CN103232608B - Method for preparing faceted heater from ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting three-dimensional (3D) printing mode - Google Patents
Method for preparing faceted heater from ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting three-dimensional (3D) printing mode Download PDFInfo
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Abstract
The invention relates to a method for preparing a faceted heater from an ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting a three-dimensional (3D) printing mode. The method comprises the following steps: a, stirring and mixing 100 parts of polyolefin and/or ethylene-propylene-diene-terpolymer rubber, 15-30 parts of carbon powder, 1-1.5 parts of an ultraviolet initiator and 1-1.5 parts of a crosslinking agent to form a mixed material; b, pouring the mixed material and 100 parts of tetrahydrofuran into an internal mixer to internally mix, and pulping the mixture in a three-roll mill after cooling so as to form a PTC size; c, preparing a PTC faceted heating body from the PTC size through 3D printing; d, irradiating the formed PTC faceted heating body through an ultraviolet light source to form a crosslinking PTC faceted heating body; and e, laminating the crosslinking PTC faceted heating body through laminating equipment to form the faceted heater. By utilizing the method, various 3D printing materials can be provided, and macromolecular PTC materials and devices thereof are simple in technology, energy-saving and environmental-friendly.
Description
Technical field
The invention belongs to high molecular PTC material technology field, relate in particular to a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type.
Background technology
" 3D printing " is popular call, academic name is called rapid shaping technique, also referred to as increasing material manufacturing technology, that a kind of traditional cutter, fixture and lathe of no longer needing just can be created arbitrary shape, according to the three-dimensional modeling data of part or object, make the technology of mock-up in the cumulative mode of material by molding device.The article that 3D printer can be made are more and more, from automobile, airplane parts, to food, arrive human organ etc.3D printing technique is an important breakthrough in world's manufacturing technology field over the past two decades.Be the integrated of the multidisciplinary technology such as mechanical engineering (accurate manufacture), computer technology (Software development), Numeric Control Technology, Materials science, it is the most difficult, is also that the technology of thinking most crucial is the limitation of printed material, and 3D prints the reality of having to face.The expansion of 3D printed material, has determined the capability boundary of 3D printer.Therefore the more various 3D printed material of exploitation.As intelligent material, Functionally Graded Materials, nano material, heterogeneous material and matrix material etc. become research from now on and focus and the key point applied.
Conventionally high molecular PTC material adopts Polyethylene-Carbon Black system, and crosslinking technological is that high-energy radiation is crosslinked, and the electronic component that it is prepared and ptc heater are applied to various occasions.
In addition, what existing high molecular PTC material and device thereof generally used is by polymkeric substance and electroconductive particle melting mixing, then utilizes the method for extrusion machine moulding.And existing high molecular PTC material and device thereof are not suitable for manufacturing out-of-shape product, even if create, its technique is also quite complicated.Particularly need Heating element make hemispherical or be approximately oval, almost cannot realize by prior art.
Therefore, be badly in need of providing a kind of high molecular PTC material of the 3D of can be used for printing and the production method of PTC planar heater thereof.
Summary of the invention
The object of this invention is to provide that technique is simple, a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type of energy-conserving and environment-protective.
Basic conception of the present invention is: about can be used for the high molecular PTC material of 3D printing and the production method of PTC planar heater thereof, be that the present invention is the high molecular PTC material that a kind of applicable 3D prints, adopt 3D printing type can prepare various obform body planar heaters.This high molecular PTC planar heater can obtain has the warm heat characteristic of good limit certainly, and its 3D prints manufacturing process and obviously demonstrates managerial great advantages.Can use on Domestic floor, roof thaw ice and snow, the snow melting in parking lot and the removal that auto mirror condenses steam, as special case more by dexterously for the manufacture of life health fields such as transfusion device thermal insulation nursing bottles.Ultraviolet light irradiation causes crosslinked polyolefine material and has been widely used in many fields, compares with chemical crosslink technique with high-energy radiation method, and photo-crosslinking has many advantages: (l) installation of ultraviolet source generating unit, operation are easier to, and less investment; (2), in cross-linking process, the side reactions such as degraded and oxidation are few.In recent years, polyethylene body ultraviolet light cross-linking new technology is successfully applied in cable industry, there is a large amount of materials such as Low Density Polyethylene and high density polyethylene(HDPE) to be made into crosslinked polyethylene, and be widely used in wire cable insulating material, heat-shrinkable tube, film and foam.Ranby study group is the progress of making a breakthrough property in this respect, and the research of domestic main Shi Qubaojun seminar is comparatively deep.Vinyl-vinyl acetate copolymer (EVA) is mainly used in the electric wire and cable industry of producing insulation.The crosslinked of appropriateness can increase the performances such as the thermostability of EVA, anti-electric discharge, resistance to solvent and resistance to creep, expands its Application Areas.But the photo-crosslinking research of high molecular PTC material is still blank at home.The present invention, taking EVA as raw material, adopts uv irradiation method to prepare crosslinked EVA high molecular PTC product.Cross-linked polymer ptc material possesses electrical property excellence, life-time service temperature advantages of higher, is widely used in the application of circuit protection, the heating of middle cryogenic thermostat.What high molecular PTC material and device thereof generally used is by polymkeric substance and electroconductive particle melting mixing, then utilizes the method for extrusion machine moulding.Moulding is compared with extrusion machine, utilize printing or print process to manufacture Heating element and have various advantages: while being applicable to manufacturing planar heating element in irregular shape, for example, while manufacturing as the permanent wave moisture eliminator of planar heating element, because the Heating element making is hemispherical, so, make the planar heating element that can make hemisphere face expand into plane, this situation utilizes print process just relatively good.In addition as the radiator of auto mirror anti-steam need to be approximately oval, and be not that simple electrode forms, now utilize printing or print process also very effective. utilize this method directly on article, the parts etc. of need heating, to print or to print.The feature that ultraviolet light cross-linking high molecular PTC material of the present invention and 3D print the production method of planar heater is to adopt ultraviolet initiator to coordinate specific UV light source to carry out the method for ultraviolet light irradiation cross-linking, the method equipment investment cost is low and cross-linking radiation cost is low, and technique is simple, energy-conserving and environment-protective, product cost inferior quality are good.In order to make high molecular PTC material become the material that can print, must be prepared into slurry or ink mode because polythene material is dissolved in any solvent hardly, in order to realize the ink of high molecular PTC material, must abandon the use of polythene material.Because high molecular PTC material must promote reliability of material by crosslinking technological, extend the life-span of PTC device.
The present invention will adopt vinyl-vinyl acetate copolymer (EVA) to replace polyethylene (PE), adopt ultraviolet light irradiation to cause crosslinking technological simultaneously.Because vinyl-vinyl acetate copolymer (EVA) dissolves in tetrahydrofuran (THF), thereby pave road for high molecular PTC material ink.High molecular PTC material ink makes the 3D printing that realizes planar heater become possibility.The inkization of high molecular PTC can make ptc material more homogenize, thereby more evenly heating is more even, each point temperature is more balanced for the heating member resistivity of preparation.
The present invention is cross-linked by ultraviolet-crosslinkable technology replacement high-energy radiation in high molecular PTC material or chemically crosslinked has promoted high molecular PTC reliability of material, has extended the life-span of PTC planar heater.Ultraviolet-crosslinkable technology lead in material, introduce under ultraviolet light irradiation, complete after ultraviolet initiator and linking agent mixing moulding last.The photo-crosslinking research of high molecular PTC material is still blank at home, and the present invention has filled up this blank.
Polyolefine material optical cross-linking method is the new cross-linking method that just starts in recent years to realize application. carry out the three-dimensional netted crosslinking structure of rapid composition generation by the macromolecular radical that adds light trigger in polyolefine material base-material or photosensitizer to absorb to occur after UV-light a series of optical physics and photoprocess to produce.
Polyolefine material itself is the chromophore with absorbing UV-light not, must rely on additional light trigger to cause crosslinked.So-called light trigger refers to after the ultraviolet luminous energy that absorbs suitable wavelength and intensity, self be cracked into the material that free radical or the energy by excited state shifted and then caused a series of free radical reactions, but only still can not meet industrial requirement with light trigger, must adopt the crosslinked light initiation system of strengthening.In the crosslinked light initiation system of strengthening, at least having increased a new component is multi-group crosslink agent.Photo-crosslinking process has been accelerated in adding of linking agent widely, especially at the initial stage of crosslinking reaction, compared with not adding the system of linking agent, added the system of linking agent after 5s illumination, gel content sharply rises to more than 65% from not enough l0%, allows the present invention have unforeseeable technique effect.Linking agent all contains two or more unsaturations, and linking agent mainly participates in crosslinking reaction by forming allyl radical.
In strengthening cross-linking system, the effect of linking agent is mainly manifested in the following aspects:
(1) quantum yield of raising light trigger.According to polyethylene photo-crosslinking kinetic equation, the quantum yield K of light trigger
lcan be expressed as:
In formula, T is linking agent; P is light trigger; k
1for light trigger decay rate constants; k
2for the reaction rate constant of polymkeric substance and initiator; k
3for the reaction rate constant of linking agent.Because the allylic hydrogen in linking agent is more active than the hydrogen atom on polymer chain, the light trigger of the state that is more easily excited is captured, i.e. k
3>=k
2.So k
1≈ l.This explanation multi-group crosslink agent's participation has suppressed the reaction of deactivating of excited state light trigger, makes more excited state light trigger for initiation reaction.
(2) speed of quickening crosslinking reaction.In the time not there is not linking agent, be only cross-linked and can form by two macromolecular radical direct combinations.Because macromolecular chain reactivity is poor, the probability of two macromolecular radical collisions is very low.Secondly,, because cross-linker molecules has multiple functional groups, therefore can be used as bridge and realize the connection of two macromolecular radicals; Micromolecular reactivity is much better, and much bigger with the probability of macromolecular radical collision again, this has accelerated crosslinked formation greatly.
(3) improve crosslinked homogeneity.The linking agent allyl radical of light-initiated generation is relatively stable, do not disappear immediately, can continue to react with other linking agent, free radical is introduced to the deep layer of sample, increase the probability of deep polyethylene crosslinking, this has solved the poor shortcoming of UV-light penetrance to a great extent, has improved crosslinked homogeneity.
Ketyl is compounded to form initiator photolytic product:
Macromolecular radical is compounded to form cross-link bond:
In recent years, ultraviolet light irradiation causes crosslinked polyolefine material and has been widely used in many fields, compare with chemical crosslink technique with high-energy radiation method, photo-crosslinking has many advantages: (l) installation of ultraviolet source generating unit, operation are easier to, and less investment; (2), in cross-linking process, the side reactions such as degraded and oxidation are few.
Specifically, a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type of the present invention, is characterized in that making according to following steps:
A, batch mixing: by weight, 100 parts of polyolefine and/or terpolymer EP rubber, 15 ~ 50 parts of carbon dusts, 0.5 ~ 4 part of ultraviolet initiator, 0.5 ~ 4 part of linking agent are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound; Optimally, 20～30 parts of carbon blacks; 1～1.5 part of ultraviolet initiator; 1～1.5 part of linking agent;
B, make slurry: compound and 100 parts of tetrahydrofuran (THF)s are poured in Banbury mixer, at 100～160 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9; Optimally, at 130 DEG C of temperature, carry out banburying;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Be of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 120～160 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.Optimally, at 130 DEG C of temperature, use equipment for coating film overlay film.
Be selected from a kind of or its combination in following material at polyolefine described in step a of the present invention: ethene one acetate ethylene copolymer (EVA), ethene one methyl acrylate copolymer (EMA), Ethylene ethylacrylate copolymer (EEA), ethene one butyl acrylate copolymer (EBA), ethylene-propylene diene copolymer (E Β DM).Better preferably ethene one acetate ethylene copolymer (EVA).
Be selected from a kind of or its combination in following material at carbon dust described in step a of the present invention: the fine element of carbon black, graphite and carbon element.Better preferably carbon black, 20～30 parts of content.
Be a kind of or its combination in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, grace ketone, Fluorenone or benzophenone and derivative thereof at ultraviolet initiator described in step a of the present invention.Better preferably benzophenone BP; 1～1.5 part of content.
Be cyanacrylate (TAIC), Viscoat 295 (PMPTA), pentaerythritol triacrylate (PETA) or Viscoat 295 (TMPTA) at linking agent described in step a of the present invention.Better preferably Viscoat 295 (TMPTA); 1～1.5 part of content.
Be the solvent of polyolefine and/or ethylene propylene diene monomer (EPDM) material at tetrahydrofuran (THF) described in step b of the present invention.
Adopt thermoelectron to excite middle pressure mercuryarc lamp in ultraviolet light irradiation described in steps d of the present invention system, H type lamp is housed, is added with the D type lamp of ferro element or is added with the V-type microwave-excitation Non-polarized lamp of gallium element.The ultraviolet light irradiation cross-linking apparatus of these specific light sources carries out cross-linking radiation to the PTC Surface shape heater forming.
In ultraviolet light irradiation step described in steps d of the present invention, system carries out on-line continuous ultraviolet light irradiation 0.5 ~ 20 second to PTC Surface shape heater, can be also 1～10 second, to make Surface shape heater obtain deep-crosslinked, is optimally 5 seconds.Light intensity 400-4000mW/cm
2, wavelength: 300-500nm.
Compared with the aforementioned existing similar products, the present invention not only provides more various 3D printed material, and allows the simpler and energy-conserving and environment-protective of high molecular PTC material and device technology thereof.
Content of the present invention is further described with the following Examples, but content of the present invention is not limited only to content related in embodiment.
Embodiment
By describing technology contents of the present invention in detail, being realized object and effect, be explained in detail below in conjunction with embodiment, but protection domain of the present invention is not limited to the following example.
Embodiment 1: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 20g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 400mW/cm
2, wavelength 300nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, finally form the exhausted rafter protective membrane of one deck on crosslinked PTC Surface shape heater surface, and naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=720 Ω; PTC effect=5.3*10
2; Use temperature scope-55 ~ 125 DEG C; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=15.6MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 2: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 4000mW/cm
2, wavelength 500nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=220 Ω; PTC effect=2.3*10
2; Use temperature scope-55 ~ 125 DEG C; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=14.3MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 3: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 30g carbon black, 1g benzophenone BP, 1.5g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 1000mW/cm
2, wavelength: 400nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=40 Ω; PTC effect=51; Use temperature scope-55 ~ 125 DEG C; ; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=13.6MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 4: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1g benzophenone BP, 1.5g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 2000mW/cm
2, wavelength: 350nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=470 Ω; PTC effect=6.7*10
2; Use temperature scope-55 ~ 125 DEG C; ; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=13.9MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 5: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1.5g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 3000mW/cm
2, wavelength: 450nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=310 Ω; PTC effect 4.8*10
2; Use temperature scope-55 ~ 125 DEG C; ; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=13.8MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 6: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 15g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 400mW/cm
2, wavelength: 300nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=1.04M Ω; PTC effect=1.8*10
4; Use temperature scope-55 ~ 125 DEG C; ; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=16.6MPa; By 125 DEG C of * 168h thermal ageing tests.
Embodiment 7: a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type described in the present embodiment, is characterized in that making according to following steps:
A, batch mixing: by weight, 100g terpolymer EP rubber, 25g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D; PTC Surface shape heater print thickness is controlled at 0.05mm left and right; Experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation; Light intensity 4000mW/cm
2, wavelength: 500nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ, naturally cooling sizing forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and result is as follows: sheet resistance=980 Ω; PTC effect=32; Use temperature scope-55 ~ 125 DEG C; ; Insulation voltage>=1500V; Insulation resistance>=10
8Ω .cm; Tensile strength=17.6MPa; By 125 DEG C of * 168h thermal ageing tests.
In sum, the feature that ultraviolet light cross-linking high molecular PTC material of the present invention and 3D print the production method of Surface shape heater body is to adopt ultraviolet initiator to coordinate specific UV light source to carry out the method for ultraviolet light irradiation cross-linking, the method equipment investment cost is low, technique simple, energy-conserving and environment-protective and cross-linking radiation cost low; It is the desirable mode of production of producing Surface shape heater of new generation.This product cost is low, good quality, has the very strong market competitiveness; Meet the characteristics of the times of personalized customization, market outlook are very wide.
The preferred benzophenone BP of ultraviolet initiator, selected specific UV light source carries out ultraviolet light irradiation cross-linking, and can to solve UV-light deep layer penetrativity poor and cause the serious deteriorated key technical problem of PTC performance and material mechanical performance.
The present invention is not limited in above-mentioned specific embodiment, and those skilled in the art also can make multiple variation accordingly, but any and the present invention are equal to or similar variation all should be encompassed in the scope of the claims in the present invention.
Claims (7)
1. adopt 3D printing type to prepare a method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100 parts of polyolefine and/or terpolymer EP rubber, 15～30 parts of carbon dusts, 1～1.5 part of ultraviolet initiator, 1～1.5 part of linking agent are put into homogenizer and be uniformly mixed at normal temperatures, mixing time 3 minutes, forms compound;
B, make slurry: compound and 100 parts of tetrahydrofuran (THF)s are poured in Banbury mixer, at 130 DEG C of temperature, are carried out banburying, 15 minutes banburying time, then allow it naturally cool to normal temperature, cooling after slurrying in three-high mill
,repeat-rolling forms PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9;
C, 3D printing shaping: PTC slurry is printed to preparation PTC Surface shape heater through 3D;
D, ultraviolet light irradiation: the PTC Surface shape heater of formation is formed to crosslinked PTC Surface shape heater through ultraviolet source irradiation;
E, overlay film, cooling and shaping: will be cross-linked PTC Surface shape heater and use equipment for coating film overlay film at 130 DEG C of temperature, thickness 20 μ m, naturally cooling sizing forms planar heater.
2. a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type as claimed in claim 1, is characterized in that in step
a, described in polyolefine be selected from a kind of or its combination in following material: ethylene-vinyl acetate copolymer EVA, ethylene-methyl acrylate copolymer EMA, ethylene-ethyl acrylate copolymer EEA, ethylene-butyl acrylate copolymer EBA, ethylene-propylene diene copolymer EPDM.
3. a kind of as described in claim 1 adopts 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that step a, described in carbon dust be selected from a kind of or its combination in following material: the fine element of carbon black, graphite and carbon element.
4. a kind of as described in claim 1 adopts 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that step a, described in ultraviolet initiator be a kind of or its combination in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, Fluorenone or benzophenone and derivative thereof.
5. a kind of as described in claim 1 adopts 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that step a, described in linking agent be cyanacrylate TAIC, pentaerythritol triacrylate PETA or Viscoat 295 TMPTA.
6. as claimed in claim 1ly a kind ofly adopt 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that adopting thermoelectron to excite middle pressure mercuryarc lamp in the system of ultraviolet light irradiation described in steps d, H type lamp is housed, is added with the D type lamp of ferro element or is added with the V-type microwave-excitation Non-polarized lamp of gallium element.
7. a kind of method of preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type as claimed in claim 1, its feature is carried out on-line continuous ultraviolet light irradiation 5 seconds in the system of ultraviolet light irradiation described in steps d to PTC Surface shape heater.
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| CN103819656B (en) * | 2014-02-18 | 2017-06-23 | 青岛科技大学 | A kind of graphene oxide/light-cured resin composite and its preparation method and application |
| CN103923470B (en) * | 2014-04-01 | 2015-11-25 | 江苏科技大学 | A kind of bio-based degradation material printed for 3D |
| CN103937026B (en) * | 2014-04-08 | 2016-09-21 | 中山职业技术学院 | A kind of preparation method of compact structure 3D printed product |
| CN104029391B (en) * | 2014-04-30 | 2016-08-24 | 中国科学院化学研究所 | A kind of 3D printing shaping polyolefine material and preparation method thereof |
| CN103991217B (en) * | 2014-04-30 | 2017-03-15 | 中国科学院化学研究所 | A kind of 3D printing forming method |
| WO2015165363A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Material for 3d printing and preparation method therefor and product thereof |
| WO2016106062A1 (en) | 2014-12-23 | 2016-06-30 | Bridgestone Americas Tire Operations, Llc | Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes |
| CN105462478A (en) * | 2015-12-14 | 2016-04-06 | 天津凯华绝缘材料股份有限公司 | Ultraviolet light cured PPTC electrode slurry and preparation method thereof |
| WO2017105960A1 (en) | 2015-12-17 | 2017-06-22 | Bridgestone Americas Tire Operations, Llc | Additive manufacturing cartridges and processes for producing cured polymeric products by additive manufacturing |
| WO2018081053A1 (en) | 2016-10-27 | 2018-05-03 | Bridgestone Americas Tire Operations, Llc | Processes for producing cured polymeric products by additive manufacturing |
| CN108411296A (en) * | 2018-02-13 | 2018-08-17 | 上海楚越机械设备有限公司 | A kind of preparation method of stratie |
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| CN101434728B (en) * | 2008-12-04 | 2012-01-18 | 黑龙江沃尔德电缆有限公司 | Ultraviolet light crosslinked EPT rubber cable insulation material and preparation thereof |
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