CN101495282B - The use of microwave energy to selectively heat thermoplatic polymer systems - Google Patents
The use of microwave energy to selectively heat thermoplatic polymer systems Download PDFInfo
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- CN101495282B CN101495282B CN200780027771.8A CN200780027771A CN101495282B CN 101495282 B CN101495282 B CN 101495282B CN 200780027771 A CN200780027771 A CN 200780027771A CN 101495282 B CN101495282 B CN 101495282B
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Abstract
The invention discloses a method for processing a thermoplastic material that comprises a microwave-sensitive polymeric region, wherein the method includes exposing the microwave-sensitive polymeric region to microwaves; wherein the exposing results in an increase in the temperature of the polymeric region; and processing the thermoplastic material.
Description
Cross reference to related application
The application requires the U.S. Provisional Application sequence number No.60/809 that submits to and be incorporated herein by this reference separately on May 31st, 2006 separately, and 520, No.60/809,526 and No.60/809,568 priority.
Technical field
The present invention relates generally to the use microwave energy to selectively heat thermoplatic polymer systems.This polymeric system can respond microwave energy or inherently by in this polymer or introduce suitable responding microwave additive as the component on the polymer backbone and come modification.
Background technology
Thereby the thermoplastic polymer pill usually must preliminary conversion method as extrude or injection moulding in parts with commercial value of fusion, reshaping and cooling manufacturing.In some cases, need comprise the secondary operations method of further heating, reshaping and cooling, as hot forming to obtain parts with commercial value.In preliminary and secondary method, all thermoplastic is applied heat energy, and after reshaping takes place, remove subsequently.
The traditional heating mechanism of thermoplastic polymer systems depends on contact or radiant heat source in many cases.Often be known as that infrared radiant energy has 1 to 10 micron wave length and before half utilisable energy is as heat dissipation the osmotic absorption material to about 1 to 2 micrometer depth.Diabatic process by conduction method (under the situation of solid material) or under the situation of melted material the combination by conduction, convection current and mechanical mixture continue.Contact heating depends on conduction (or combination of conduction, convection current and mixing) from the thermo-contact surface equally with heating material " body ".
The rate of heat transfer relevant with radiant heat method (RHT) described by following relationship usually: RHT=f (A, Ct, Δ T), wherein A is can be for the area that conducts heat, Ct is the thermal diffusion coefficient of this material, and Δ T is the effective temperature driving force, and it raises along with temperature of heated material and along with the time reduces.The thermal diffusion coefficient Ct of unmodified thermoplastic is low inherently, hinders the heat transfer in traditional radiation or the contact heating system thus.In addition, radiant heat method may cause unacceptable thermograde, and wherein the surface of heated parts (as sheet material) is obviously than heated parts center heat, and highly depends on the thickness distribution of heated parts.
As a comparison, microwave has about 12.2 centimetre wavelengths, grows up than infrared waves.Compare with infrared or radiant energy, microwave can infiltrate into the degree of depth much bigger in the absorbing material before utilisable energy is as heat dissipation, several centimetres usually.In microwave absorbing material, microwave energy is used to " volume (volumetrically) " and heats this material owing to microwave permeates this material.But if a kind of material is not good microwave absorption, it is basic " can be saturating " to microwave energy.
Some potential problems relevant with heating using microwave comprise inhomogeneous heating and heat dissipation.Usually the inhomogeneous heating that sees through this parts uneven distribution by microwave energy and cause can be overcome to a certain extent, for example overcomes by adopting turntable to carry heated object (item) in traditional household microwave oven.Heat dissipation may be owing to inhomogeneous heating listed above with the combination of temperature change dielectric loss factor.
Used microwave energy for example dry planar structure as wet fabric.Water is microwave susceptible, and if in enough microwave energies, expose enough durations, then can evaporate.But fabric normally microwave can be saturating, thereby microwave is concentrated on be substantially the waterborne of unique microwave susceptible component in this material.Microwave energy also has been used to heat other material, as in following list of references.
U.S. Patent No. 5,519,196 are disclosed in the polymer that contains iron oxide, calcium carbonate, water, alumina silicate, ethylene glycol and Mineral spirits (mineral spirits) that is used as internal layer in the food containers.This coating can be heated by microwave energy, makes the food browning look in the container thus or burns.
U.S. Patent No. 5,070,223 disclose microwave susceptor material and as the purposes of the heat reservoir in the toy.Disclosed microwave susceptor material comprises ferrite and Alfer, carbon, polyester, aluminium and slaine.U.S. Patent No. 5,338,611 disclose the polymer strip that contains carbon black (a strip of polymer) that is used in conjunction with thermoplastic substrate.
WO 2004048463A1 discloses polymeric compositions and associated uses and the processing method that can heat rapidly under electromagnetic radiation.
The critical limitation of using the heating using microwave polymeric material is the low microwave sensitivity of many available polymer.Therefore the low microwave sensitivity of polymer need high power or long radiated time to heat this class polymerization system.Absorbing in the polymer of design at microwave specially, usually between its microwave properties and machinery or thermal property, trade off (trade-off), namely machinery and thermal property are usually not quite desirable.
Therefore, need be conducive to use method and the polymeric material of the rapid volume heated polymerizable of microwave energy thing.In addition, need only to heat or fusion part polymeric material, thus the moulding that is enough to that bulk material can be flowed and is conducive to polymer or further method for processing and polymeric material.
Summary of the invention
On the one hand, embodiment disclosed herein relates to the method for the thermoplastic of processing the zone of convergency that comprises microwave susceptible, and wherein this method comprises that the zone of convergency that makes microwave susceptible is exposed in the microwave; Wherein this exposure causes this zone of convergency to heat up; And process this thermoplastic.
From following description and claims, know and find out other side and advantage.
Description of drawings
Fig. 1 has shown microwave heating equipment available in the embodiment as herein described.
Fig. 2 has shown an embodiment introducing the multi-layer sheet of microwave susceptible layer.
Fig. 3 is that the diagram of infrared heating/cooling curve and heating using microwave/cooling curve is compared, it shows owing to use the pulse microwave heating or heat relatively is provided in parts and than the alternate manner of cool region, is reduced by " heat is converged (heat sink) " the cooling cycle time decreased that concept causes and possible energy in the polymeric system.
Figure 4 and 5 have shown the modeling result of the thermal response of three-layer tablet material system in the microwave heating system.
Fig. 6 and 7 has shown the modeling result of the thermal response of three-layer tablet material system in the traditional radiation heating system.
Fig. 8 has shown the modeling result of the thermal response of three-layer tablet material system, wherein based on sheet thickness and required rated output requirement heat time heating time.
Fig. 9 has shown an embodiment of the method for hot forming of the selective heating using microwave of introducing multi-layer sheet.
Figure 10 has shown izod (Izod impact) data that contain and do not contain PP and the ABS of microwave susceptible additive.
Figure 11 has shown the time-temperature-responsive of the heating using microwave of crystalline p p sheet available in the embodiment as herein described.
Figure 12 has shown the rate of heat addition measured value that several polymer of containing zeolite A (a kind of microwave is experienced additive) become with microwave power.
Figure 13 has shown the Temperature Distribution that the samples of sheets that heats is recorded in microwave heating equipment, it shows with the attainable even heating of selective heating using microwave.
Figure 14 has shown the Temperature Distribution that the A/B/A sheet material interlayer sample that heats is recorded in microwave heating equipment, it shows with the attainable even heating of selective heating using microwave.
Figure 15 has shown two heat characteristics that the PP sample records to the three-layer tablet material that comprises the microwave susceptor material sandwich layer.
Figure 16 has shown the temperature snapshot that adds heat distribution of one of two PP samples among Figure 15, wherein obtains snapshot in the time of two minutes entering heating.
Figure 17 has shown the temperature snapshot that adds heat distribution of the PP sample of similarly heating using microwave shown in use and Fig. 1/thermal forming device heating.
Figure 18-23 has shown the heating using microwave result of the various samples of dynamic machining, wherein makes the microwave susceptible polymeric sheet pass through microwave cavity with fixed speed according to embodiment as herein described.
The specific embodiment
On the one hand, embodiment as herein described relates on polymer backbone or as the polymerization in the polymeric matrix or non-polymeric additive introduces the polymer that microwave is experienced component, and this component can heat this polymer by applying microwave energy rapidly and controllably.In aspect other, embodiment as herein described relates to processing and introduces the method that microwave is experienced the polymer of component.
With other heating, to compare as radiation, convection current or contact heating, the use of microwave energy can realize that the volume that is exceedingly fast heats.The use of microwave energy can overcome two basic restrictions of traditional heating system: to the dependence of polymer from the thermal conductivity of parts surface transporting heat energy; With the maximum safety temperature of polymer surfaces, it has determined the maximum effective temperature driving force again.
Polymer can be experienced microwave inherently based on its chemical composition.Perhaps, can be by microwave being experienced the polymer composition that additive and the base polymer of not experiencing microwave or microwave " can thoroughly " merge to form microwave susceptible.Describe below that suitable base polymer, microwave available in embodiment of the present invention are experienced polymer and microwave is experienced additive.Can use microwave energy to replace radiation, convection current or contact heating or with radiation, convection current or contact and add thermal and heat the impression of gained microwave or microwave susceptible polymer.The polymer of heating is can be subsequently mixed, transfer, moulding, punching press, injection, shaping, molded, extrude or otherwise further processing, as in preliminary conversion method or secondary operations method like that, with the formation useful article.
Many materials can absorb by microwave and heat.This can heat mechanism by dipole realizes, and comprises the movement of being excited of permanent dipole and/or electric charge, because they attempt as one man to vibrate with the oscillating electromagnetic wave that passes this material.Therefore this material stirs by molecule and heats to the viscous heat transmission of adjacent atom and molecule subsequently.Other material can heat by ohm (resistance), because the electric current in this material of electromagnetic electrical field stimulation.And other heating using microwave mechanism comprise Maxwell-Wagner and magnetic heating mechanism.The degree of heat of any material in the presence of microwave field is by its dielectric loss factor (be also referred to as loss angle tangent or complex dielectric permittivity, it is the measuring of interaction strength between material and the electromagnetic wave actually) regulation.Crucially, this heating is bulk effect, that is to say, this material is " volume " heating effectively, and therefore temperature required distribution can realize by suitable parts design in parts.
For example, in being designed for hot formed co-extrusion sheet material, the microwave susceptible sandwich layer can make this sheet material from inside to outside heat, thereby produces colder more desirable sheet surface temperature.In some embodiments, the Temperature Distribution of the sheet material that comprises sheet surface can be accurately controlled in heating using microwave.The control (by width, thickness and/or length) that sheet temperature distributes can realize the gained thickness of resulting part or the control of distribution of polymer.Owing to contacted and displacement by mould, colder crust temperature for example can change the gained distribution of material.
Microwave is experienced additive
The microwave acceptor or the additive that form the microwave susceptible polymer can be mixed or react with the basal heat thermoplastic polymer and conduction or magnetic material, for example metal can be comprised, slaine, metal oxide, zeolite, carbon, the hydration mineral, the hydrated salt of metallic compound, polymerization sensitivity material, clay, silicate, pottery, sulfide, titanate, carbide, sulphur, inorganic solid acid or salt, polymeric acid or salt, inorganic or polymerization plasma exchanger, with the compound modified clay of microwave impression, inorganic or the polymeric material that contains molecule or polymer microwave acceptor, organic conductor, or can effectively serve as other compound that to give polymeric material sensitivity and the selective microwave acceptor that heats.
Above-mentioned any additives can use or unite use separately so that required selective heating effect to be provided.In some embodiments, microwave is experienced additive and can be shown narrowband response to electromagnetic energy.In other embodiments, microwave experience additive can be by crossing over wide band radiation heating.In one embodiment, this additive is considered to have sensitivity in 1MHz to 300GHz or higher frequency range.In other embodiments, this additive can 0.1 to 30GHz or higher frequency range in heat; In other embodiments in the frequency range of 400MHz to 3GHz; In other embodiments in 1MHz to 13GHz or higher frequency range.In other embodiments again, this additive can heat in 1 to 5GHz frequency range.
More above-mentioned microwaves are experienced additive can contain the water of combining closely, as zeolite and clay.These materials also can comprise the excessive adsorption water that can discharge from this additive when heating.In some embodiments, microwave experience additive can be dry before merging with polymer.In some embodiments, microwave is experienced additive and can and be removed and anhydrate with the polymer merging, for example by using the exhaust extrusion system.In other embodiments, contain have experience parts or the sheet material of the polymer of additive in conjunction with the microwave of water can be in this sheet material first being processed drying in microwave device.Thus, the undesired bubble that is caused by excessive water forms and can be minimized or avoid.
Polymer
Can experience additive with one or more microwaves is combined the polymer that forms the microwave susceptible polymer and comprises and be selected from polyolefin, polyamide, Merlon, polyester, the resin of PLA or polylactide polymer, polysulfones, polylactone, poly-acetal, acrylonitrile-butadiene-styrene resin (ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), SAN (SAN), polyimides, maleic anhydride of styrene (SMA), aromatics polyketone (PEEK, PEK and PEKK), ethylene vinyl alcohol copolymer, with their copolymer or mixture.In certain embodiments, can with microwave experience polymer that additive is combined comprise polyethylene, polypropylene, polystyrene, ethylene copolymer, propylene copolymer, styrol copolymer, and composition thereof.In other embodiments, can comprise with the polymer of microwave receptors bind acrylonitrile based polymer, hydroxyl polymer, acryloyl group or acrylate based polyalcohol, contain maleic anhydride or maleic anhydride modified polymer, acetate groups polymer, polyether-based polymer, polyketone based polyalcohol, polyamide-based polymers and polyurethane-base polymer.
In some embodiments, the microwave susceptible polymer can be used as that discrete layer in the sandwich construction (or which floor) is introduced so that this discrete layer (or which floor) can preferentially heat in follow-up first being processed.Can make whole polymer architecture reach required processing temperature quickly than traditional heating system thus the adjacent polymer layers of heat energy from these layer guiding microwave energies basic " can thoroughly " then.
In certain embodiments, the microwave susceptible polymer can be experienced additive in conjunction with 0.1 to 200 weight portion microwave by per hundred parts of polymer and forms.In other embodiments, the microwave susceptible polymer can be experienced additive in conjunction with 1 to 100 weight portion microwave by per hundred parts of polymer and forms; In other embodiments again 2 to 50 parts; In other embodiments again 3 to 30 parts.
In certain embodiments, microwave is experienced 0.1 to the 25 weight % that content of additive can account for the microwave susceptible polymer.In other embodiments, microwave is experienced 1 to the 20 weight % that content of additive can account for the microwave susceptible polymer; In other embodiments again, 2 to 15 weight %.
In some embodiments, the microwave susceptible polymer can be powder, particle, pill, inhomogeneous fragment, liquid, sheet material or gel form.The microwave susceptible polymer can be crystallization, hypocrystalline or amorphous.In some embodiments, the microwave susceptible polymer can comprise colouring agent, enhancing or increment (extending) filler and other functional additive, as fire retardant or nano composite material.
Microwave heating equipment
Above-mentioned microwave susceptible polymeric material can use the microwave heating equipment heating so that further processing.Referring now to Fig. 1, shown the microwave heating equipment 10 that can use according to the embodiment of method disclosed herein.The parts of microwave heating equipment 10 comprise tuning plunger 11, EH tuner 12, coupling iris plate 13, waveguide 14, angle (horn) 15, microwave strangler 17 and lower moveable piston 18.Polymer sheet can be by coming 10 processing of heated by microwave device with sample through sample charging slit 19 chargings (thereby making sample through resonant cavity 20).Can regulate the performance variable of heater 20 in resonant cavity 20, to produce standing wave.
In some embodiments, in some embodiments used microwave heating equipment can be rapidly even heated polymerizable thing, and can comply with the character (acceptor type, acceptor density, substrate types etc.) of microwave susceptible polymer and the form (thickness, shape etc.) of rapidoprint.Rapid heating used herein can refer to that at least a portion sheet material is with at least 5 ℃/seconds in some embodiments; At least 10 ℃/seconds in other embodiments; At least 20 ℃/seconds in other embodiments; At least 30 ℃ in other embodiments; With at least 50 ℃ speed heating in other embodiments again.Even heating used herein refers to the heating of the selected portion at least of sheet material or sheet material, and wherein the maximum temperature difference of heating part is 10 ℃ or lower in some embodiments; Be 7.5 ℃ or lower in other embodiments; Be 5 ℃ or lower in other embodiments; Be 4 ℃ or lower in other embodiments; And in other embodiments again, it is 3 ℃ or lower.Compare with the traditional infrared heating, the rate of heat addition that the various embodiments of microwave heating equipment disclosed herein provide and temperature contrast can provide advantage aspect cycle time, reduce because excessive heat exposes the illeffects to polymer, and improved processing is provided.
The rated power of used microwave emitter depends on composition, size or the thickness of heated polymer samples and temperature required in the microwave heating equipment.Also can according to as in the heating period upstream or the variable of cycle time of the operation that takes place of downstream and so on select rated power.In certain embodiments, can use the variable power source, thereby technological flexibility is provided, for example change the ability of part dimension or composition (microwave is experienced amount or the type of additive) or the ability of the little local difference in the adaptation material composition, or temperature required.
Use
Embodiment disclosed herein relates to uses electromagnetic energy to come effective critical heat plastic material by the part of selective heating thermoplastic material volume, and this part is enough to make this material can process in follow-up forming technique.Used herein process the abundant melt attitude that refers to provide at least a portion thermoplastic or softening so as with the mixing of body plastics, transfer, moulding, punching press, inject, extrude etc. to form product.The heating of thermoplastic substrate can by thermoplastic is exposed to can permeate whole substrate volume and preferential absorption in the microwave susceptible zone electromagnetic energy such as microwave in realize.
By applying the microwave radiation, can in volume, body or the presumptive area partly of polymer samples, produce heat in the part.Therefore, can carefully control and concentrate the amount of the energy that applies because other zone can by used radiation can be saturating non-absorbing material constitute.For example, untreated polypropylene and polyethylene are that the microwave radiation can be saturating.Experience the material of microwave by use, can reduce used energy, shorten cycle time, and can regulate and optimize machinery and other character of final material at various requirement and purposes.
Position (sites) in the microwave susceptor material can be to be conducive to or the non-absorption that is conducive to electromagnetic energy.Heat under the electromagnetic energy influence easily and rapidly the position that is conducive to absorb.In other words, compare with other zone of material, have only the specified portions of substrate volume to be subjected to the strong influence of electromagnetic energy.
Thus, electromagnetic energy only with some regional interaction of substrate, temperature that should the zone when having electromagnetic energy can raise.Subsequently because the heating of adjacent area in the bulk material takes place in heat conduction and other this class mechanism.Because bulk material is heated by volume, compares with the traditional heating technology, this material can change into sooner can process attitude.In addition, because this material may contain the less heat energy of heat energy of normal presence than via the whole bulk material of surface conductive (infrared heating) heating the time, can significantly save energy.For example, infrared heating makes quite a large amount of energy losses in atmosphere, and require the parts surface temperature apparently higher than required body temperature to realize the acceptable rate of heat transfer from parts surface to the parts center and central temperature risen to the required temperature of processing.On the contrary, the temperature that makes the microwave susceptible polymer rapidly and the volume microwave selective that is heated to processing temperature heat and may cause significantly lower polymer surfaces temperature, especially comprising microwave thoroughly under the situation of superficial layer.Heating using microwave also may have the lower trend from this system loss energy, and energy is mainly transferred to the position that needs it, i.e. the microwave susceptible polymer.The cycle time of conversion method also can be significantly saved in heating using microwave.Not only because heating using microwave mechanism takes place rapidly by (opposite with the heat conduction), also because the total energy content of parts is lower, heat time heating time can be reduced in whole body.Also can reduce the cooling cycle, converge with heat sucking-off from adjacent heating region because the not heating region of material effectively serves as heat, thereby significantly improve the overall cooldown rate of bulk material.
Microwave susceptible polymer of the present invention can use in preliminary conversion or secondary processing process.For example, in some embodiments, this microwave susceptible polymer can be at polymeric object, comprise film, foam, section bar, compounding pill, fiber, yarn fabric and adhesive-bonded fabric, moulding part, composite, laminated material or the manufacture process of other goods of being made by one or more polymeric materials in use.In other embodiments, this microwave susceptible polymer can be used on conversion method, as sheet material extrude, in co-extrusion, foam extrusion molding, injection moulding, foam-formed, blowing, injection drawing blow and hot forming etc.
As mentioned above, can heat microwave susceptible polymer disclosed herein so that follow-up processing, for example mixed, transfer, moulding, punching press, injection, shaping, molded, extrude or otherwise further processing.In some embodiments, the microwave susceptible polymer can be used in the sheet method for hot forming, for example is used to form refrigerator lining.In other embodiments, microwave susceptible polymer disclosed herein can be used for for example processing of the adhesive fiber of air lay (air laid binderfibers).In other embodiments, microwave susceptible polymer disclosed herein can be used for blow moulding, for example is used to form blow molded bottle.
In other embodiments, microwave susceptible polymer disclosed herein can be used in the purposes of processed polymer incomplete fusion.For example, the microwave susceptible polymer can selectively be heated, and only heating makes heat energy only concentrate on the part that will further process through the selected polymer moieties of this device thus, for example by be shaped, molded or pressing further processes.This can improve the structural intergrity of the material of handling in the process, can reduce cycle time, and can reduce this materials processing is become the required energy of required form.
In other embodiments, microwave susceptible polymer disclosed herein can be used in the embossed flakes (embossed sheets).In traditional infra-red heat was shaped, hot input must be passed sheet surface, and usually reduces the reservation (retention) of patterned structure or surface detail.Except the heating cycle of reduction as mentioned above, the reservation that this microwave susceptible polymer can improve patterned structure in the process owing to give the energy footprint (energy footprint) of the reduction of this sheet material.For example, in being designed for hot formed co-extrusion sheet material, the microwave susceptible sandwich layer can make this sheet material from inside to outside heat, thereby produces colder more desirable sheet surface temperature.
In other embodiments, selective heating can allow to use the microwave susceptible layer of the polymer of interspersing with non-sensitive layer.The layering polymer can be realized: optimum temperature profile; The utilization of pulse microwave energy in the polymer processing; Be used for the selective placement of the microwave emitter of heater block specific region; With preferential or selective other performance of heating of the microwave susceptible realization that can utilize one or more thermoplastic components or layer.
As the example that sheet material is extruded, the microwave susceptible layer can be introduced in the multi-layer sheet.For example, Fig. 2 has shown an embodiment introducing the multi-layer sheet of microwave susceptible layer.Microwave susceptible layer B can constitute and the sheet material core that the insensitive outer A of heating using microwave is combined.The introducing of microwave susceptible sandwich layer can promote the follow-up processing of sheet material, as in sheet material hot forming process.In some embodiments, by using the microwave selective polymer, can promote the sheet material hot forming by the even heating rapidly that realizes sheet hot forming, selective tensility and sheet material.
Layering sheet material disclosed herein can comprise 2 layers or more multi-layered, and wherein one or more layers can comprise or be formed by the microwave susceptible polymer composition.For example, the layering sheet material can comprise 3,4,5,6 ..., nearly 1000 layers or more.In some embodiments, each layer can have 0.1 micron to 25 millimeters average thickness, and the sheet material gross thickness can be 100 microns to 25 millimeters.
Although be shown as the three-layer tablet material among Fig. 2, in other embodiments, the microwave susceptible polymer can form one or more zones in polymer architecture.For example the microwave susceptible polymer can form discrete layer in having two-layer or more multi-layered sheet material.In other embodiments, the microwave susceptible polymer can form the specific region than macrostructure, thereby makes these regioselectivity heating so that further processing.In other embodiments again, the microwave susceptible polymer can form a side of aligned fiber structure.In other embodiments again, the microwave susceptible polymer can form core or the skin of core/hide fiber structure.
In the foam extrusion molding, for example, the introducing of microwave susceptible layer can realize the selective heating of foam core and the non-selective cortex of solid, and this can shorten heating cycle, prevents the foaming structure avalanche simultaneously.In other embodiments, the microwave absorbent class of introducing variable concentrations in each layer can realize the difference heating of each layer and therefore optimize any follow-up procedure of processing, as hot forming.In other embodiments, the introducing of microwave susceptible layer can realize the selective foaming of postforming sheet material.
In other embodiments such as injection moulding or injection drawing blow, the introducing of microwave susceptible layer can realize the shorter cycle that wherein the non-sensitive part of these parts can be served as the cool time that heat is converged and therefore minimizing is provided owing to the inside cooling of polymer.Also can use pulse microwave can promote injection moulding, produce fusion and the semi-molten mixtures of material of injection moldable, this semi-molten material serves as heat and converges in the follow-up cooling procedure of parts.Injection drawing blow also can benefit to heat the optimized thermal gradient that causes by microwave selective, thereby improves the engineering properties of final products.
Fig. 3 has shown that the obtainable cooling of comparing with the traditional heating cycle reduces according to one embodiment of the invention.Except rapid heated polymerizable thing (this can reduce heating cycle and energy requirement), also can will have sheet material, pill or the fiber heating of microwave susceptible core may cause the cooling cycle of reduction similarly.Infrared heating/cooling curve " IR " is as shown in Figure 3 compared with heating using microwave/cooling curve " MW ", can the heating core polymer, energy is exported to outside non-sensitive layer.When fully being heated to melt temperature " MT ", these parts can be shaped injection etc.Because the continuous conduction from warm core to non-sensitive polymer, these parts can be cooled to calcining temperature " DMT " quickly than the cooling of parts after traditional heating, reduce " dt. " cycle time thereby make.Area dE representative between curve IR and the MW has the thermic load of the attainable reduction of polymer of microwave susceptible core by heating using microwave.
In some embodiments, can before hot forming, selectively heat the layering thermoplastic sheets that contains microwave susceptible and non-microwave susceptible layer.The thermoplastic pill that can selectively add in other embodiments, thermally stratified layer or coextrusion in follow-up first being processed in the injection moulding for example.These can cause the acceleration cooling that the existence by above-mentioned " internal heat remittance " causes and the cycle time that therefore reduces similarly with above-mentioned layering sheet material situation.
In other embodiments, can use pulse microwave can create not molten polymer " layer (slices) " or the zone of dispersion interspersed of layer of molten polymer of usefulness in follow-up first being processed.This also can cause the cycle time of accelerating cooling and therefore reducing similarly with above-mentioned layering sheet material situation.
In other embodiments, the selective placement of one or more microwave emitters can realize the selective heating of the specific region of sheet material or other thermoplastic component in follow-up first being processed.This is particularly useful for method for hot forming, and wherein this sheet material must deep-draw in the specific region.
In other embodiments, a kind of method can be used the selective heating of absorbent core and fixed, as contains used absorbent core in the health product of the bicomponent binder fiber (particularly polypropylene fibre or contain microwave susceptor material such as the fiber of maleic anhydride grafts or other polarity thing class) of microwave susceptible component and cellulose fibre.For example, in the fibre forming method, planar materials can be by having the microwave applicator that is enough to utilize its intrinsic moisture content partial melting polymer fiber and heats the energy of cellulose fibre.Subsequently, fiber can be consolidated into the absorbent core with polymer fiber and cellulosic integrated network.Perhaps, this structure can be technical fabrics, wherein can use the microwave susceptible fiber to weave or the on-woven structure is bonded together as covering thread (covered yarn).
In other embodiments, this method can be used the blend of two kinds of polymer, and a kind of polymer is experienced microwave energy, and another kind can be saturating, thereby can selectively heat microwave impression zone.The rate of heat addition that the relative scale of each polymer, phase morphology, microwave susceptible component concentrations and applied power can be used for controlling the microwave susceptible rate of heat addition mutually and therefore control total composite.
In other embodiments, selective heating can allow using microwave to experience reinforcement in the polymeric matrix thoroughly.Reinforcement can present continuous mesh or network (mesh ornet), weaving or adhesive-bonded fabric, continuous filament yarn or interrupted chopped strand form.Reinforcement can be polymerization in nature also, maybe can comprise other non-polymeric microwave susceptor material, as carbon or metal.
In other embodiments, microwave is experienced in the cortex and/or core that polymer can be used on three layers of (or more multi-layered) foaming structure (for example sheet material) that comprise solid cortical and foam core.Can change microwave in each layer experiences component concentrations and selects microwave power to realize the rapid heating of each layer and the temperature required distribution in the total being about to follow-up first being processed.Therefore do not need heating gradually required in the infrared heating can under the situation that does not have too early foam avalanche, realize required hot forming Temperature Distribution.
In some embodiments, can use the microwave of zeolite, inorganic hydrate or polymer water compound form in polymer thermoplastic matrix (for example, thermoplastic sheets) to experience component.Zeolite can use the microwave energy heating at the zeolite structured water that contains, and subsequently with the thermoplastic matrix reshaping.For example, under the sheet material situation, this sheet material can be shaped as container.Container molding can heat subsequently again, discharges water with vapor form from the hydration additive, and it can serve as the blowing agent that makes thermoplastic matrix expand into foam.
In other embodiments, use microwave to experience material in the aseptic packaging method of food on the cortex of used package sheet material and not needing to cause hydrogen peroxide or steam sterilizing with selective heating cortex.
Embodiment
In some embodiments, the microwave susceptible polymer can be introduced in the sandwich construction, so that the microwave susceptible layer can preferentially heat in follow-up manufacturing or first being processed as discrete layer (or which floor).Heat energy from these layer guiding microwave energies basic " can's thoroughly " adjacent polymer layers, makes whole polymer architecture reach required processing temperature than traditional heating system subsequently thus quickly.In some embodiments, the A/B/A structure can be used for the hot forming those semi-crystalline materials, as polyolefin or polyamide.
The following example comprise pulse microwave in the modeling and forecasting of sandwich construction and experimental result and the process of injection molding can the example of cycle time.
Embodiment 1: the modeling of microwave selective heating
With reference to Fig. 4-7, shown and the heating using microwave of similar three layers of A/B/A sheet material system and the modeling result of radiation heating shown in Fig. 2 that wherein the A layer can be that microwave energy substantially can be saturating, the B layer can be to the microwave energy sensitivity.This multilayer A/B/A structure can be by the microwave energy heating with preferential heating B layer.A layer subsequently can lead heat energy.
For example, above contact the microwave heating equipment that Fig. 1 describes and can be used for heated polymerizable thing sheet material.In hot forming, be useful with this or similar fashion heating A/B/A structure, because it is with traditional radiation or contact heating and compare in whole sheet material cross section generation " oppositely " Temperature Distribution.By Figure 4 and 5 and Fig. 6 and 7 are compared, can show this reverse Temperature Distribution better, wherein for heating using microwave, the A layer is colder than B layer, and for radiation heating, outermost layer is the warmmest.
As shown in Figures 4 and 5, heating using microwave causes heating as shown in Figures 4 and 5 middle part microwave susceptible layer.Then with thermal conductance to skin.For this simulation, make sheet material in microwave energy, expose 20 seconds so that the core temperature reaches 160 ℃.Top layer cuts off at microwave power and reached peak temperature in back 10 seconds.Conduction makes whole sheet material reach about 160 ℃ after about 30 seconds total elapsed time, and the temperature difference in the whole multilayer tablet thickness is less than about 20 degree.
As shown in Fig. 6 and 7, radiation heating is exposed to top layer to pine for, this heat below layer that must lead subsequently.Conduction to the sheet material bottom may need relatively large time quantum, and 150 seconds, so that the core temperature reaches 160 ℃.Whole sheet material reached 160 ℃ at about 170 seconds, had about 70 ℃ of temperature difference between top layer and bottom.
Above-mentioned analog result shows, heating using microwave can cause that more uniform temperature distributes in heating cycle and sample faster.Observed another difference is the response of sample after heating when comparing microwave and radiation heating.For heating using microwave, be immediately to the response of power shutoff state, and contain the melt zone as shown in Figures 4 and 5.On the contrary, for radiation heating, difficult realization makes an immediate response to the power shutoff state, and does not contain the melt zone as shown in Fig. 6 and 7.
As shown in Fig. 4-7, selective heating using microwave may cause the A layer colder than B layer, and may cause melt strength higher in the A layer and so wideer range of work (processingwindow).This sandwich construction also can specialized designs ratio and the applied power level of contained microwave susceptible additive provides in whole sheet material the best Temperature Distribution of hot forming with quantity, position and the thickness of each layer by changing the microwave susceptible polymer, in separately.Whole sheet material can be heated to rapidly thus hot forming temperature required and can not make sheet surface be exposed to the radiation heating system intrinsic guarantee abundance " temperature-driven power " so that minimize under the required excessive temperature required heat time heating time.Hierarchy selectively add thermal concept also owing to be shaped and follow-up cooling stage process in the acceleration of heat energy colder from hotter (heating using microwave) course (microwave can thoroughly) after layer conduction promotes shaping cool off.Microwave layer thoroughly serves as " internal heat remittance " substantially in polymer architecture.
Embodiment 2: time heating cycle of minimizing
Model for generation of The above results also is used to assess the microwave susceptible polymer to the hot forming cycle, the especially influence of heating cycle.Assessment is heated to layering sheet material (A/B/A crystalline p p sheet, wherein 60% of thickness is microwave susceptible core B) the required time of typical heat forming temperature: the required wattage of sheet material of heating appointed thickness in calculating at the appointed time, its result is presented among Fig. 8.The result shows that about 100 kilowatts power requirement may cause time heating cycle that is low to moderate 3 seconds, but the remarkable minimizing of this indication cycle's time.For sheet (10 millimeters or bigger), can under low power requirements, realize the 300 second cycle time suitable with the traditional heating system.
For the sheet material in the table 1, will cycle time and the traditional hot shaping heating system of microwave heating system assessment be compared.Again, be for A/B/A layering crystalline p p sheet, wherein the B layer be microwave susceptible and for sheet thickness about 60%.Heating using microwave can be used with similar 12-chamber (cell) microwave heating system shown in above-mentioned Fig. 4 and carry out.This selective heating may cause time heating cycle reduction 90% or more, and energy that may heating is required reduces by 75%.
Table 1
Contain the microwave susceptible polymeric layer sheet material selective heating can with similarly carry out in the method shown in Fig. 9.Sheet stock 102 can be fed in the microwave array 104, sheet material can be heated to temperature required at this.The raw material of heating is fed under this temperature in the hot forming device mould bed 106 that has low-power IR transmitter subsequently, and with postforming, cooling and release 108 to form moulding part 110.
The top of Fig. 9 shows above-mentioned steps to use the selective heating corresponding estimation time that the hot formed embodiment of sheet material is required and the estimation polymer temperature in the entire method.For the time-hygrogram shown in Fig. 9, this sheet material is 6 millimeters thick crystalline p p sheets with microwave susceptible polypropylene inner sandwich layer (A/B/A=1.5 millimeter/3 millimeter/1.5 millimeters).The heating using microwave array is in 22 kw of power settings.
Time-hygrogram among Fig. 9 has shown the heat time heating time of the polyacrylic remarkable minimizing of microwave susceptible, about 30 seconds.On the contrary, according to estimates, use traditional hot forming/heating, for the polypropylene that has similar thickness separately and polystyrene, it spends about 200 seconds and 85 seconds respectively.The heat time heating time of the remarkable minimizing of microwave susceptible polymer may be owing to realizing low parts cost the cycle time of the minimizing that is caused by the heat time heating time that reduces.
Compare in table 2 with traditional injection moulding heating system the cycle time (for example, in above Fig. 5) of the pulse microwave heating system estimation that injection molding apparatus is used.This microwave susceptible polymer can heat with pulse microwave, will contain the pill fusion of non-sensitivity and sensitivity polymer, then melt is injected cavity.Because heat is from the sensitivity polymer non-sensitivity polymer that leads, pill/melt has internal heat and converges, thereby improves time cooling cycle.The minimizing of cycle time is estimated as about 25% for being estimated as 60% than thick parts to small parts.
Table 2
| PP component thickness (millimeter) | Initial cold core (non-sensitivity) pellet size (millimeter) | Total (outward) pellet diameters (millimeter) | The time of injection point (second) | Traditional cycle time (second) | The cycle time (second) that inner cooling improves | Reduce percentage (%) |
| 10 | 6 | 6.93 | 10 | 300 | 120 | 60 |
| 5 | 4 | 2.24 | 1 | 72 | 57 | 21 |
| 2 | 2 | 2.24 | 1 | 10 | 7.5 | 25 |
Embodiment 3: the heat test of microwave susceptible polymer
Evaluation and test zeolite A and iron oxide (Fe in selective heating
3O
4).Be used for to select the standard of this two sections additive to comprise that validity (to the response of microwave energy), cost and desired additives carrying capacity, EHS consider.Also consider the anticipated impact (based on granularity, form and other character) that additive may have polymer property.For example, Figure 10 has shown the laboratory data of the izod reduction effect that shows that the PP of zeolite A and ABS produce.
Selected additive uses with four kinds of carrying capacity levels (about 3,6,10 and 14 volume %) in the polymer sheet with variable thickness (3,6 and 10 millimeters), and wherein polymer comprises ABS, HIPS, PP and conduction TPO.Then with the similarly heating using microwave (microwave heating equipment 20 comprises as lower member: tuning plunger 21, EH tuner 22, coupling iris plate 23, waveguide 24, angle 25, microwave strangler 27, lower moveable piston 28 and sample charging slit 29) of test polymer sheet material in the device shown in above-mentioned Fig. 1.By sample is come heated by microwave device working sheet through sample charging slot-fed.Experimental rig is even heated polymerizable thing rapidly, and can compliant materials character and form (acceptor type, acceptor density, substrate types and thickness of sample and shape).Experimental rig comprises 2.54GHz variable power source and is connected to the WG9A waveguide at angle, thereby provides homogeneous energy density to disperse.Iris plate and EH tuner can tuning emission wavelengths.Also provide analysis to measure equipment (not shown) in order to compare the temperature of especially monitoring processed polymer sheet with other variable.
Referring now to Figure 11, heating contains the 6 millimeters thick crystalline p p sheets of 6 volume % zeolite A to use microwave heating equipment to arrange down in 1100 watts, and measures sheet temperature in time.This sheet material rose to about 155 ℃ from room temperature in about 17 seconds, show rapid heating cycle.
With reference to Figure 12, shown the rate of heat addition that several samples of containing zeolite A record with microwave power.8 kinds of samples shown in the preparation table 3.When sample heats, measure the intensification of sample under constant microwave power.Under moderate paramount power setting, sample 1,3 and 7 shows the rapid rate of heat addition (being higher than about 7 ℃/second); Sample 2,6 and 8 shows the moderate rate of heat addition (2 to 6 ℃/second); And sample 4 and 5 shows the slow rate of heat addition (being lower than about 2 ℃/second).
Table 3
| Sample No. | Polymer base | Sheet thickness | Zeolite A content |
| (#) | (type) | (millimeter) | (volume %) |
| 1 | |
6 | 14 |
| 2 | |
6 | 6 |
| 3 | |
6 | 14 |
| 4 | |
10 | 14 |
| 5 | |
3 | 3 |
| 6 | |
3 | 10 |
| 7 | |
6 | 10 |
| 8 | |
6 | 0 |
With reference to Figure 13, shown the Temperature Distribution that the sample in the running of heating is recorded in microwave heating equipment.This sample is the nylon strip of 6 millimeters thick, 85 mm wides and 500 millimeters long.This sample passes this device with 400 mm/min speed under the 500W power setting.Figure 13 has shown the time snapshot of the stabilization temperature distribution that is produced by heating, and has shown with the attainable even heating of selective heating using microwave.
With reference to Figure 14, shown the Temperature Distribution that the A/B/A interlayer sample that heats is recorded in microwave heating equipment; The A layer is not experienced microwave, and the B layer is sensitivity.Experimental result confirms, similar with by above-mentioned E-field modeling and forecasting, and concept hierarchy provides even heating tape.
Referring now to Figure 15, shown comprising and microwave energy two 3 millimeters heat characteristics that the PP sample records of the three-layer tablet material of the polymeric outer layer microwave susceptor material sandwich layer of being combined thoroughly.For these two kinds of samples, sandwich layer all contains 10 volume % zeolite A.Sample 9 has top layer (crust), and sample 10 does not have top layer.Sample is being exposed under the microwave energy under the 500W power setting.Sample 9 with top layer than the sample 10 that does not have top layer slowly heat with Duoing.Figure 16 shown from 2 minutes on-tests, the heating of sample 9 time-the temperature snapshot, shown again how skin falls behind when thermal conductivity makes heat be delivered to skin from the microwave susceptible layer.Thus, skin can serve as the carrier of low melt strength core.
Referring now to Figure 17, shown the temperature snapshot of similar microwave heating equipment shown in use and Fig. 1 and hot forming station heating polypropylene specimen (4 millimeters thick, the 20/60/20 co-extrusion PP material that in core, contains 14% zeolite A).Crystalline p p sheet contains 14 weight % microwaves and experiences additive (zeolite A) and heat in polymer sheet has the microwave heating equipment of 1.5 kilowatts of rated power during by microwave heating equipment with 3 mm/second speed.With only lead sheet material middle part of microwave energy, molded sheet material part is wanted in selective heating.As can be seen from Figure 17, the Temperature Distribution on the whole heating part differs only 4 ℃, shows on the whole sample width forming the enough heating uniformly of required moulding part.
Referring now to Figure 18-23, shown with the similar result of the dynamic heat of microwave susceptible polymerization sample in the microwave heating equipment shown in Fig. 1.Heating has 3 to 14 weight % zeolite (zeolite A) carrying capacity in microwave heating equipment individual layer and co-extrusion crystalline p p sheet (20/60/20 coextruded structure) crystalline p p sheet (PP D114) wherein make sheet material pass through resonant cavity with 10 mm/second speed.Behind heating steps, make polymer sheet be fed in the mould by the identical transfer rate of the feed rate of loader (applicator).The position of mould is apart from 300 millimeters distances of loader.Change the power level of microwave generator, and measure the gained temperature of polymer sheet.1) in resonant cavity inside, 2) when polymer leaves this chamber and 3) at the die location place, measure temperature.The temperature of various samples is presented among Figure 18 (co-extrusion PP sample) and Figure 19-22 the power level result.Speed with 5 mm/second heats other individual layer sample, and its result is presented among Figure 23.
As another example, sheet material is thermoformed into this polymer of refrigerator lining requirement has the well balanced of rigidity and toughness, sufficiently high low-temperature impact character, good ESCR and good temperature tolerance.In addition, this polymer must have the deep-draw range of work, has good melt strength and limited sag (sag).Since oppositely Temperature Distribution and in the hot forming process, have improved melt strength and reduction sag A/B/A layering polymer can at refrigerator lining and similarly the sheet purposes with the hot forming of TPO sheet material.
Embodiment of the present invention provide the rapid volume heating of thermoplastic.Embodiment provides thermoplastic structure's discrete portions, as the selective heating of the independent stratum in stratiform or the co-extrusion sandwich construction.Other embodiments provide and produce heating and do not heat the pulse microwave energy that microwave is experienced material area.Some embodiments provide the selective placement of the microwave emitter of the heating that realizes the parts specific region.In other embodiments, the selective heating using microwave with high infiltration efficient has realized the almost heating simultaneously of sandwich layer and cortex, especially slowly conducts to shift by polymer from one of two skins or both with radiant heat and compares.
Embodiment disclosed herein can be used for the selective heating using microwave of thermoplastic, polymeric materials.For Polymer Processing, this technology provides many advantages for designer and processor, comprises selective heating rapidly; Heating/time cooling cycle (at a high speed) that reduces; Energy-efficient and other environmental benefit are as the discharging (because it is dry method and smokeless method) that reduces and the recirculation potentiality that improve (owing to single material component that can more widely-used self-reinforcing); The character of self-reinforcing parts is preserved (the reverse risk of reduction); The productivity ratio that improves; Improved part quality and intensity; Minimize with the thermal degradation that is caused by the time of staying of reducing in the hot method and therefore can reduce thermal stabilization additive in the polymer formulations.
Advantageously, embodiment disclosed herein can provide the heat time heating time of minimizing, thereby reduces total time process-cycle and therefore reduce cost of parts.Embodiment disclosed herein also can be introduced " heat is converged " owing to using selective heating that be provided the cool time of minimizing in material processed.In addition, the volume heating not needing to cause " surface " or " contact " heating also therefore to eliminate the possible illeffects of high polymer surface temperature.Unacceptable thermograde in the sheet thickness has also been eliminated in the volume heating.
Embodiment disclosed herein also can advantageously require to provide improved productivity ratio by the total cycle time of minimizing and the system capacity of reduction.Embodiment disclosed herein also can provide special heat distribution, thereby for all thermoplastics provide the optimal heat molding condition, and especially can the thick TPO sheet material of hot forming, otherwise this can have the unacceptable narrow range of work.
Although the disclosure comprises the embodiment of limited quantity, those skilled in the art will appreciate that under the situation of the present disclosure benefiting from, can design other embodiment that does not deviate from the scope of the present disclosure.Correspondingly, this scope should be limited by claims only.
Claims (24)
1. the method for a processing thermoplastic material, this method comprises:
Make the microwave susceptible thermoplastic pass through microwave heating equipment;
Described microwave susceptible thermoplastic is exposed in the microwave to improve the temperature of described microwave susceptible thermoplastic; With
Process described microwave susceptible thermoplastic,
Wherein said microwave susceptible thermoplastic comprises at least a microwave and experiences additive and at least a thermoplastic polymer,
Wherein said at least a microwave is experienced additive and is selected from zeolite, hydration mineral, polymerization sensitivity material, clay, silicate, pottery, sulfide, titanate, carbide, sulphur, inorganic solid acid or salt, polymeric acid or salt, inorganic or polymerization plasma exchanger, and organic conductor
Wherein said thermoplastic polymer comprises and is selected from one or more following polymer: polyethylene, polypropylene, polystyrene, ethylene copolymer, propylene copolymer, styrol copolymer, and composition thereof.
2. method according to claim 1, wherein said clay are with the compound modified clay of microwave impression.
3. method according to claim 1, wherein said polymerization sensitivity material comprises polymer microwave acceptor.
4. method according to claim 1, it comprises that further producing frequency is the microwave of 1MHz to 300GHz.
5. method according to claim 4, it further comprises the tuning microwave heater.
6. method according to claim 1, wherein said microwave is experienced additive and is experienced additive for the hydration microwave.
7. method according to claim 1, it further comprises the microwave susceptible thermoplastic is arranged in the multilayer materials with layer form.
8. method according to claim 7, wherein multilayer materials comprise microwave susceptible thermoplastic material layer and at least one microwave can be thoroughly layer.
9. method according to claim 1 wherein the microwave susceptible thermoplastic is configured to comprise 2 layers or more multi-layered layering sheet material, and wherein one or more layers is formed by the microwave susceptible thermoplastic.
10. method according to claim 9, wherein the layering sheet material has 100 microns to 25 millimeters gross thickness.
11. method according to claim 10, it further comprises formation layering sheet material.
12. method according to claim 11, it further comprises the layering sheet drying, in degassing extruder the layering sheet material is shaped, and microwave is experienced the additive drying, or its combination.
13. method according to claim 11, it comprises that further the layering sheet material that uses shaping is as the parts in the refrigerator.
14. method according to claim 1, wherein the processing thermoplastic material comprises at least a in mixing, transfer, moulding, punching press, injection, the molded and extruded thermoplastic material and combination thereof.
15. method according to claim 1, wherein the processing thermoplastic resin comprises the melt process technology.
16. method according to claim 15, wherein the melt process technology be selected from injection moulding, extrude, transfer moulding, blowing, hot forming, foam-formed or its combination.
17. method according to claim 16, wherein said extrude be selected from that sheet material is extruded, co-extrusion and combination thereof.
18. method according to claim 16, wherein said foam-formed be the foam extrusion molding.
19. method according to claim 16, wherein said blowing is selected from extrusion-blown modling, injection drawing blow and combination thereof.
20. method according to claim 1, wherein said processing produce at least a in film, foam, section bar, compounding pill, fiber, yarn fabric, adhesive-bonded fabric, moulding part, composite and the laminated material.
21. method according to claim 20, wherein weaving or adhesive-bonded fabric further comprise cellulose fibre.
22. method according to claim 1, wherein said at least a microwave are experienced additive and are selected from the inorganic substances that contain molecule microwave acceptor.
23. method according to claim 15, wherein the melt process technology is selected from injection-expansion molding.
24. method according to claim 1, wherein said processing produces yarn.
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| US60/809,526 | 2006-05-31 | ||
| US60/809,520 | 2006-05-31 | ||
| US60/809,568 | 2006-05-31 | ||
| PCT/US2007/012817 WO2007143015A2 (en) | 2006-05-31 | 2007-05-31 | The use of microwave energy to selectively heat thermoplastic polymer systems |
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| CN103435896A (en) * | 2013-09-16 | 2013-12-11 | 黑龙江省润特科技有限公司 | Microwave induced crosslinking polyolefin insulation material and preparation method thereof |
| CN105542320B (en) * | 2016-03-17 | 2018-08-10 | 上海日之升科技有限公司 | A kind of halogen-free anti-flaming polypropylene material and preparation method thereof of low cigarette rate of release |
| JP6499808B2 (en) | 2016-10-27 | 2019-04-10 | リンテック株式会社 | Dielectric heating adhesive film and bonding method using dielectric heating adhesive film |
| CN106696299B (en) * | 2017-01-17 | 2023-10-27 | 罗松 | Modeling processing process flow of packaging container made of foamed polyethylene |
| KR102467095B1 (en) * | 2017-04-03 | 2022-11-14 | 린텍 가부시키가이샤 | High-frequency dielectric heating adhesive sheet, and bonding method using the high-frequency dielectric heating adhesive sheet |
| CN107892293A (en) * | 2018-01-08 | 2018-04-10 | 韩笑峰 | A kind of method that graphene is prepared using coal as raw material |
| CN108219202B (en) * | 2018-01-17 | 2019-11-15 | 科迈特新材料有限公司 | Low zinc sulfide active agent of a kind of high dispersive and preparation method thereof |
| CN109096712B (en) * | 2018-07-13 | 2021-01-22 | 安徽理工大学 | Polylactic acid-ferroferric oxide nano composite foam material and preparation method thereof |
| CN110406134B (en) * | 2019-08-01 | 2021-08-13 | 帝国理工创新有限公司 | Method for forming carbon fiber reinforced thermoplastic composite material part |
| CN112024629B (en) * | 2019-12-18 | 2022-11-11 | 哈尔滨理工大学 | Method for preparing semi-solid blank by pulse current |
| CN113150354A (en) * | 2021-05-10 | 2021-07-23 | 武汉金牛经济发展有限公司 | Microwave treatment method for low-temperature-resistant high-performance PP-R pipe |
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