(19)
(11)EP 3 286 263 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 16717642.9

(22)Date of filing:  21.04.2016
(51)Int. Cl.: 
C08L 67/02  (2006.01)
C08J 3/28  (2006.01)
C08L 101/00  (2006.01)
(86)International application number:
PCT/EP2016/058884
(87)International publication number:
WO 2016/170046 (27.10.2016 Gazette  2016/43)

(54)

HEATING OF POLYMERIC MATERIALS

ERWÄRMUNG VON POLYMERMATERIALIEN

CHAUFFAGE DE MATÉRIAUX POLYMÈRES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 22.04.2015 EP 15164680
22.04.2015 EP 15164684

(43)Date of publication of application:
28.02.2018 Bulletin 2018/09

(73)Proprietor: University of Limerick
Limerick (IE)

(72)Inventors:
  • MCGRAIL, Patrick Terence
    Salburn-by-the-Sea North Yorkshire TS13 5LX (GB)
  • ROY, Dipa
    Annacotty Limerick (IE)
  • ROY, Ananda
    Annacotty Limerick (IE)
  • HANLY, Richard
    Shannon County Clare (IE)
  • STANLEY, Walter
    Corbally Limerick (IE)

(74)Representative: Appleyard Lees IP LLP 
15 Clare Road
Halifax HX1 2HY
Halifax HX1 2HY (GB)


(56)References cited: : 
US-A- 4 141 879
US-A- 5 854 347
  
  • WU G ET AL: "Carbon black-loading induced phase fluctuations in PVDF/PMMA miscible blends: dynamic percolation measurements", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 42, no. 7, 1 March 2001 (2001-03-01), pages 3271-3279, XP004227293, ISSN: 0032-3861, DOI: 10.1016/S0032-3861(00)00417-1
  • CARMEN DEL RIO ET AL: "EXTRINSIC CONDUCTING AND SUPERCONDUCTING POLYMER SYSTEMS-II. EFFECTOF COPPER AND CARBON BLACK ON THE COMPATIBILITY AND THE MORPHOLOGY OF PVDF/PS BLENDS", EUROPEAN POLYMER JOURNAL, PERGAMON PRESS LTD. OXFORD, GB, vol. 31, no. 6, 1 June 1995 (1995-06-01), pages 581-587, XP000502860, ISSN: 0014-3057, DOI: 10.1016/0014-3057(94)00206-1
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Introduction



[0001] The invention relates to the heating of polymeric materials. More particularly, the invention relates to heating polymeric materials utilising electromagnetic radiation, such as Radio Frequency (RF) radiation, for example radiation having a frequency of for example in the range 10 MHz to 30 MHz, for purposes such as moulding, forming, flowing or curing or for any other purpose. The invention also relates to heating said polymeric materials utilising microwave radiation (MW) having a frequency of for example in the range 900 MHz to 2.45 GHz, for said purposes.

[0002] [1] describes the use of microwave irradiation to heat polymers containing components such as talc, zinc oxide and carbon black. For example, the carbon black proportion may be in the range of 5 to 30 percentage by weight (wt%). [2] describes the heating of a combination of a polymer with an inorganic salt as a "dielectric heating promoter". [3] discloses a composition comprising base polymers and a RF susceptible polymer.

[0003] The invention is directed towards achieving improved heating of polymers by radio frequency or microwave frequency radiation.

References



[0004] 
  1. [1] "Use of Fillers to Enable the Microwave Processing Of Polyethylene", John Harper, Duncan Price and Jie Zhang, Journal of Microwave Power & Electromagnetic Energy, Vol. 40, No. 4, 2007
  2. [2] GB2065138 (Polymer Laboratories).
  3. [3] US 5,854,347

Summary of the Invention



[0005] A material susceptible to dielectric heating by electromagnetic radiation, the material comprising:

a base polymeric material, and

a dielectric heating susceptor comprising:

polymeric material different from the base polymeric material and having a higher dielectric loss factor than the base polymeric material, and

electrically polarisable entities dispersed within the base polymeric material; wherein the dielectric heating susceptor polymeric material is present in the form of discrete phases in the base polymeric material, forming a multiple phase morphology; and wherein the electrically polarisable entities are present in a proportion of 0.1 to 10 wt% of the material.



[0006] The material is susceptible to radio frequency heating. The material may be susceptible to microwave heating. The material may be susceptible to both radio frequency heating and microwave heating.

[0007] Suitably the dielectric heating susceptor is a material which is susceptible to dielectric heating. Suitably the dielectric heating susceptor is a material which can absorb electromagnetic radiation and convert said electromagnetic radiation to heat. Suitably the dielectric heating susceptor can absorb radio frequency radiation and/or microwave radiation and convert said radiation to heat. The dielectric heating susceptor may be an RF susceptor. The dielectric heating susceptor may be a microwave susceptor. The dielectric heating susceptor may be both an RF susceptor and a microwave susceptor.

[0008] Suitably the electrically polarisable entities are dispersed individually within the base polymeric material. Additionally or alternatively the electrically polarisable entities may be considered as discrete entities within the base polymeric material.

[0009] Suitably the electrically polarisable entities are capable of producing high interfacial polarisation loss, when dispersed within the base polymeric material.

[0010] The electrically polarisable entities may be electrically conductive entities. By electrically conductive entities we mean that the material from which the electrically conductive entities are formed is capable of conducting electricity, when present as a continuous bulk material for example. However, when present as the electrically polarisable entities of the present invention, the electrically conductive entities are suitably not capable of conducting electricity through the material of the present invention, as further described herein, due to the electrically conductive entities being present as discrete and/or dispersed entities not forming a continuous network.

[0011] In one embodiment, the base polymeric material is a thermoplastic polymer.

[0012] In one embodiment, the dielectric heating susceptor polymeric material is present in a proportion of 1 to 30 wt%, preferably 5 to 25 wt%.

[0013] According to the invention, the electrically polarisable entities are present in a proportion of 0.1 to 10 wt%, preferably 0.5 wt% to 5 wt%.

[0014] According to the invention, the dielectric heating susceptor polymeric material is present in the form of discrete phases in the base polymeric material, forming a multiple phase morphology.

[0015] Suitably the base polymeric material is a thermoplastic polymer or copolymer or blend.

[0016] Suitably the base polymeric material is a thermosetting polymer or copolymer or blend. Suitably the base polymeric material is a blend of a thermosetting polymer with a thermoplastic polymer or copolymer.

[0017] Suitably the base polymeric material is selected from polyesters, polyolefins, polyphenylene sulfide, polyetherketones, polyethers, polyamides, polyetherimide, polyacrylonitrile, polystyrene, polyacrylates, polyethersulfones, polycarbonates, natural polymers, copolymers and blends/mixtures thereof.

[0018] Suitably the base polymeric material is selected from polyethylene terephthalates (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyetherimide (PEI), polystyrene (PS and ABS), polyacrylates (e.g. PMMA), polycarbonate (PC), polyphenylene sulphide (PPS) or blends/mixtures thereof. In some embodiments, the base polymeric material may be a copolymer of one or more of these polymers.

[0019] Suitably the base polymeric material is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyphenylene sulphide (PPS), polyetherimide (PEI), polystyrene (PS), acrylonitrile/butadiene/styrene (ABS), polyacrylates (e.g. PMMA), polyacrylonitrile (PAN), polycarbonate (PC) or blends/mixtures thereof.

[0020] Suitably the base material includes PET.

[0021] Suitably the base polymeric material is selected from but not restricted to epoxies, vinyl esters, unsaturated polyesters, phenolics, cyanate esters, bismaleimides, polyimides, and blends/mixtures thereof.

[0022] Suitably the base polymeric material is selected from but not restricted to blends of epoxies, vinyl esters, unsaturated polyesters, phenolics, cyanate esters, bismaleimides, polyimides, and blends/mixtures thereof with polyethersulphones, polycarbonates, polyetherimides, polyetherketones, polyesters, polyacrylics and blends/mixtures thereof.

[0023] Suitably the dielectric heating susceptor polymeric material is a polar polymer.

[0024] Suitably the base polymeric material is a thermoplastic polymer or copolymer and the polymeric material of the dielectric heating susceptor is a polar polymer.

[0025] Suitably the polymeric material of the dielectric heating susceptor is a polar polymer comprising one or a combination of polyvinylidine fluoride (PVDF), polyurethane (PU), and polyamide imide (PAI).

[0026] Suitably the dielectric heating susceptor is an RF susceptor and the polymer material of the RF susceptor is a polar polymer comprising one or a combination of PVDF, PU, and PAI.

[0027] In one embodiment, the base material is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyetherimide (PEI), polystyrene (PS), polyacrylates (e.g. PMMA), polycarbonate (PC) or blends/mixtures thereof; and the dielectric heating susceptor is a polar polymer comprising one or a combination of PVDF, PU and PAI.

[0028] In one embodiment, the base material is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyphenylene sulphide (PPS), polyetherimide (PEI), polystyrene (PS), acrylonitrile/butadiene/styrene (ABS), polyacrylates (e.g. PMMA), polyacrylonitrile (PAN), polycarbonate (PC) or blends/mixtures thereof; and the dielectric heating susceptor is a polar polymer comprising one or a combination of PVDF, PU and PAI.

[0029] In one embodiment, the base material is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyphenylene sulphide (PPS), polyetherimide (PEI), polystyrene (PS), acrylonitrile/butadiene/styrene (ABS), polyacrylates (e.g. PMMA), polyacrylonitrile (PAN), polycarbonate (PC), epoxies, vinyl esters, unsaturated polyesters, phenolics, cyanate esters, bismaleimides, polyimides, and blends/mixtures thereof; and the dielectric heating susceptor is a polar polymer comprising one or a combination of PVDF, PU, PAI, PA, cellulose esters, PVC, acrylics, PVC/acrylic alloy.

[0030] In one embodiment, the base material includes PET and the dielectric heating susceptor polymer material is a polar polymer comprising one or a combination of PVDF, PU, and PAI.

[0031] The polymeric material of the dielectric heating susceptor may be additionally or alternatively selected from cellulose esters, polyamides (PA), polyvinyl chloride (PVC), acrylics, PVC/acrylic alloy.

[0032] In one embodiment, the electrically polarisable entities are present in the form of discrete entities (or units) not forming a conductive network. Suitably the material susceptible to dielectric heating of the present invention is not conductive, for example it does not conduct electricity through the material. In one embodiment, the size of the electrically polarisable entities is in the range of 10 nm to 100µm. Suitably the electrically polarisable entities are particles having a size in the range of 10 nm to 100µm.

[0033] In one embodiment, the electrically polarisable entities comprise carbon black.

[0034] Suitably the electrically polarisable entities have high interfacial polarisation loss properties.

[0035] In one embodiment, the electrically polarisable entities are of conductive material having interfacial polarisation loss properties.

[0036] In one embodiment, the base polymeric material is modified with an elastomer.

[0037] In one embodiment, the material further comprises a filler material to provide desired mechanical properties and/or flame-retardency and/or environmental resistance and/or chemical resistance, said filler material comprising particles and/or platelets and/or tubes and/or fibres to provide a composite material.

[0038] In another aspect, the invention provides a process for heating a material as defined above in any embodiment, the process comprising irradiating the material with electromagnetic radiation until a desired temperature is achieved. In one embodiment, the electromagnetic radiation is RF radiation with a frequency in the range of 10MHz to 30MHz, and preferably in the range of 13.54 MHz to 27.12 MHz. In one embodiment, the electromagnetic radiation is MW radiation with a frequency in the range 900 MHz to 2.45 GHz.

Detailed Description of the Invention



[0039] The invention will be more clearly understood from the following description of some embodiments thereof, given by way of example only with reference to the accompanying drawings in which:-

Fig. 1 is a schematic illustrating a base polymeric material containing discrete phases of a polar dielectric heating susceptor polymeric material and separate, discrete entities of an electrically polarisable material such as particles of certain grades of: carbon, polyaniline, polyaniline coated carbon black, polypyrrole coated carbon black, graphene, metals, metal coated polymers and other metallic entities etc. remaining dispersed in the base polymeric material. Suitably such materials are capable of producing high interfacial polarisation loss in response to an applied electric field;

Figs. 2 to 4 are plots showing compositions and heating performance values;

Fig. 5 is a set of images showing the material phases;

Figs. 6 to 11 are further plots showing measured values for tests;

Fig. 12 is a diagram showing heating and pressing of a dielectric heating susceptible material as sheaths around non-heating cores in fibres, and Fig. 13 is an image showing fibre cross sections with dielectric heating susceptible sheath around cores.

Fig. 14 is a flow diagram showing heating and pressing of a dielectric heating susceptible material in the surface layers of a tri-layer tape in a woven form; and

Figs. 15 shows the cross section of the tri-layer tape based laminate before and after consolidation in an RF press.

Figs. 16, 17 and 18 show the results of microwave heating trials.



[0040] We describe polymeric materials which are susceptible to dielectric heating and methods of heating these materials.

[0041] Polymeric materials and processes for the heating of polymeric materials by dielectric heating are described. The polymeric materials comprise a base polymeric material and a dielectric heating susceptor. The dielectric heating susceptor comprises of a combination of i) a polymeric material, different from the base polymeric material, which has the ability to polarise in response to an applied electric field and has high dielectric loss properties, and ii) discrete electrically polarisable entities, which suitably have the capability of producing high interfacial polarisation loss in an applied electric field. Filler-type materials, including particles and/or fibres and/or platelets and/or tubes, may also be incorporated into the polymeric materials. The base polymeric material and the susceptor polymeric material form an immiscible blend and the discrete electrically polarisable entities locate themselves preferentially in the base polymeric material phase. The susceptor polymeric material has a high dielectric loss factor and is responsive to an electromagnetic, for example an RF or microwave, field and provides high dielectric loss to the compounded material. High dielectric loss means higher ability of a material to dissipate a significant part of the applied electromagnetic energy in the form of heat. A material with high dielectric loss will thus heat up more in an electromagnetic field than a material with low dielectric loss. The presence of dispersed phases of such high dielectric loss materials in the base polymer will thus heat up the surrounding base polymer in an electromagnetic, for example an RF or microwave, field. The concentration of the discrete electrically polarisable entities is preferably kept at less than 5wt% so that they can have a significant interfacial polarisation loss which adds to the overall dielectric loss of the material. Without being bound by theory, it is believed that the electrically polarisable entities (including electrically conductive entities), when present discretely in a polymeric matrix, and therefore separated by insulating layers of the polymer, undergo interfacial polarisation in an electromagnetic, for example an RF or microwave, field due to entrapment of the free charges between the polar/non-polar interfaces. The interfacial polarisation is caused by an enhancement in the motion of the trapped virtual charges at the interface of the components of the multiphase material of different polarity leading to a high interfacial polarisation loss.. When an optimum combination of these two materials is incorporated in a base polymeric material as an electromagnetic, for example an RF or microwave, susceptor there is a surprising synergy between these two materials which results in a maximised heating effect in an electromagnetic, for example an RF or microwave, field which is significantly higher than that provided by either of these susceptors when used individually. Incorporating these susceptors in a base polymeric material can be achieved by any industrially viable route such as melt mixing, etc.

[0042] The base polymeric material and the susceptor polymeric material form an immiscible blend and the electrically polarisable entities preferentially locate in the base polymeric material, remaining isolated from one another. These electrically polarisable entities may range in size and form. For example, particles or platelets from 10 nm to 100 µm in diameter and fibres or tubes from 10nm to 10mm in length are suitable and may be used either alone or in combination. However, such electrically polarisable entities are not limited to these forms and sizes and may be in any other physical form or size which is compatible with the polymeric materials and the blending process being used, and which satisfy the dispersibility and conductive requirements described herein.

[0043] The radiation to heat the material may be, for example, either RF radiation having a frequency preferably in the range 10MHz to 30MHz, and more preferably in the range of 13.54MHz to 27.12MHz, or may be, for example, MW radiation having a frequency in the range 900 MHz to 2.45 GHz.

[0044] The base polymeric material may be selected from a broad range of thermoplastic semicrystalline or amorphous polymers such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyetherimide (PEI), polystyrene (PS), polyacrylates (e.g. PMMA), polycarbonate (PC) etc. or blends of any such polymers. In addition, such susceptors can be incorporated into thermosetting resins to enable their heating and curing in an electromagnetic, for example an RF or microwave, field. Thermoset-thermoplastic resin blends can also be used as the base polymeric material. The base polymeric material may contain filler-type materials used in the trade such as particles and/or fibres to form composite materials. Such fillers may be used to enhance or otherwise modify mechanical and/or thermal properties and/or environmental resistance and/or fire resistance and/or to provide functionality and other special effects and/or to modify processability and/or to reduce cost.

[0045] The choice of the susceptor materials will vary depending on the base polymeric material and any filler-type materials incorporated into it.

[0046] The susceptors may be present in the base polymeric material where heating of the bulk is required or may be incorporated into a base polymeric material which forms an outer layer in a tri-layer tape or a sheath around a material which is not to be substantially heated, such as a fibre, for example, or in any other form where selective heating or melting is required. Different thermoplastic polymers such as PET, PE, PP, PA, PEEK, PPS, PEI, PS, ABS, PMMA, and PC, or blends thereof, or thermosetting resins such as epoxies, vinyl esters, unsaturated polyesters, phenolics, cyanate esters, bismaleimides or blends thereof, or thermoset/thermoplastic blends can be made dielectric heating susceptible by the incorporation of suitable susceptors.

[0047] In more detail, the dielectric heating susceptor includes at least:
  1. i) A susceptor polymer. This may be a polar polymeric material with high dielectric loss factor (DLF) such as PVDF, a PU, a PAI, PA, cellulose esters, PVC, acrylics, PVC/acrylic alloy suitably in 1-30 wt% ratio with the base polymeric material. The susceptor polymeric material is immiscible with the base polymeric material and together they preferably form a two-phase morphology. The susceptor polymeric material preferably exhibits high dipolar loss in an electromagnetic, for example an RF or microwave, field and increases the overall dielectric loss of the material.
  2. ii) Entities of an electrically polarisable material (used at 0.1 to 10 wt%). These polarisable entities remain dispersed in the base polymeric material, in other words as individual units, and their concentration is such that it is not adequate to form a conductive network throughout the material, yet they have an interfacial polarisation loss in an electromagnetic, for example an RF or microwave, field which adds to the overall dielectric loss of the material.


[0048] The susceptor components can be incorporated into the base polymeric material by any industrially viable process. The dielectric heating susceptor is formulated in such a way that minimum amounts of the component materials are required to attain high dielectric loss leading to a significant amount of heating in an electromagnetic, for example an RF or microwave, field in a significantly shorter period of time compared to the unmodified base material. Minimum concentration of the susceptor components in the base polymeric material is desirable in order to have minimal effect on the base polymeric material properties.

[0049] The selection of the base polymeric material (suitably 70-99 wt%) and the susceptor polymeric material (suitably 1-30 wt%) is done in such a way that they are immiscible. The polarisable entities preferentially remain dispersed in the base polymeric material. The susceptor polymeric material (1 to 30 wt%) forms discrete phases in the base polymeric material to produce a morphology which may be of the particulate or so-called sea-island type and the polarisable entities reside individually in the base polymer phase without forming any percolating or conducting network, for example a continuous network of such entities throughout the material which would be able to conduct electricity through the material if the polarisable entities are conductive. This is shown schematically in Fig. 1 where a base polymeric material (1) contains a discrete phase (2) of the susceptor polymeric material and the polarisable entities (3) remain dispersed in the base polymeric material without forming any continuous and/or conductive network.

[0050] For dielectric heating, the material dielectric property of interest is the dielectric loss factor or DLF (ε"), which principally determines the amount of energy absorbed by the material for a given electric field. This absorption of electrical energy eventually manifests itself as heat and the higher the DLF the more heat is generated in the material in an electric field. Dielectric loss results from the inability of the polarization process in a polar molecule to follow the rate of change of the oscillating applied electric field. This is related to the relaxation time of a polymer, which is the time taken for the dipoles to return to their original random orientation. It does not occur instantaneously but the polarization diminishes exponentially. If the relaxation time is smaller or comparable to the oscillating rate of the electric field then there is either no loss or minimum loss. However, when the electric field oscillates faster than the relaxation time the polarization cannot follow the oscillating frequency and this results in energy absorption and its dissipation as heat. There is no dipole polarization contribution for non-polar polymers, hence non-polar polymers have a low DLF and do not heat rapidly in an electric field. In addition to dipolar loss in an electric field there is also interfacial polarisation loss which originates from an excessively polarised interface between dispersed polarisable entities and the base polymeric material. Dipolar loss and interfacial polarisation loss are the two major mechanisms which contribute to the overall dielectric loss of a material. A polar polymer like polyvinylidene difluoride (PVDF) has a high dipolar loss and electrically polarisable materials such as some grades of carbon black exhibit high interfacial polarisation loss. Dipolar loss and interfacial polarisation loss effects have been maximised here by the selection of a suitable combination of susceptor material components to produce a synergistic effect.

[0051] One example of a base polymeric material is polyethylene terephthalate (PET). A broad range of compositions were studied to optimise the formulation including different susceptor polymers and different polarisable entities. The base polymer content was varied between 67 to 94 wt% and the susceptor polymer was varied between 5 to 30 wt%. The polarisable material content was varied between 0 and 3 wt%. A dielectric heating susceptor formulation which has been evaluated with PET is a combination of functionalised PVDF (Kynar® ADX 111 from Arkema with a measured DLF above 0.08 at 27.12 MHz at room temperature) used at 5 to 15 wt% with polarisable entities comprising particles of a suitable grade of carbon black (CB) (Black Pearl® 2000 from Cabot Corporation) used at 1 to 3 wt%. This grade of CB is a furnace process carbon black designed for critical applications and is capable of undergoing high interfacial polarisation loss in an electric field. It has good physical properties, making it suitable for compounding with polymeric materials and a highly aggregated structure comprising very fine (12 nm) individual carbon particles of high surface area (1487 m2g-1). The CB contributes to the interfacial polarisation loss and an overall increase in the dielectric loss of the whole material. The grade of PVDF used here contains functional groups which impart strong interfacial properties with the base polymer.

[0052] The compositions of some of the materials based on PET and utilising the PVDF and CB grades described above and which were tested for RF heating are as follows:
Table 1: Polymer blend compositions (PET-PVDF-CB) designed to develop RF susceptible formulation
Base polymer PET (wt%)RF Susceptor
PVDF (wt%)Carbon black (wt%)
100 0 0
99 0 1
97 0 3
95 5 0
94 5 1
92 5 3
85 15 0
84 15 1
82 15 3
70 30 0
69 30 1
67 30 3

Dielectric Measurement



[0053] Table 2 shows the DLF for all the compositions measured at room temperature at 27.12 MHz frequency using an HP 4917 Impedance Gain Analyser. It will be seen from this table that the DLF values are particularly high where the CB proportion is at 3wt%.
Table 2: DLF values of the blend compositions at 27.12 MHz frequency at room temperature.
CompositionDLF at 27.12 MHz frequency
PET (wt%)PVDF (wt%)CB (wt%)
100 0 0 0.03501
99 0 1 0.04748
95 5 0 0.04430
94 5 1 0.05392
92 5 3 0.35197
85 15 0 0.03193
84 15 1 0.04896
82 15 3 0.44501
70 30 0 0.04367
69 30 1 0.04628
67 30 3 0.44793

RF Heating



[0054] The blend compositions were tested for their heating ability in an RF press using a pressure of 450 kPa. Test blocks (50 mm × 20 mm × 10 mm) were manufactured by extrusion and compression moulding. Table 3 shows the RF heating test parameters.
Table 3: RF heating test parameters
 RF Power (kW)-Time (sec)
Set I 0.00 kW-5 sec
0.20 kW-10 sec
0.35 kW-30 sec
Set II 0.00 kW-5 sec
0.20 kW-10 sec
0.35 kW-60 sec
Set I III 0.00 kW-5 sec
0.20 kW-10 sec
0.45 kW-30 sec
Set I IV 0.00 kW-5 sec
0.20 kW-10 sec
0.45 kW-60 sec


[0055] The RF heating results of the (PET-PVDF) blends are given in Table 4.
Table 4: Effect of PVDF on RF heating of PET, values are the highest temperature achieved (in °C) measured by an IR thermometer.
 Highest Temperature (°C)
PET-PVDF-CB Blend Compositions0.35 kW-30 sec0.35 kW-60 sec0.45 kW-30 sec0.45 kW-60 sec
100-0-0 31.0 49.0 39.0 61.0
95-5-0 48.0 70.0 57.0 74.0
85-15-0 60.0 94.0 76.0 90.0
70-30-0 82.0 104.0 85.0 99.0


[0056] The results are also shown in Figs. 2 and 3. The effects of increasing PVDF content in the blends are shown in Figs. 2 and 3 at two different RF power levels and times. These plots show the temperature rise in PET with different PVDF contents at two different RF power levels (0.35 kW and 0.45 kW) and two different times (30 sec and 60 sec). The vertical axes of these plots are the highest temperatures attained by the test samples in the RF field as measured by an IR thermometer.

[0057] The effect of combination of (PVDF-CB) susceptor on the RF heating is given in Table 5.
Table 5: Effect of the combination of (PVDF-CB) on the RF heating of PET, values are the highest temperature achieved (in °C) measured by an IR thermometer
PET-PVDF-CB Blend Compositions0.35 kW-30 sec0.35 kW-60 sec0.45 kW-30 sec0.45 kW-60 sec
100-0-0 31.0 49.0 39.0 61.0
99-0-1 46.0 63.0 56.0 75.0
95-5-0 42.0 60.0 58.0 49.0
94-5-1 96.0 117.0 115.0 127.0
92-5-3 113.0 arcing arcing arcing
85-15-0 53.0 88.0 69.0 71.0
84-15-1 76.0 109.0 102.0 100.0
82-15-3 111.0 arcing arcing arcing
70-30-0 60.0 95.0 76.0 94.0
69-30-1 85.0 105.0 90.0 102.0
67-30-3 125.0 arcing arcing arcing


[0058] The results are also shown in Figs. 4a, b and c. Fig. 4 shows the temperature rise in PET-PVDF blend compositions with different CB contents at two different RF power levels (0.35 kW and 0.45 kW) and times (30 sec and 60 sec). The samples with 3 wt% CB showed arcing and could not be tested.

Morphology



[0059] The morphology of a test sample with the composition PET-PVDF-CB 84-15-1 was determined using SEM (Scanning Electron Microscopy). The sample was prepared for SEM analysis by removing the PVDF fraction using solvent extraction with dimethylacetamide. In Fig. 5 micrographs from this SEM analysis show the presence of dispersed CB particles in the PET phase.

DoE Analysis



[0060] Design of Experiments (DoE) were employed to gather information on the interactions between the elements in the design (PVDF and CB content) and how these interactions affected the variation in the output measure (DLF). Fig. 6 shows the contribution of the individual PVDF and CB components compared with the combined PVDF and CB interactions in the material, which has significant influence on the DLF of the material in an applied electric field at room temperature at 27.12 MHz frequency. The variables along the X axis of these plots are the components PVDF and CB used in the formulation, either taken individually or in combination. The Y axis shows the contribution of the components, individually or in combination, to the DLF gain variability of the material.

[0061] Fig. 6 shows the contribution of the individual and combined PVDF and CB contents on the DLF of the material. The graph clearly indicates that the combined interaction of the PVDF and CB components has a more pronounced effect on the DLF value of the material than the individual contribution of each component.

[0062] Design of Experiments (DoE) was also employed to gather information on the interactions between the PVDF and CB content in the design and how these interactions influenced the variation in the output measure (temperature rise in the RF field). Figs. 7 and 8 show the contribution of the individual and combined interactions in raising the temperature of the material under RF field. The variables along the X axes of these plots are the amounts of PVDF and CB used in the formulation, either taken individually or in combination. The Y axes represent the contribution of the components, individually or in combination, to the temperature gain variability of the material in the RF field.

[0063] Fig. 7 shows the contribution of the individual and combined PVDF and CB interactions on the temperature gain variability of the material in the RF field at 0.35 kW RF power.

[0064] Fig 8 shows the contribution of the individual and combined PVDF and CB interactions on the temperature gain variability of the material at 0.45 kW RF power.

[0065] The contribution of the combined interactions of PVDF and CB were found to be predominant across all formulations and for all RF test parameters (0.35 kW and 0.45 kW power levels and 30 sec and 60 sec times).

Thermal Imaging



[0066] The RF heating ability of the different blend compositions were also tested with a thermal imaging camera. The tests were done for 60 sec at two power levels, 0.35 kW and 0.45 kW.

[0067] The highest temperatures measured by the thermal imaging camera are plotted in Figs. 9 and 10. Fig. 9 and 10 show the temperature rise in the material with increase in PVDF content (0-30 wt%) at two different RF power levels of 0.35 kW and 0.45 kW respectively for 60 sec.

[0068] Fig. 11 shows the temperature rise in PET-PVDF blend compositions with different CB contents when tested in RF field at (a) 0.35 kW (b) 0.45 kW power levels for 60 sec.

[0069] In general terms the preferred ranges of proportions of the components for the RF susceptible formulation in this example are PET (84-94 wt%), PVDF (5-15 wt%) and CB (1 wt%).

[0070] In one example, a PET-PVDF-CB composition of 84-15-1 was selected for making a core:sheath type bicomponent fibre. This RF susceptible formulation formed the sheath of the coaxial fibres to render the sheath RF susceptible whilst the core was made of pure PET. The material was thus designed to melt selectively in the sheath layer with no melting of the core occurring during processing.

[0071] Fig. 12 shows schematically a core/sheath type bi-component fibre with an RF susceptible sheath layer (11) around a continuous fibre core (12). Only the sheath layer heats in an RF field and so melts to form a composite. On RF heating (13) and pressing (14) a consolidated composite (15) is produced.

[0072] Fig.13 shows the cross section of actual core:sheath bi-component fibres. Such fibres were woven into fabric and layers of this fabric were placed in an RF press and consolidated by pressure. During this process the RF susceptible sheath layer of the bi-component fibres melted to form a matrix leaving the core fibres unaffected to act as the reinforcement of the resulting "self-reinforced" composite. In this example the materials used were:

Core material: PET with intrinsic viscosity (IV) ranging from 0.65 - 0.80

Sheath material: PET with IV ranging from 0.65 - 0.8; PVDF (Kynar® ADX 111 grade from Arkema) and carbon black (Black Pearl® 2000 from Cabot Corporation). The composition is given in Table 6.

Table 6: Composition of co-axial fibre
 PET (wt%)PVDF (wt%)Carbon black (wt%)
RF susceptible sheath 84.0 15.0 1.0
Core 100.0 - -
Fibre diameter (core + sheath): Unstretched: ~350 µm
Core diameter: ∼220 µm
Sheath thickness: ∼65 µm


[0073] The specification range may change depending on the desired ratio of matrix and reinforcement. Fibres, after melt spinning, were subjected to a stretching operation maintaining an optimum draw ratio to get a highly stretched fibre with high mechanical strength properties. The diameter of the fibre reduces on stretching. The fibre specification after stretching is given below. This form of fibre is used for RF heating.
Fibre diameter (core + sheath) after stretching: Stretched: ∼30 µm
  Core diameter: ∼22-26 µm
  Sheath thickness: ∼2-3 µm


[0074] Relative mass proportion (core:sheath 65-75:35-25); relative volume proportion (core:sheath 60-70:40-30). The core:sheath ratio may be varied depending on the application. The sheath should form a minimum of 10 wt% of the whole material.

[0075] Another suitable form can be a layered tape like material. Tri-layer coextruded tapes with RF susceptible surface layers and their consolidation in an RF field is shown schematically in Fig. 14. As an example, PET-PVDF-CB of 84-15-1 composition was selected for making a tri-layer tape where the two outer layers contain the RF susceptors. The materials used were:
Core layer: PET with intrinsic viscosity (IV) ranging from 0.65 - 0.80.

[0076] RF susceptible surface layers: PET with IV ranging from 0.65 - 0.8; PVDF (Kynar® ADX 111 grade from Arkema) and carbon black (Black Pearl® 2000 from Cabot Corporation). The composition used is given in Table 7.
Table 7: Composition of co-extruded tri-layer tapes
 PET (wt%)PVDF (wt%)Carbon black (wt%)
RF susceptible surface layers 84.0 15.0 1.0
Core layer 100.0 - -


[0077] Tape thickness: In stretched condition, thickness of the tape approximately 55 µm; with the core layer nearly 35 µm and the RF susceptible surface layers approximately 10 µm each on the top and the bottom surfaces of the tape. Tape width: 22 mm.

[0078] Relative mass and volume proportions between the middle layer and the surface layers: mass proportion 60:40; volume proportion 70:30.

[0079] The specification may vary based on the application process. The specification may range between 2.5 - 25 mm width and 65 - 120 µm thickness, but not limited to this.

RF Processing



[0080] RF heating energy input and time: The heating energy input and time changes for the design and thickness of the material, e.g. in this case, fifteen layers of tri-layer tape consolidated into a 2.5 mm thick laminate required 0.45 kW of RF power for 30 sec.

[0081] RF heating and joining trials were conducted with the tri-layer tapes. Fifteen layers of tapes with RF susceptible formulation were stacked in the RF oven and pressed for less than 30 sec to form a laminate.

[0082] The power used was 0.45 kW and frequency used was 27.12 MHz. The RF susceptible surface layers melted and fused in 30 seconds showing that the temperatures of the surface layers increased above 248 °C (melting point of the surface layers) in 30 seconds under RF radiation, leading to the joining of the fifteen layers of tapes and formation of a consolidated laminate in 30 seconds. The cross section of the laminate consolidated in the RF press is shown in Fig. 15.

[0083] The invention is not limited to the embodiments described but may be varied in construction and detail. In addition to PET the invention is applicable to other thermoplastics such as PE, PP, PA, PEEK, PEI, PS, PMMA or blends thereof as well as thermosetting resin materials and thermoplastic:thermoset blends.

Microwave Heating Trial



[0084] A microwave heating trial of the formulated PET compounds was conducted using a CEM Discover SP microwave synthesiser. In this particular trial, the microwave frequency was 2.45GHz.
Table 8: Polymer blend compositions (PET-PVDF-CB) designed to develop MW susceptible formulation
Base polymer PET (wt%)MW Susceptor
PVDF (wt%)Carbon black (wt%)
100 0 0
85 15 0
84 15 1
82 15 3
70 30 0


[0085] Fig. 16 shows the effect of PVDF on MW heating of PET. The results for highest temperature achieved by each polymer blend composition show that increasing PVDF content in PET base polymer increases the heating effect under MW irradiation.

[0086] Fig. 17 shows the effect of increasing CB content on the MW heating of PET based blend. The presence of CB in addition to PVDF in the PET base polymer significantly enhances the heating effect under MW irradiation.

[0087] Design of Experiments (DoE) was also employed to gather information on the interactions between the PVDF and CB content in the compositions and how these interactions influenced the variation in the output measure (temperature rise in the MW field). Fig. 18 shows the contribution to temperature gain variability in 50W power MW irradiation for 60 sec (PET:PVDF:CB :: 82:15:3). The Figure shows the contribution of the individual and combined interactions in raising the temperature of the material under MW field. The variables along the X axes of this plot is the amounts of PVDF and CB used in the formulation, either taken individually or in combination. The Y axes represent the contribution of the components, individually or in combination, to the temperature gain variability of the material in the MW field. CB is found to have a more dominating influence on the heating of the material under MW field, but PVDF-CB combination has a higher effect. This effect can be maximised with further optimisation in formulation.

[0088] Throughout this specification, the term "comprising" or "comprises" means including the component(s) specified but not to the exclusion of the presence of other components. The term "consisting essentially of" or "consists essentially of' means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention. Typically, when referring to compositions, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1% by weight of non-specified components.

[0089] The term "consisting of' or "consists of' means including the components specified but excluding addition of other components.

[0090] Whenever appropriate, depending upon the context, the use of the term "comprises" or "comprising" may also be taken to encompass or include the meaning "consists essentially of' or "consisting essentially of', and may also be taken to include the meaning "consists of' or "consisting of'.

[0091] The optional features set out herein may be used either individually or in combination with each other where appropriate and particularly in the combinations as set out in the accompanying claims. The optional features for each aspect or exemplary embodiment of the invention as set out herein are also to be read as applicable to any other aspect or exemplary embodiments of the invention, where appropriate. In other words, the skilled person reading this specification should consider the optional features for each exemplary embodiment of the invention as interchangeable and combinable between different exemplary embodiments.

[0092] Although a few preferred embodiments have been shown and described, it will be appreciated by those skilled in the art that various changes and modifications might be made without departing from the scope of the invention, as defined in the appended claims.

[0093] All of the features disclosed in this specification (including any accompanying claims, and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.


Claims

1. A material susceptible to dielectric heating by electromagnetic radiation, the material comprising:

a base polymeric material (1), and

a dielectric heating susceptor comprising:

polymeric material (2) different from the base polymeric material and having a higher dielectric loss factor than the base polymeric material, and

electrically polarisable entities (3) dispersed within the base polymeric material;

wherein the dielectric heating susceptor polymeric material (2) is present in the form of discrete phases in the base polymeric material (1), forming a multiple phase morphology; and

wherein the electrically polarisable entities (3) are present in a proportion of 0.1 to 10 wt% of the material.


 
2. A material as claimed in claim 1, wherein the dielectric heating susceptor polymeric material is present in a proportion of 1 to 30 wt%, preferably in a proportion of 5 to 25 wt%.
 
3. A material as claimed in any preceding claim, wherein the electrically polarisable entities are present in a proportion of 0.5 wt% to 5 wt%.
 
4. A material as claimed in any preceding claim, wherein the base material is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamides (PA), polyetheretherketone (PEEK), polyphenylene sulphide (PPS), polyetherimide (PEI), polystyrene (PS), acrylonitrile/butadiene/styrene (ABS), polyacrylates (e.g. PMMA), polyacrylonitrile (PAN), polycarbonate (PC), epoxies, vinyl esters, unsaturated polyesters, phenolics, cyanate esters, bismaleimides, polyimides, and blends/mixtures thereof; and the dielectric heating susceptor is a polar polymer comprising one or a combination of PVDF, PU, PAI, PA, cellulose esters, PVC, acrylics, PVC/acrylic alloy.
 
5. A material as claimed in any preceding claim, wherein the base material includes PET and the dielectric heating susceptor polymer material is a polar polymer comprising one or a combination of PVDF, PU, and PAI.
 
6. A material as claimed in any preceding claim, wherein the electrically polarisable entities are present in the form of discrete entities, not forming a conductive network.
 
7. A material as claimed in any preceding claim, wherein the size of the electrically polarisable entities is in the range of 10 nm to 100 µm.
 
8. A material as claimed in any preceding claim, wherein the electrically polarisable entities comprise carbon black and/or wherein the electrically polarisable entities are of conductive material having interfacial polarisation loss properties.
 
9. A material as claimed in any preceding claim, wherein the base polymeric material is modified with an elastomer.
 
10. A material as claimed in any preceding claim, further comprising a filler material to provide desired mechanical properties, said filler material comprising particles and/or platelets and/or tubes and/or fibres to provide a composite material.
 
11. A process for heating a material of any preceding claim, the process comprising irradiating the material with electromagnetic radiation until a desired temperature is achieved.
 
12. A process as claimed in claim 11, wherein the electromagnetic radiation has a frequency in the range of 10 MHz to 30 MHz, preferably in the range of 13.54 MHz to 27.12 MHz.
 
13. A process as claimed in claim 11, wherein the electromagnetic radiation has a frequency in the range 900 MHz to 2.45 GHz.
 


Ansprüche

1. Material, das für dielektrische Erwärmung durch elektromagnetische Strahlung geeignet ist, wobei das Material umfasst:

ein Grundpolymermaterial (1) und

einen dielektrischen Wärmesuszeptor, umfassend:

Polymermaterial (2), das von dem Grundpolymermaterial verschieden ist und einen höheren dielektrischen Verlustfaktor als das Grundpolymermaterial aufweist, und

elektrisch polarisierbare Einheiten (3), die in dem Grundpolymermaterial dispergiert sind;

wobei das dielektrische Wärmesuszeptor-Polymermaterial (2) in der Form von diskreten Phasen in dem Grundpolymermaterial (1) vorliegt, um eine Mehrphasenmorphologie zu bilden; und

wobei die elektrisch polarisierbaren Einheiten (3) in einem Anteil von 0,1 bis 10 Gew.-% des Materials vorhanden sind.


 
2. Material gemäß Anspruch 1, wobei das dielektrische Wärmesuszeptor-Polymermaterial in einem Anteil von 1 bis 30 Gew.-%, vorzugsweise in einem Anteil von 5 bis 25 Gew.-%, vorhanden ist.
 
3. Material gemäß einem der vorstehenden Ansprüche, wobei die elektrisch polarisierbaren Einheiten in einem Anteil von 0,5 Gew.-% bis 5 Gew.-% vorhanden sind.
 
4. Material gemäß einem der vorstehenden Ansprüche, wobei das Grundmaterial ausgewählt ist aus Polyethylenterephthalat (PET), Polyethylen (PE), Polypropylen (PP), Polyamiden (PA), Polyetheretherketon (PEEK), Polyphenylensulfid (PPS), Polyetherimid (PEI), Polystyrol (PS), Acrylnitril/Butadien/Styrol (ABS), Polyacrylaten (z. B. PMMA), Polyacrylnitril (PAN), Polycarbonat (PC), Epoxiden, Vinylestern, ungesättigten Polyestern, Phenolen, Cyanatestern, Bismaleimiden, Polyimiden und Gemischen/Mischungen davon; und der dielektrische Wärmesuszeptor ein polares Polymer ist, das eines oder eine Kombination von PVDF, PU, PAI, PA, Celluloseestern, PVC, Acrylen, PVC/Acryl-Legierung umfasst.
 
5. Material gemäß einem der vorstehenden Ansprüche, wobei das Grundmaterial PET enthält und das dielektrische Wärmesuszeptor-Polymermaterial ein polares Polymer ist, das eines oder eine Kombination von PVDF, PU und PAI umfasst.
 
6. Material gemäß einem der vorstehenden Ansprüche, wobei die elektrisch polarisierbaren Einheiten in der Form von diskreten Einheiten, die kein leitfähiges Netzwerk bilden, vorliegen.
 
7. Material gemäß einem der vorstehenden Ansprüche, wobei die Größe der elektrisch polarisierbaren Einheiten in dem Bereich von 10 nm bis 100 µm liegt.
 
8. Material gemäß einem der vorstehenden Ansprüche, wobei die elektrisch polarisierbaren Einheiten Ruß umfassen und/oder wobei die elektrisch polarisierbaren Einheiten aus einem leitfähigen Material mit Grenzflächenpolarisations-Verlusteigenschaften bestehen.
 
9. Material gemäß einem der vorstehenden Ansprüche, wobei das Grundpolymermaterial mit einem Elastomer modifiziert ist.
 
10. Material gemäß einem der vorstehenden Ansprüche, ferner umfassend ein Füllstoffmaterial, um gewünschte mechanische Eigenschaften bereitzustellen, wobei das Füllstoffmaterial Partikel und/oder Plättchen und/oder Röhrchen und/oder Fasern umfasst, um ein Verbundmaterial bereitzustellen.
 
11. Verfahren zum Erwärmen eines Materials gemäß einem der vorstehenden Ansprüche, wobei das Verfahren Bestrahlen des Materials mit elektromagnetischer Strahlung, bis eine gewünschte Temperatur erreicht ist, umfasst.
 
12. Verfahren gemäß Anspruch 11, wobei die elektromagnetische Strahlung eine Frequenz in dem Bereich von 10 MHz bis 30 MHz, vorzugsweise in dem Bereich von 13,54 MHz bis 27,12 MHz, aufweist.
 
13. Verfahren gemäß Anspruch 11, wobei die elektromagnetische Strahlung eine Frequenz in dem Bereich von 900 MHz bis 2,45 GHz aufweist.
 


Revendications

1. Matériau sensible au chauffage diélectrique par un rayonnement électromagnétique, le matériau comprenant :

un matériau polymérique de base (1), et

un suscepteur de chauffage diélectrique comprenant :

un matériau polymérique (2) différent du matériau polymérique de base et possédant un facteur de perte diélectrique plus élevé que le matériau polymérique de base, et

des entités électriquement polarisables (3) dispersées dans le matériau polymérique de base ;

le matériau polymérique (2) de suscepteur de chauffage diélectrique étant présent sous forme de phases distinctes dans le matériau polymérique de base (1), formant une morphologie à phases multiples ;

et

les entités électriquement polarisables (3) étant présentes en une proportion de 0,1 à 10 % en poids du matériau.


 
2. Matériau selon la revendication 1, le matériau polymérique de suscepteur de chauffage diélectrique étant présent en une proportion de 1 à 30 % en poids, préférablement en une proportion de 5 à 25 % en poids.
 
3. Matériau selon l'une quelconque des revendications précédentes, les entités électriquement polarisables étant présentes en une proportion de 0,5 % en poids à 5 % en poids.
 
4. Matériau selon l'une quelconque des revendications précédentes, le matériau de base étant choisi parmi le poly(téréphtalate d'éthylène) (PET), le polyéthylène (PE), le polypropylène (PP), les polyamides (PA), la polyétheréthercétone (PEEK), le poly(sulfure de phénylène) (PPS), le polyétherimide (PEI), le polystyrène (PS), l'acrylonitrile/butadiène/styrène (ABS), les polyacrylates (par ex. le PMMA), le polyacrylonitrile (PAN), le polycarbonate (PC), les époxys, les esters de vinyle, les polyesters insaturés, les phénoliques, les esters de cyanate, les bismaléidimides, les polyimides, et des assemblages/mélanges correspondants ; et le suscepteur de chauffage diélectrique étant un polymère polaire comprenant l'un ou une combinaison parmi PVDF, PU, PAI, PA, les esters de cellulose, PVC, les acryliques, un alliage PVC/acrylique.
 
5. Matériau selon l'une quelconque des revendications précédentes, le matériau de base comprenant du PET et le matériau polymérique de suscepteur de chauffage diélectrique étant un polymère polaire comprenant l'un ou une combinaison parmi PVDF, PU, et PAI.
 
6. Matériau selon l'une quelconque des revendications précédentes, les entités électriquement polarisables étant présentes sous forme d'entités distinctes, ne formant pas de réseau conducteur.
 
7. Matériau selon l'une quelconque des revendications précédentes, la taille des entités électriquement polarisables se situant dans la plage de 10 nm à 100 µm.
 
8. Matériau selon l'une quelconque des revendications précédentes, les entités électriquement polarisables comprenant du noir de carbone et/ou les entités électriquement polarisables étant composées d'un matériau conducteur possédant des propriétés de perte de polarisation interfaciale.
 
9. Matériau selon l'une quelconque des revendications précédentes, le matériau polymérique de base étant modifié avec un élastomère.
 
10. Matériau selon l'une quelconque des revendications précédentes, comprenant en outre un matériau de charge pour fournir des propriétés mécaniques souhaitées, ledit matériau de charge comprenant des particules et/ou des plaquettes et/ou des tubes et/ou des fibres pour fournir un matériau composite.
 
11. Procédé pour le chauffage d'un matériau selon l'une quelconque des revendications précédentes, le procédé comprenant l'irradiation du matériau avec un rayonnement électromagnétique jusqu'à ce qu'une température souhaitée soit atteinte.
 
12. Procédé selon la revendication 11, le rayonnement électromagnétique possédant une fréquence dans la plage de 10 MHz à 30 MHz, préférablement dans la plage de 13,54 MHz à 27,12 MHz.
 
13. Procédé selon la revendication 11, le rayonnement électromagnétique possédant une fréquence dans la plage de 900 MHz à 2,45 GHz.
 




Drawing













































REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description




Non-patent literature cited in the description