。
首先，将热塑性聚氨酯分散在环己酮中，将导电的煤基纳米碳分散在热塑性聚氨酯溶液中，采用标准液浆成膜工艺，制备了一种可拉伸的柔性中红外发射膜。所得薄膜的方阻为26±2Ω/□且厚度为80±2μm，并且制备了电阻为6Ω、尺寸为156cm 2的中红外发射膜。当外加电压为5V时，通过中红外发射膜的电流为0.83A，额定功率和单位面积功率分别为4.2W和0.027W/cm 2。
中红外发射膜由两层薄薄的聚丙烯夹在中间，包裹的中红外发射膜被穿孔，以实现透气性。然后，在透气中红外发射膜上涂上一层带有白色染料的聚酯稀溶液，用于对穿孔的侧壁进行电绝缘，并对封装中红外发射膜的最顶部表面进行工程设计，使其具有接近100％的中红外发射率。使用聚酯也是因为它具有亲水性和舒适的耐磨性。随后，中红外发射器的底部表面涂上一层含有锆、氮、碳和氧的超薄层，以形成一个中红外发射率接近0的耐用表面。
所合成的SEME具有可拉伸性和透气性，并具有与穿戴者接触的亲水表面。在全功率中红外发射器操作下，将与穿戴者接触的表面温度升高到46℃，并调整功率使其保持在理想温度。如图2所示，当表面温度为46℃时，以基准黑体为校准基准，SEME的面向穿戴者顶面的中红外辐射的红外发射率为96％，金属涂层表面的中红外发射率为5％。在这一系列操作条件下，中红外辐射到人体的功率密度约为55mW/cm 2。这种中红外辐射的功率密度远高于市场上常见的红外治疗灯。通常，这种红外光规定其发射光谱范围为3-25μm，光谱灵敏度峰值为5μm，建议功率密度小于30mW/cm 2。应注意的是，根据普朗克定律，发射光谱峰值为5μm的黑体的温度约为300℃；因此，这种红外线灯的热源在超过300℃以上的温度工作。相比之下，本实施例中的SEME发射具有9μm光谱峰值和接近46℃的工作温度的中红外。与普通的红外治疗灯相比，SEME的工作更安全，其中红外信号与人体的发射/吸收特征匹配得更好。
图9为相同功率下本实施例SEME与市场竞品的测量特性对比。由图9可以看出，本发明的SEME面向穿戴者的一面的温度达到46℃、中红外发射率达到98％，而背向穿戴者的一面或装饰面的温度维持在较低的31℃，中红外发射率更是低至10％，即功率损失非常之低。相比之下，竞品正面的温度为38℃、中红外发射率仅有93％，即对穿戴者的加热功率较为低下；而反面的中红外发射率高达93％，存在极高的功率损失。
实施例2
一种具有顶底相反功能结构的SEME的生产和性能验证，其穿戴者正面朝前，视觉外观为黑色，中红外发射率接近100％，其相反的面中红外发射率接近0。
在本发明的优选实施例中，制造了高性能的SEME。生产工艺与实施例1相同，只是白色聚酯被黑色聚酯取代。如图2所示，以基准黑体作为校准基准，表面温度为46℃的SEME中红外辐射的中红外发射率为97％，金属涂层表面的中红外发射率为5％。在这一操作条件下，中红外辐射到人体的功率密度约为56mW/cm 2。
实施例3
一种具有顶底相反功能结构的SEME的生产和性能验证，其穿戴者正面朝前，视觉外观为红色，中红外发射率接近100％，其相反的面中红外发射率接近0。
在本发明的这个具体实施例中，制造了高性能的SEME。生产工艺与实施例1相同，只是白色聚酯被红色聚酯取代。如图2所示，以基准黑体作为校准基准，表面温度为46℃时，SEME的中红外辐射的中红外发射率为92％。在这一操作条件下，中红外辐射到人体的功率密度约为53mW/cm 2。
实施例4
一种具有顶底相反功能结构的SEME的生产和性能验证，其穿戴者正面朝前，视觉外观为绿色，中红外发射率接近100％，其相反的面中红外发射率接近0。
在本发明的这个具体实施例中，制造了高性能的SEME。生产工艺与实施例1相同，只是在生产过程中，聚酯被绿色聚酯取代。如图2所示，以基准黑体作为校准基准，表面温度为46℃时，SEME的中红外辐射，中红外发射率为91％。在这一操作条件下，中红外辐射到穿戴者身上的功率密度约为52mW/cm 2。
比较例1
一种无顶底相反功能结构设计的SEME生产与性能验证
在本发明的这个实施例中，一个试验SEME被生产出来。生产工艺与实例1相同，只是与穿戴者反向的SEME表面没有被有光泽的富金属覆盖层覆盖。因此，这个表面也是高辐射的。维持相同操作温度46℃的额定功率约为实例1中SEME的1.6倍。显然，顶底相反功能结构的设计降低了能源消耗。
比较例2
一种用合金线加热器代替薄膜加热器的SEME生产及性能验证
在本发明的这个比较实施例中，一个试验SEME被生产出来。生产工艺与实例1相同，只是电转中红外发射膜被具有相同电阻的细长锯齿形电热金属丝代替。用红外摄像机拍摄了从这个电热金属丝发热器的中红外辐射，穿戴者正面的表面温度为46℃。中红外成像证实表面温度和中红外辐射不均匀。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明，本领域技术人员可以在不脱离本发明的精神和范围的情况下作出各种修改和变型，这样的修改和变型均落入由所附权利要求所限定的范围之内。

Claims (14)

  1. 一种低成本可拉伸穿戴式电转中红外发射器，其特征在于，所述发射器包括依次层叠设置的顶面覆盖层、第一绝缘层、电转中红外发射膜层、第二绝缘层及底面覆盖层，每层都可拉伸和透气；
    所述发射器包括沿层叠方向相对设置的第一表面和第二表面，所述顶面覆盖层靠近所述第一表面，所述底面覆盖层靠近所述第二表面，所述第一表面面向穿戴者，所述第一表面的中红外发射率≥90％，所述第二表面的中红外发射率≤10％；
    所述顶面覆盖层的亲水接触角小于90°；
    所述电转中红外发射膜层包括低成本煤基纳米碳聚合物复合材料，所述电转中红外发射膜层的中红外发射率≥90％；
    所述第一绝缘层和第二绝缘层包覆整个所述电转中红外发射膜层；
    所述发射器还包括温度传感器和电力管理组件。
  2. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述中红外的光谱波长范围为3-50μm波段。
  3. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述顶面覆盖层、第一绝缘层、电转中红外发射膜层、第二绝缘层及底面覆盖层中的其中一层或多层为单层或多层结构。
  4. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述第一表面的中红外发射率≥95％。
  5. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述电转中红外发射膜层的中红外发射率≥95％。
  6. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述电转中红外发射膜层的薄层电阻≤100Ω/□，厚度≤200μm，弹性拉伸应变不少于10％。
  7. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述复合材料中的纳米碳包括从煤或焦炭中获得的包括石墨烯、碳纳米管、碳纳米纤维中的其中一种或几种的多形貌导电纳米碳。
  8. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述复合材料中的聚合物包括热塑性聚氨酯、热塑性聚苯乙烯、热塑性聚酯、碳基橡胶、硅基橡胶、聚丙烯、聚乙烯、聚乙烯醇、聚对亚苯基对苯二甲酰胺中的其中一种或多种。
  9. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述顶面覆盖层的结构材料包括聚酯、热塑性聚酯、热塑性聚氨酯、碳基橡胶、硅基橡胶其中的一种或多种；所述顶面覆盖层的染色材料包括无铅和无铬颜料、铝颗粒、涂层铝颗粒、二氧化钛颗粒、涂层二氧化钛颗粒、纳米碳黑、苝红、醌酞黄，铋黄、靛蓝、酞菁蓝、钴蓝、铜酞菁绿、氧化铁橙、氧化铁棕、无铅黄83其中的一种或多种。
  10. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述第一绝缘层和第二绝缘层的材料包括聚丙烯、聚乙烯、聚酯、热塑性聚酯、碳基橡胶、硅基橡胶中的其中一种或几种。
  11. 根据权利要求1所述的可拉伸穿戴式电转中红外发射器，其特征在于，所述底面覆盖层的材料包括含锆的富金属氧碳氮化物、锆、铝、铜、锆合金、铝合金、铜合金、铬合金、不锈钢中的其中一种或几种；所述底面覆盖层的厚度≤100nm。
  12. 一种可穿戴式制品，其特征在于，所述可穿戴式制品包括权利要求1-11任一项所述的可拉伸穿戴式电转中红外发射器。
  13. 根据权利要求12所述的可穿戴式制品，其特征在于，所述可穿戴式制品包括服装、服装配饰、床上用品、理疗装置中的其中一种或几种。
  14. 一种用于制备权利要求1-11任一项所述的可拉伸穿戴式电转中红外发射器的方法，其特征在于，所述方法包括：
    (1)采用纳米碳聚合物复合材料制备电转中红外发射膜层：将所述复合材料中的聚合物分散在有机溶剂中形成第一混合液，再将所述复合材料中的纳米碳分散在上述第一混合溶液中形成第二混合液；采用标准液浆成膜工艺制备所述电转中红外发射膜层；
    (2)在所述电转中红外发射膜层的上下两面分别叠置第一绝缘层和第二绝缘层以得到依次为第一绝缘层、电转中红外发射膜层和第二绝缘层的层叠结构，其中，所述电转中红外发射膜层被第一绝缘层和第二绝缘层包裹，在所述层叠结构中形成多个沿层叠方向延伸的透气孔以得到透气结构；
    (3)在所述透气结构靠近所述第一绝缘层的一侧形成顶面覆盖层，并在所述透气结构靠近所述第二绝缘层的一侧形成底面覆盖层。
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