The KNN base energy storage microcrystal glass materials and preparation method of a kind of ultralow dielectric loss
【Technical field】
The present invention relates to microcrystal glass material field, and in particular to a kind of KNN base energy storage crystallite glass of ultralow dielectric loss
Glass material and preparation method.
【Background technology】
The pulse power is the core technology of pulse power system, and capacitor is the important storage of pulse power system prioritizing selection
Energy element, and high-energy-density capacitor is one of key factor of restriction highpowerpulse technology success or failure.Therefore, high-energy-density electricity
Vessel media material has turned into the focus [1] of the developed countries such as U.S. research.(Smith,N.J.,B.Rangarajan,
M.T.Lanagan,C.G.Pantano.Alkali-free glass as a high energy density dielectric
material[J].Materials Lerrers,2009,(63):1245-1248.)
Though currently used as foil structure capacitance or the metallization film capacitor volume production of great power pulse power source system,
Unit volume energy storage density does not all include height (generally below 1.0J/cm3), and there is break down explosive and discharge current
It is small, [2] (Zhu Zhifang, Lin Fuchang, performance [J] for wearing tinkling of pieces of jade high energy density ceramic capacitors swash by force the shortcomings of discharge life is short
Light and the particle beams, 2004,16 (10):1341-1344.).Although ceramic capacitor has dielectric constant high, but because ceramics are situated between
Material exists and is difficult to the gas hole defect that eliminates, cause material resistance to breakdown strength relatively low [3] (Beall, G.H.,
L.R.Pinckney.Nanophase glass-ceramics[J].Journal of the American Ceramic
Society, 1999,82 (1):5-16.), therefore the space that rises of the actual energy storage density of such material is smaller, this will be increasingly difficult to
To meet requirement of the highpowerpulse equipment to high-energy-density capacitor.Current people are just being actively developed high energy storage density Novel electric
Vessel media material, used as high-energy-density impulse capacitor, (ratio of impulse capacitor can refer to what capacitor unit volume was stored
Energy, its size is proportional to ε Ε2.Wherein ε is the dielectric constant of medium, and Ε is the working field strength of medium) dielectric material
Developing way, ferroelectric glass-ceramic (also known as devitrified glass) material is with the breakdown strength high of pore-free mode collection glass state material
Based on both high-ks of dielectric ceramic system advantage, focus [4-5] as high energy storage material research (Chu,
B.J.,X.Zhou,K.L.Ren,B.Neese,M.Lin,Q.Wang,F.Bauer,Q.M.Zhang.A dielectric
polymer with high electric energy density and fast discharge speed[J]
.Science,2006,313(5785):334-336.Graca,M.P.F.,M.G.Ferreira da Silva,
A.S.B.Sombra,M.A.Valente.Electric and dielectric properties of a
SiO2Na2ONb2O5glass subject to a controlled heat-treatment process[J].Physica
B,2007,396(1-2):62-69.)。
Current niobates glass ceramics is the hot research of energy storage glass ceramics, but mostly around strontium barium niobate glass powder
Or ceramics launch research, but strontium barium niobate belongs to tungsten bronze structure, and dielectric constant and ferroelectricity all can not show a candle to perovskite sections
Electric material.Potassium-sodium niobate (i.e. (K, Na) NbO3, abbreviation KNN in text) and belong to typical perovskite crystal structure.ABO3The perovskite of type
Crystal structure is a kind of stabilization and widely used crystal formation is typical ferroelectric, not only have in terms of ferroelectricity, piezoelectricity, pyroelectricity compared with
Many research, also there is more novel research concern temperature in terms of photocatalysis, energy storage.With regard to Ca-Ti ore type (K, Na) NbO3Material
For, just there is its hotter research and development prospect in terms of piezoelectricity, PTC originally, cannot also prepare at present a kind of with height
The potassium-sodium niobate glass ceramics of disruptive field intensity and high-k.
【The content of the invention】
It is an object of the invention to overcome defect present in prior art, there is provided a kind of KNN bases of ultralow dielectric loss
Energy storage microcrystal glass material and preparation method, the reaction of the method raw material high uniformity, utilization rate is high, and obtained glass
Ceramic material, with dielectric constant higher.
To achieve the above object, the technical scheme of microcrystal glass material use of the present invention is:
The microcrystal glass material be by glass phase and crystalline phase be blended, melting, cooling shaping, annealing and crystallization and thermal treatment system
;Wherein, by mole percent, glass mutually accounts for 20~50%, balance of crystalline phase;Crystalline phase be by mol ratio be (3-x):
(3-x):6:The K of 2x2CO3、Na2CO3、Nb2O5And BaCO3Composition, 0 < x≤2.5.
Further, glass be mutually by mol ratio be (2~4):1 SiO2And H3BO3Composition.
Further, also it is added with the glass nucleus for accounting for glass phase and crystalline phase integral molar quantity 0~4% in glass phase and crystalline phase
Agent.
Further, glass Nucleating Agent is CeO2。
The technical scheme of preparation method of the present invention is to comprise the following steps:
1) it is (3-x) according to mol ratio:(3-x):6:2x takes K2CO3、Na2CO3、Nb2O5And BaCO3Mixing, obtains crystalline phase,
Wherein 0 < x≤2.5;Crystalline phase and glass are mixed, mixture A is obtained, mixture A integral molar quantities are accounted for being added in mixture A
0~4% glass Nucleating Agent is simultaneously well mixed, and obtains mixture B;
2) by step 1) in mixture B heating until forming uniform melt;Melt is poured into the shaping of mould chilling, is obtained
To glass sample, glass sample is made annealing treatment;
3) Crystallizing treatment will be carried out by the glass sample of annealing, the KNN base energy storage for obtaining ultralow dielectric loss is micro-
Crystal glass material.
Further, step 1) glass be mutually by mol ratio be (2~4):1 SiO2And H3BO3It is mixed to get;Step
5~10h of ball milling is well mixed after glass Nucleating Agent is added in rapid mixture A 1).
Further, step 2) in heating process be:Silica crucible or alumina crucible are heated to stove from room temperature
At 900~1200 DEG C, be initially added into mixture B, then proceed to be heated to 1300~1400 DEG C, make mixture B fully melt and
Bubble-free.
Further, mixture B is incubated 20~40min at 1300~1400 DEG C.
Further, step 2) in annealing be 500~700 DEG C be incubated 5~10h.
Further, step 3) in Crystallizing treatment be 800~1000 DEG C be incubated 1~6h.
Compared with prior art, the beneficial effects of the present invention are:
The obtained KNN base energy storage microcrystal glass material porositys of the invention are minimum, meanwhile, dielectric loss is extremely low.In composition
On, have selected the K not appeared in the newspapers2O-Na2O-Nb2O5-BaO-SiO2-B2O3System.Wherein, SiO2-B2O3It is brilliant to form glass
The main formula of phase, and K2O-Na2O then not only served as the network outer body in glass system but also turn into separate out KNN crystalline phases it is main into
Point, the most excellent part of the glass formula is to introduce BaO, not only to potassium-sodium niobate system regulation crystalline phase composition, and for analysis
Brilliant process has certain facilitation, and the network outer body that alkaline-earth metal ions had both turned into glass (is also likely to become centre
Body), accelerate crystallization, pinning effect can be caused again, weaken interfacial polarization to puncturing the adverse effect of deterioration, finally give dielectric high
Constant microcrystal glass material.Knowable to test, two kinds of crystalline phases, i.e. potassium-sodium niobate are separated out in the glass ceramic material that the present invention is obtained
(Na0.9K0.1NbO3) perovskite ferroelectric crystalline phase and barium sodium niobate (BNN) (Ba2NaNb5O15) tungsten bronze ferroelectric crystalline phases coexist, and tungsten bronze
Maximum performance advantage be its ultralow dielectric loss, can as little as less than 0.006, and the dielectric properties of material of the present invention exist
Step up.Such formula design improves dielectric constant while keeping higher puncturing from can fundamentally reduce dielectric loss
Field intensity, realizes the raising of energy storage.
Preparation method of the present invention only needs to mix each raw material, ball milling, melting, shaping, annealing and Crystallizing treatment, i.e.,
KNN base energy storage microcrystal glass materials are can obtain, the present invention uses melting-crystallization and thermal treatment method, and the reaction of raw material high uniformity is utilized
Rate is high, and experimental implementation is simple, and forming method is more, by can effectively eliminate internal stress after annealing, after Crystallizing treatment, allows crystalline substance
Mutually more completely, crystallization is more thorough for growth, and internal grain is thinner, homogenization degree is higher and energy storage density is higher beneficial to obtaining
Glass ceramics.At present, the ultralow method for connecing electrical loss KNN base energy storage devitrified glasses is prepared using melting-crystallization and thermal treatment method
Have not been reported.
【Brief description of the drawings】
Fig. 1 is the XRD spectrum of KNN bases energy storage microcrystal glass material of the present invention.
Fig. 2 is the dielectric constant of KNN bases energy storage microcrystal glass material of the present invention with frequency variation curve.
Fig. 3 is the dielectric loss of KNN bases energy storage microcrystal glass material of the present invention with frequency variation curve.
【Specific embodiment】
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
The present invention is by K2CO3、Na2CO3、Nb2O5、BaCO3、SiO2、H3BO3And CeO2Blended melting, shaping, annealing
And obtained in Crystallizing treatment.It is comprised the following steps that:
1) analytically pure commercially available K is weighed2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And CeO2And carry out ball milling 5
~10h mixes, and obtains mixture;Wherein, K2CO3、Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, 0
< x≤2.5, constitute crystalline phase;SiO2And H3BO3Mol ratio be (2~4):1, constitute glass phase;With the total of crystalline phase and glass phase
Mole is 100% meter, and glass mutually accounts for 20~50%, balance of crystalline phase;CeO2Addition be glass phase and crystalline phase total moles
0~the 4mol%, CeO of amount2Can be without it is added as Nucleating Agent herein, also dielectric constant can both be carried with fluxing
It is high helpful.
Zirconium dioxide ballstone is used during ball milling, medium is distilled water, and mass ratio is material:Ballstone:Distilled water=1:1.5:2.
2) by silica crucible or alumina crucible with stove from room temperature be heated to 900~1200 DEG C when, be initially added into step 1)
In mixture, then proceed to be heated to 1300~1400 DEG C, and be incubated 20~40min, mixture is fully melted and without gas
Bubble finally obtains well mixed melting charge;Mixed melting material is poured on copper coin mould is at room temperature molded, then be put into stove rapidly
In at 500~700 DEG C anneal 5~10h, to eliminate internal stress, obtain glass sample;
3) smashed by taking the obtained glass sample of a small amount of present invention and do DSC differential scanning calorimetries and test, obtained
Substantially recrystallization temperature to glass sample under exothermic peak, it is necessary to carry out insulation heat treatment.
By the above-mentioned glass sample by annealing in 800~1000 DEG C of insulations, crystallization and thermal treatment is carried out, carry out crystallization
The total time for the treatment of is about 1~6h, and then furnace cooling obtains K to room temperature2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The present invention is described in further details below in conjunction with specific embodiment.
Embodiment 1:
The preparation method of the present embodiment glass ceramic material comprises the following steps:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.25:0.25:0.6:0.1:0.6:0.2,
Take K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、
Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=0.5;SiO in glass phase2And H3BO3Mol ratio
It is 3:1, glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 600 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 850 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The potassium-sodium niobate glass ceramics cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 1~1.2mm, thin slice
After through polishing, cleaning, silver electrode paste is uniformly coated in thin slice tow sides, 20 minutes are incubated in 600 DEG C, obtain glass to be measured
Ceramics sample.
Embodiment 2:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.2:0.2:0.6:0.2:0.6:0.2, take
K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、Na2CO3、
Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=1;SiO in glass phase2And H3BO3Mol ratio be 3:1, glass
Glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 650 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 850 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The potassium-sodium niobate glass ceramics cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 1~1.2mm, thin slice
After through polishing, cleaning, silver electrode paste is uniformly coated in thin slice tow sides, 20 minutes are incubated in 600 DEG C, obtain glass to be measured
Ceramics sample.
Embodiment 3:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.15:0.15:0.6:0.3:0.6:0.2,
Take K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、
Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=1.5;SiO in glass phase2And H3BO3Mol ratio
It is 3:1, glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 600 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 850 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The potassium-sodium niobate glass ceramics cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 1~1.2mm, thin slice
After through polishing, cleaning, silver electrode paste is uniformly coated in thin slice tow sides, 20 minutes are incubated in 600 DEG C, obtain glass to be measured
Ceramics sample.
Embodiment 4
The preparation method of the present embodiment glass ceramic material comprises the following steps:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.1:0.1:0.6:0.4:0.6:0.2, take
K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、Na2CO3、
Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=2;SiO in glass phase2And H3BO3Mol ratio be 3:1, glass
Glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 600 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 750 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The potassium-sodium niobate glass ceramics cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 1~1.2mm, thin slice
After through polishing, cleaning, silver electrode paste is uniformly coated in thin slice tow sides, 20 minutes are incubated in 600 DEG C, obtain glass to be measured
Ceramics sample.
Embodiment 5
The preparation method of the present embodiment glass ceramic material comprises the following steps:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.05:0.05:0.6:0.5:0.6:0.2,
Take K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、
Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=2.5;SiO in glass phase2And H3BO3Mol ratio
It is 3:1, glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 600 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 850 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
Embodiment 6 (G0)
The preparation method of the present embodiment glass ceramic material comprises the following steps:
1) the present embodiment KNN bases glass ceramic material be by material amount ratio be 0.15:0.15:0.3:0:0.3:0.1, take
K2CO3, Na2CO3, Nb2O5, BaCO3, SiO2, H3BO3And 0.2mol%CeO2Mixing.Now, in crystalline phase, K2CO3、Na2CO3、
Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=0;SiO in glass phase2And H3BO3Mol ratio be 3:1, glass
Glass mutually accounts for the 40% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1100 DEG C when, be initially added into mixture, then proceed to be heated to
1350 DEG C, and 30min is incubated at 1350 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 7h that annealed at 600 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 5h at 850 DEG C2O-Na2O-Nb2O5-SiO2-B2O3System glass is made pottery
Ceramic material.
Embodiment 7-9
Material rate in crystalline phase successively according to the form below is adjusted, other conditions are same as Example 6.
Raw material |
|
|
|
|
|
|
Embodiment 6 (G0) |
0.15 |
0.15 |
0.3 |
0 |
0.3 |
0.1 |
Embodiment 7 (G1) |
0.12 |
0.12 |
0.3 |
0.06 |
0.3 |
0.1 |
Embodiment 8 (G2) |
0.06 |
0.06 |
0.3 |
0.18 |
0.3 |
0.1 |
Embodiment 9 (G3) |
0.03 |
0.03 |
0.3 |
0.24 |
0.3 |
0.1 |
The potassium-sodium niobate glass ceramics cutting machine that above example is obtained is switched to the thin slice that thickness is 1~1.2mm, thin
After piece is through polishing, cleaning, silver electrode paste is uniformly coated in thin slice tow sides, 20 minutes are incubated in 600 DEG C, obtain glass to be measured
Glass ceramics sample.
BaCO in embodiment 6-93Addition increase successively, after tested understand, the dielectric constant without barium source sample compared with
It is low.
Two kinds of crystalline phases, i.e. potassium-sodium niobate have been separated out in the glass ceramic material according to obtained in Fig. 1 can obtain the present invention
(Na0.9K0.1NbO3) perovskite ferroelectric crystalline phase and barium sodium niobate (BNN) (Ba2NaNb5O15) tungsten bronze ferroelectric crystalline phases coexist, and tungsten bronze
Maximum performance advantage be its ultralow dielectric loss, thus explain well Fig. 3 dielectric loss reduction phenomenon, and
And dielectric properties are being stepped up as can be seen from Figure 2.Such formula design is improved from can fundamentally reduce dielectric loss
Dielectric constant keeps disruptive field intensity higher simultaneously, realizes the raising of energy storage.
The present invention minimum dielectric loss of glass ceramics sample to be measured can as little as less than 0.006.
Embodiment 10:
1) first it is following raw material mixing during prepared by the present embodiment KNN bases energy storage microcrystal glass material:In crystalline phase, K2CO3、
Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=1.5;SiO in glass phase2And H3BO3Mol ratio
It is 2:1, glass mutually accounts for the 20% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 900 DEG C when, be initially added into mixture, then proceed to be heated to 1300
DEG C, and 20min is incubated at 1300 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material on copper coin
Shaping, then be put into rapidly in stove in the 4h that annealed at 700 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 1h at 800 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
Embodiment 11:
1) first it is following raw material mixing during prepared by the present embodiment KNN bases energy storage microcrystal glass material:In crystalline phase, K2CO3、
Na2CO3、Nb2O5And BaCO3Mol ratio be (3-x):(3-x):6:2x, x=1.5;SiO in glass phase2And H3BO3Mol ratio
It is 4:1, glass mutually accounts for the 50% of crystalline phase and glass phase total amount.
2) by silica crucible with stove heat from room temperature to 1200 DEG C when, be initially added into mixture, then proceed to be heated to
1400 DEG C, and 40min is incubated at 1400 DEG C makes mixture melt uniformly, obtains mixed melting material;By mixed melting material in copper
It is molded on plate, then is put into rapidly in stove in the 6h that annealed at 800 DEG C, glass after being annealed;
3) furnace cooling obtains K to room temperature after being incubated 6h at 1000 DEG C2O-Na2O-Nb2O5-BaO-SiO2-B2O3System glass
Glass ceramic material.
The present invention generates high-k high strike by the ratio of rationally control ferroelectricity potassium-sodium niobate crystal and glass content
Wear the ferroelectric glass-ceramic of field intensity and low-dielectric loss.Also, sample is prepared using fusion method, technique is easy, forming method compared with
Many, resistance to breakdown strength is high, is the important method for preparing high energy storage density material.High-k high breakdown fields prepared by the present invention
It is technically and economically and excellent as energy storage material that strong potassium-sodium niobate glass ceramics is expected to substitute traditional ferroelectric ceramic material
One of important candidate material.
The present invention prepares KNN base energy storage microcrystal glass materials using fusion method, the advantage is that preparation method is simple, technique
Flow is simple, and shaping can be controlled arbitrarily as needed, with short production cycle, be particularly suitable for industrialized production.In the present invention at crystallization
Reason is that crystallization is more thorough in order to allow crystalline phase to grow more completely using segmentation insulation, and is tested and can also be obtained by the later stage,
When in two recrystallization temperatures isothermal holding simultaneously, the potassium-sodium niobate glass ceramics sample interior crystal grain for obtaining is thinner, homogenizes journey
Du Genggao, energy storage density is higher.KNN base energy storage microcrystal glass materials prepared by the present invention are a kind of with high-k high strike
Wear the ferroelectric glass-ceramic of field intensity and low dielectric loss.
One embodiment of the present invention is the foregoing is only, is not all of or unique implementation method, this area leads to skill
Any equivalent conversion that art personnel are taken technical solution of the present invention by reading description of the invention, is of the invention
Claim is covered.