CN104105239A - Microwave heating device and microwave heating method - Google Patents
Microwave heating device and microwave heating method Download PDFInfo
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- CN104105239A CN104105239A CN201410100661.1A CN201410100661A CN104105239A CN 104105239 A CN104105239 A CN 104105239A CN 201410100661 A CN201410100661 A CN 201410100661A CN 104105239 A CN104105239 A CN 104105239A
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- cooling
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Abstract
The present invention aims at providing a microwave heating device capable of reducing damages caused by heat and heating an expected processed object at the same time, and a microwave heating method. The microwave heating device is characterized by comprising: a roller used for keeping the processed object; a microwave irradiating device for irradiating microwaves to the roller; a rotating device for enabling the roller to rotate; a stirring piece arranged inside the roller; and a cooling device for cooling the roller.
Description
Technical field
The present invention relates to microwave heating equipment and microwave heating method.
Background technology
Microwave heating technique is as the technology of heated food and development.Microwave heating is compared with the common heating of being undertaken by infrared ray, hot blast etc., has as inferior feature:
■ can optionally heat the material of easy absorption microwave;
The ■ efficiency of heating surface is high, and heating time is short.
At present, owing to having above-mentioned such feature, microwave heating technique is in the field widely such as synthesizing of the sintering of industrial dry, the sterilization that is applied to timber etc., pottery etc., macromolecular material.Wherein, the example being used in the burning disposal of discarded object describes (for example, with reference to patent documentation 1) to microwave heating equipment.
Fig. 5 means the key diagram of the structure of the microwave heating equipment that patent documentation 1 is recorded.In shell 2, be provided with barrel 10 and the backing roll 11 that can rotate.In the inner side of barrel 10, be provided with multi-disc stirring vane 19, the discarded object 40 of putting in barrel 10 is stirred.In the bottom of shell 2, be connected with suction mechanism 31, on the top of shell 2, be connected with waste gas cleaning mechanism 35.The microwave irradiation radiating from magnetron 21 is to the discarded object 40 in barrel 10.Can heat discarded object 40 thus.
2004-No. 183989 communiques of [patent documentation 1] TOHKEMY
Yet, at object being treated, be when being difficult to absorb the material of microwave and easily absorbing the mixture of material of microwave, be desirably in not the material combustion that only makes easily to absorb microwave in the situation that causes fire damage to being difficult to absorb the material of microwave.
Yet, in device in the past, there is following problem: from the heat of the material of easy absorption microwave, by heat, conduct to the material that is difficult to absorb microwave and conduct, and cause fire damage to being difficult to absorb the material of microwave.
Summary of the invention
The present invention is used for solving above-mentioned problem, and its object is to provide a kind of minimizing to being difficult to absorb microwave heating equipment and the microwave heating method of fire damage of the material of microwave.
To achieve these goals, microwave heating equipment of the present invention is characterised in that to possess: for keeping the cylinder of object being treated; Microwave applicator to described cylinder internal radiation microwave; Make the whirligig of described drum rotating; Be arranged on the stirring piece in described cylinder; Described cylinder is carried out to cooling cooling device.
In addition, microwave heating method of the present invention heats described object being treated by the object being treated irradiating microwaves in stirring in cylinder, it is characterized in that cooling described cylinder in irradiating microwaves.
[invention effect]
As mentioned above, according to the present invention, the temperature that can suppress object being treated rises, and reduces the phenomenon that produces fire damage in object being treated.
Accompanying drawing explanation
Fig. 1 means the process chart of silicon recycling system.
Fig. 2 is the generalized section of the related microwave heating equipment of execution mode 1.
Fig. 3 is the cylinder schematic diagram of the related microwave heating equipment of execution mode 1.
Fig. 4 is the cutaway view of the related microwave heating equipment of other example of execution mode 1.
Fig. 5 means the key diagram of the structure of the microwave heating equipment that patent documentation 1 is recorded.
[symbol description]
100,101 microwave heating equipments
300 microwave generators
310 tuners
320 waveguide pipe
330 metal chambers
340 rotating mechanisms
350 cylinders
360 silicon mud
370 stirring pieces
380 cooling devices
390 water cooling tubes
391 air cooling mechanisms
400 air entries
410 exhaust outlets
420 thermometers
430 control parts
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described.
(execution mode 1)
As the accessory substance of the manufacturing process of silicon for solar cell wafer, the mixture that generates silicon, water and carbon is silicon mud.Silicon is the material that is difficult to absorb microwave, and water and carbon are the materials that easily absorbs microwave.Therefore, if can in the situation that do not cause fire damage to realize the selective combustion with carbon of removing of moisture to the silicon in silicon mud, can obtain so high-quality recycling silicon.
In the situation that silicon mud has been irradiated to microwave, although be difficult to absorb the silicon of microwave, be not easy because microwave itself is heated, due to the heat conduction of the water from easy absorption microwave, carbon, the temperature of silicon rises sometimes.On the other hand, the related microwave heating equipment of present embodiment can suppress to when being difficult to absorb the fire damage of material of microwave optionally only heating easily absorb the material of microwave.Therefore, this microwave heating equipment is useful for obtain recycling silicon from silicon mud.Below, by the example that is applicable to the operation of acquisition recycling silicon from silicon mud, this microwave heating equipment is described.
First, use Fig. 1 to describe the wafer manufacturing process of silicon for solar cell.At first, in silicon materials preparatory process (S110), prepare the few initial silicon of impurity, next, at silicon ingot, make in operation (S120) and make silicon ingot.Silicon ingot is made by cutting krousky (CZ) method etc.In silicon ingot processing, bonding process (S130), the silicon ingot of making is processed, this silicon ingot is adhesively fixed in beam.In slice processing operation (S140), use scroll saw to carry out slice processing to the silicon ingot being adhesively fixed on beam.Then, via wafer cleaning operation (S150), produce silicon for solar cell wafer.
Next, silicon recycling operation (S200) is described.Silicon recycling operation (S200) refers to, the silicon mud that will generate as accessory substance in slice processing operation (S140) is by separated, recovery process (S210) separation, recovery, and remove operation (S220), melting, solidify operation (S230) and make recycling silicon via carbon, moisture, then return to a series of operation that silicon ingot is made operation (S120).
In slice processing operation (S140), the smear metal that silicon ingot is added to the silicon producing man-hour be bonded with the beam material of silicon ingot, the water that contains cooling fluid (organic system) mixes and discharges in large quantities as silicon mud.In separation, recovery process (S210), utilize for example filter press this silicon mud to be carried out to separated, the recovery of solid state component and liquid component.The solid state component of the silicon mud after separation is recovered as the silicon mud of powdery.The organic carbon composition that contains residual cooling fluid composition in the silicon mud of this powdery, as the graphite of the material of beam, as the DIC composition of the residues such as abrasive particle of diamond fretsaw.The 7at% left and right of the silicon mud integral body that contained organic carbon component, inorganic carbon component are powdery.The moisture containing ratio of the silicon mud of powdery is 50%～60% whole left and right.
The silicon mud of the powdery after reclaiming imports the related microwave heating equipment of present embodiment as object being treated, carries out that a few minutes to the heat treated of dozens of minutes left and right is implemented carbon, moisture is removed operation (S220).By suppress the oxidation of silicon and remove carbon component and moisture in this operation simultaneously, thereby can obtain the recycling silicon that purity is high and fire damage is low.
At this, use Fig. 2 to describe the details of the related microwave heating equipment 100 of present embodiment.
Microwave heating equipment 100 possesses microwave generator 300, tuner 310, waveguide pipe 320, metal chamber 330, for keeping the cylinder 350 of object being treated (silicon mud 360), as the rotating mechanism 340 of the whirligig of cylinder 350, for the stirring piece 370 of stir silicon mud 360, there is the cooling device 380 that cylinder 350 is carried out to cooling water cooling tube 390.In addition, microwave heating equipment 100 possess by air or gas be taken into metal chamber 330 air entry 400, carry out the exhaust outlet 410 of exhaust, the thermometer 420 of instrumentation temperature.
Metal chamber 330 arranges from the mode of 30 ° of horizontal direction inclinations with central shaft, thereby easily stirs object being treated.In the inside of metal chamber 330, be provided with under the effect of rotating mechanism 340 to the rotation of paper depth direction and by stable on heating metal cylinder 350.
The microwave being produced by microwave generator 300 irradiates to the silicon mud 360 remaining in cylinder 350 by waveguide pipe 320.At this, as an example of microwave applicator, enumerate the device that combination microwave generator 300, tuner 310, waveguide pipe 320 form.
Lower surface at metal chamber 330 is provided with the air entry 400 that imports air from atmosphere.The exhaust outlet 410 that the gas producing when the upper surface of metal chamber 330 is provided with the steam producing when heating silicon mud 360 or carbon burning is discharged.By air entry 400 and exhaust outlet 410, can carry out the flow of inspiratory capacity, discharge rate adjusts.
At this, the details of cylinder 350 is described.Fig. 3 (a) is the generalized section during from transverse observation cylinder 350, is (b) schematic diagram after the opening of cylinder 350 is amplified.At the medial surface of cylinder 350 and the rotating shaft of cylinder 350, be provided with abreast stirring piece 370, become the structure that can stir object being treated by swing roller 350.Stirring piece 370 forms by having stable on heating metal, as an example, can enumerate stainless plate.At this, show following state: the degree of depth of stirring piece 370 (depth) is the degree of depth of cylinder 350 approximately 3/4 times, the height of stirring piece 370 (height from the medial surface of cylinder 350) is approximately 1/8 times of diameter of cylinder 350, and stirring piece 370 is provided with 4 at the medial surface of cylinder 350 to be positioned at the mode of cross direction.This configuration can reduce not to the shaded portions of object being treated irradiating microwaves, for carrying out processing uniformly, is therefore useful.Due to metal stirring piece 370 blocking microwaves, easily produce shaded portions, therefore as above-mentioned such configuration, can reduce as much as possible shaded portions.
By this stirring piece 370, can stir efficiently object being treated, even the different powder of particle diameter is object being treated, also can not only stir in the direction of rotation (depth direction in figure) of cylinder 350, can also stir at opening and inner portion direction (left and right directions in figure).
It should be noted that, preferably stirring piece 370 consists of the such material with thermal endurance and transmission microwave of quartz.This be because, if form stirring piece 370 by the material of transmission microwave, can not form not to the shaded portions of object being treated irradiating microwaves, can improve treatment effeciency.
In addition, at the madial wall of cylinder 350, the inner side of stirring piece 370 be provided with by plated water cooling tube 390 (magnetism servo-electric motor water-cooling).That is, cooling device 380 (Fig. 2) has the magnetism servo-electric motor water-cooling that carrys out cooling and stirring sheet 370 by cooling fluid.By cooling fluid is flowed in water cooling tube 390, thus inner side and stirring piece 370 that can chilling roll 350.Thus, near the central authorities of the cylinder 350 that chilling temperature is the highest effectively, improve the cooling effectiveness of object being treated.And then, because the chance that stirring piece 370 contacts with object being treated is more, therefore cooling object being treated more efficiently.It should be noted that, can suitable water or grease etc. as cooling fluid.
In the present embodiment, paradoxical discharge, localized heating when suppressing the microwave heating of silicon mud 360 of Fig. 2, be processed into the shot-like particle below 5mm by machine for decomposing and smashing by silicon mud 360.This silicon mud 360 of several kg is imported to cylinder 350, by rotating mechanism 340, cylinder 350 is rotated with 3～20rpm.
In microwave heating equipment 100, possesses control part 430.Control part 430 is computer.Control part 430 is rotated the driving of mechanism 340 and controls.And then control part 430 is controlled cooling device 380 also cylinder 350 is carried out to cooling mode when the microwave irradiation.And control part 430 is connected with microwave generator 300, (radiation) thermometer 420, so that becoming 600 ℃ of following modes, the surface temperature of the silicon mud 360 in processing controls cooling device 380 and microwave generator 300.The surface temperature of silicon mud 360 is measured by thermometer 420.The temperature of the part (core) that this surface temperature by microwave heating and at utmost heats up from silicon mud 360 is different.When the temperature of the part at utmost heating up rises to 900 ℃ of left and right, the aggravation of the oxidation reaction of silicon, is unsuitable for silicon recycling.The result of experiment is that the discoveries such as inventor, if surface temperature is remained on below 600 ℃, can suppress the oxidation of the silicon in silicon mud 360.
At this, the carbon of Fig. 1, moisture are removed to operation (S220) and be elaborated.
At carbon, moisture, remove in operation (S220), when carrying out cylinder 350 inside cooling of Fig. 2, to silicon mud 360, irradiate for example microwave of 3～9kW left and right.So the organic carbon component in silicon mud 360, inorganic carbon component, moisture absorption microwave and be heated, first, produce steam, and the steam producing is from exhaust outlet 410 discharge to metal chamber 330.Then, become the organic carbon component of high temperature more, inorganic carbon component evaporation or with atmosphere in oxygen generation combustion reaction, produce organic system gas or CO
2.The organic system gas or the CO that produce
2also from exhaust outlet 410, discharge.So, by prolonged exposure microwave, moisture concentration, concentration of carbon in silicon mud 360 are reduced.By carrying out the irradiation of the microwave of a few minutes, thereby can make moisture concentration in silicon mud 360 for example be reduced to below 1.5%, and can make concentration of carbon be reduced to for example 0.1at% left and right.
Originally, because silica flour is the material that is difficult to absorb microwave, thereby be difficult to directly heat by microwave, but because the heat of the carbon from high temperature is conducted, and may make the temperature of silicon increase.When silicon is applied to heat, there is rotten (oxygen concentration causing because of oxidation rises) and damage to accumulate to make the situation of the quality reduction that recycles silicon.Therefore, in the present embodiment, in order to prevent that the temperature of silicon from rising, the inner side of cylinder 350 and stirring piece 370 are carried out cooling in, the moisture in silicon mud 360, carbon burning are removed.Thus, the temperature that can suppress silicon rises, and can reduce the rotten and fire damage of silicon.
It should be noted that, be preferably configured to the conductive coefficient in outside of cylinder 350 lower than the conductive coefficient of inner side.More specifically, and the material that preferably employing is high in the inner side of cylinder 350 use thermal endurance and conductive coefficient is high (for example, stainless steel and other metal materials, or conductive coefficient is 15Wm
-1k
-1above and 500Wm
-1k
-1following material), in outside, use and be difficult to absorb microwave and the low such double-decker of material (such as quartz, zirconia, refractory plate etc.) of conductive coefficient.Particularly, more than 2 times and below 100 times of conductive coefficient that preferably conductive coefficient of the inner side of cylinder 350 is outside.By making the more than 2 times of conductive coefficient that the conductive coefficient of the inner side of cylinder 350 is outside, thereby the temperature that can also suppress to surround the metal chamber 330 of cylinder 350 rises.If temperature rises, metal may become and easily absorb microwave, but rises by suppressing the temperature of metal chamber 330, can reduce thus by the energy of the microwave of metal chamber 330 absorptions.In addition,, owing to the inner side at cylinder 350 and outside using different materials, the processing that therefore (side of cylinder 350) imbeds water cooling tube 390 between them also becomes easily, can easily make cylinder 350.By cooling device 380 being imbedded to the side of cylinder 350, can implement efficiently cooling.
In addition, microwave heating treatment also can under reduced pressure be implemented.And then, also can be to the interior oxygen gas-supplying of metal chamber 330 and the mist of inactive gas (nitrogen, argon gas etc.) or the mist of hydrogen and inactive gas etc.Thus, can suppress the oxidation of silicon.
It should be noted that, this microwave heating equipment also goes for the mud producing when the substrate manufactures such as sapphire substrate, gallium nitride (GaN) substrate, GaAs (GaAs) substrate.In these mud, comprise the material of easy absorption microwave yet and be difficult to absorb the material of microwave, this microwave heating equipment can not carried out microwave heating treatment to being difficult to absorb when the material of microwave causes fire damage.
It should be noted that, material (the first material) expression polar substances, the dielectric loss angle (Tan δ) that easily absorbs microwave is that more than 0.01 material or conductance is 10
-2above and 10
4any material in following material.And the material or the conductance that are difficult to absorb material (the second material) expression of microwave and polar substances, dielectric loss angle Tan δ and are and be more than 0.01 are 10
-2above and 10
4any in following material be different material all.Comprise above-mentioned any the first material and this two side's of the second material object being treated be suitable for processing by the related microwave heating equipment 100 of present embodiment.In this case, can in the situation that the second material not being caused to fire damage, heat the first material.
At this, use Fig. 4 to describe the related microwave heating equipment 101 of other example of present embodiment.In Fig. 4, the inscape identical with Fig. 2 used prosign and description thereof is omitted.Be with the difference of Fig. 2, cooling device 380 has the air cooling mechanism 391 of spraying refrigerating gas to cylinder 350.Air cooling mechanism 391 forms by importing cooled refrigerating gases from air entry 400 and being sprayed onto the lateral surface of cylinder 350, thus the cylinder 350 in microwave irradiation is carried out to cooling structure.It should be noted that, sometimes also by come the mechanism of chilling roll 350 by cooling fluid be that water cooling tube 390 is recited as magnetism servo-electric motor water-cooling illustrated in fig. 2.The oxygen of the burning of refrigerating gas use air, inactive gas, promotion carbon or their mist.
Therefore with regard to magnetism servo-electric motor water-cooling, cooling effectiveness is high, and can accurately carry out temperature control, is applicable to make to want the material of heating to become the situation of high temperature (more than 600 ℃) or the situation of the temperature of the material of not wanting to do one's utmost to raise etc.Yet, for magnetism servo-electric motor water-cooling being set in cylinder 350, structure complicated thereby manufacturing cost are raise.On the other hand, with regard to air cooling mechanism 391, although compare cooling effectiveness with magnetism servo-electric motor water-cooling, decline, can simplify the structure of cylinder 350, can also manufacturing cost be suppressed lowly.Therefore, air cooling mechanism 391 is applicable to want the situation of treated substance in 600 ℃ of following lower temperature.
But, preferably by magnetism servo-electric motor water-cooling and the 391 combination configurations of air cooling mechanism.That is, preferably cooling device 380 also has air cooling mechanism 391 except having magnetism servo-electric motor water-cooling (water cooling tube 390).Thus, can improve cooling effectiveness, the temperature that therefore can do one's utmost to suppress to be difficult to absorb the material of microwave rises.In addition, owing to can also reducing the temperature of metal chamber 330 integral body, therefore can also reduce the microwave being absorbed by metal chamber 330, can heat efficiently object being treated.
And then, by two systems (magnetism servo-electric motor water-cooling and the air cooling mechanism 391) cooling body that utilizes 430 pairs of cooling devices 380 of control part to possess, control, thereby can realize cooling fast.Particularly, in the microwave irradiation silicon mud 360 making from microwave generator 300, make the either party in magnetism servo-electric motor water-cooling or air cooling mechanism 391 carry out cooling.In this case, control part 430 is controlled microwave generator 300 and cooling device 380 so that the surface temperature of silicon mud 360 becomes 600 ℃ of following modes.During before moisture in silicon mud 360 evaporates completely, because heat is captured in the evaporation of moisture, therefore exist hardly the temperature of silicon mud 360 to rise, easily remain on below 600 ℃.But in the stage after moisture evaporates completely, the temperature of silicon mud 360 sharply rises.Now, only the cooling temperature that cannot tackle sharply by a system in magnetism servo-electric motor water-cooling or air cooling mechanism 391 rises, the danger that exists the temperature in silicon mud 360 to rise.Therefore,, when the temperature of silicon mud 360 sharply rises, also to implement cooling mode fast with magnetism servo-electric motor water-cooling and air cooling mechanism 391, control.By and with both, carry out cooling fast, thereby in the situation that there is variations in temperature sharply, also the temperature of object being treated can be maintained to the temperature of expectation.When in this case, the temperature (temperature of silicon mud 360) of control part 430 in cylinder 350 becomes predefined temperature, make magnetism servo-electric motor water-cooling (water cooling tube 390) and 391 these two sides of air cooling mechanism carry out cooling.With regard to predefined temperature, in the situation that object being treated is silicon mud, be for example 500 degree, and be stored in advance in control part 430.
[industrial applicibility]
The present invention can be used in the heat treatment step of the various industrial circles such as synthetic of Reuse of materials operation, functional material or macromolecular material of solar cell or semiconductor etc.
Claims (16)
1. a microwave heating equipment, is characterized in that, possesses:
For keeping the cylinder of object being treated;
Microwave applicator to described cylinder internal radiation microwave;
Make the whirligig of described drum rotating;
Be arranged on the stirring piece in described cylinder;
Described cylinder is carried out to cooling cooling device.
2. microwave heating equipment according to claim 1, is characterized in that,
Described cooling device has the magnetism servo-electric motor water-cooling that carrys out cooling described cylinder by cooling fluid.
3. microwave heating equipment according to claim 2, is characterized in that,
Described magnetism servo-electric motor water-cooling is embedded to the side of described cylinder.
4. microwave heating equipment according to claim 2, is characterized in that,
The mode that the pipe that described magnetism servo-electric motor water-cooling passes through for described cooling fluid is located at described stirring piece forms.
5. microwave heating equipment according to claim 2, is characterized in that,
Described cooling device also has the air cooling mechanism to described roller spray refrigerating gas.
6. microwave heating equipment according to claim 5, is characterized in that, possesses:
Thermometer, it is measured the temperature in described cylinder;
Control part, it is cooling that it makes either party in described magnetism servo-electric motor water-cooling or described air cooling mechanism carry out when making described microwave applicator irradiating microwaves, and the temperature in described cylinder makes described magnetism servo-electric motor water-cooling and described air cooling this two side of mechanism carry out cooling while becoming predefined temperature.
7. microwave heating equipment according to claim 1, is characterized in that,
With the conductive coefficient in outside, the mode lower than the conductive coefficient of inner side forms described cylinder.
8. microwave heating equipment according to claim 1, is characterized in that,
Possessing when making described microwave applicator irradiating microwaves makes described cooling device carry out cooling control part.
9. microwave heating equipment according to claim 1, is characterized in that,
Described stirring piece consists of the material of transmission microwave.
10. according to the microwave heating equipment described in any one in claim 1 to 9, it is characterized in that,
Described object being treated comprises the first material and the second material,
Described the first material is that polar substances, dielectric loss angle Tan δ are that more than 0.01 material or conductance is 10
-2above and 10
4any in following material,
Described the second material and polar substances, dielectric loss angle Tan δ are that more than 0.01 material or conductance is 10
-2above and 10
4any in following material is all different.
11. 1 kinds of microwave heating methods, the object being treated irradiating microwaves in stirring in cylinder heats described object being treated, it is characterized in that,
Cooling described cylinder in irradiating microwaves.
12. microwave heating methods according to claim 11, is characterized in that,
Stirring piece on described cylinder carries out by cooling settings for described cylinder cooling.
13. microwave heating methods according to claim 11, is characterized in that,
The cooling of described cylinder undertaken by cooling fluid.
14. microwave heating methods according to claim 13, is characterized in that,
The cooling of described cylinder also carries out with refrigerating gas.
15. microwave heating methods according to claim 14, is characterized in that,
Described cylinder cooling used any in described cooling fluid or described refrigerating gas to carry out in irradiating microwaves, when the temperature in described cylinder becomes predefined temperature, with described cooling fluid and this two side of described refrigerating gas, carries out.
16. according to claim 11 to the microwave heating method described in any one in 15, it is characterized in that,
Described object being treated comprises the first material and the second material,
Described the first material is that polar substances, dielectric loss angle Tan δ are that more than 0.01 material or conductance is 10
-2above and 10
4any in following material,
Described the second material and polar substances, dielectric loss angle Tan δ are that more than 0.01 material or conductance is 10
-2above and 10
4any in following material is all different.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013080936A JP6106848B2 (en) | 2013-04-09 | 2013-04-09 | Microwave heating apparatus and microwave heating method |
| JP2013-080936 | 2013-04-09 |
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| CN104105239B CN104105239B (en) | 2016-02-17 |
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| CN107006082A (en) * | 2014-10-23 | 2017-08-01 | H·D·小吉姆瑞 | RF heating system |
| CN109668186A (en) * | 2018-12-28 | 2019-04-23 | 广东美的厨房电器制造有限公司 | Microwave cavity component and micro-wave oven |
| CN109668187A (en) * | 2018-12-28 | 2019-04-23 | 广东美的厨房电器制造有限公司 | Micro-wave oven |
| CN109668185A (en) * | 2018-12-28 | 2019-04-23 | 广东美的厨房电器制造有限公司 | Microwave cavity component and micro-wave oven |
| CN115432704A (en) * | 2021-06-04 | 2022-12-06 | 丰田自动车株式会社 | Method for producing guest-free silicon inclusion compound and apparatus for producing guest-free silicon inclusion compound |
| US11955628B2 (en) | 2021-06-04 | 2024-04-09 | Toyota Jidosha Kabushiki Kaisha | Method of producing guest-free silicon clathrate, apparatus for producing guest-free silicon clathrate |
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| CN109668186B (en) * | 2018-12-28 | 2020-07-14 | 广东美的厨房电器制造有限公司 | Microwave cavity assembly and microwave oven |
| CN115432704A (en) * | 2021-06-04 | 2022-12-06 | 丰田自动车株式会社 | Method for producing guest-free silicon inclusion compound and apparatus for producing guest-free silicon inclusion compound |
| US11955628B2 (en) | 2021-06-04 | 2024-04-09 | Toyota Jidosha Kabushiki Kaisha | Method of producing guest-free silicon clathrate, apparatus for producing guest-free silicon clathrate |
| CN115432704B (en) * | 2021-06-04 | 2024-04-09 | 丰田自动车株式会社 | Method for producing guest-free silicon clathrate and apparatus for producing guest-free silicon clathrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6106848B2 (en) | 2017-04-05 |
| CN104105239B (en) | 2016-02-17 |
| JP2014203762A (en) | 2014-10-27 |
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