1. The intelligent dynamic dimming film is characterized by being prepared from the following raw materials in parts by weight: 30-50 parts of porous glass beads, 10-18 parts of lithium hydroxide, 20-40 parts of nano tungsten trioxide, 6-12 parts of polypyrrole, 40-60 parts of silica sol and 5-10 parts of silane coupling agent.

2. The intelligent dynamic dimming film of claim 1, wherein the average porosity of the porous glass beads is 45% -55%.

3. The intelligent dynamic dimming film according to claim 1, further comprising 2 to 8 parts by weight of an activator, wherein the activator is at least one of persulfate and trimethylchlorosilane.

4. The intelligent dynamic dimming film according to claim 1, further comprising microcrystalline cellulose in an amount of 18 to 24 parts by weight.

5. The intelligent dynamic dimming film according to claim 5, wherein the average degree of polymerization of the microcrystalline cellulose is 120-180.

6. The intelligent dynamic dimming film according to claim 1, wherein the silane coupling agent is selected from any one of methyltris (trimethylsiloxy) silane and silane coupling agent KH-550.

7. The intelligent dynamic dimming film according to claim 1, wherein the porous glass beads are prepared according to the following steps:

(1) heating the glass beads at the temperature of 450-600 ℃ for 30-45h, and cooling the glass beads after heating;

(2) will cool down2 mol. L of glass beads are put into the glass beads at room temperature^-1And (3) carrying out acid washing in a hydrochloric acid solution, taking out the glass beads after 1.5-2h of acid washing, washing and drying to obtain the porous glass beads.

8. The intelligent dynamic dimming film according to claim 7, wherein in the preparation of the porous glass beads, the temperature of the glass beads is reduced at a rate of 20-35 ℃/min in step (1).

9. The method for manufacturing an intelligent dynamic dimming film according to any one of claims 1 to 8, comprising the steps of:

(1) uniformly mixing the porous glass beads and lithium hydroxide, and heating at the temperature of 240-280 ℃ for 8-14h to obtain a mixture 1;

(2) dissolving the mixture 1, nano tungsten trioxide, a conductive additive and a silane coupling agent in silica sol, heating for 1.5-2.5h at 40-60 ℃ and continuously stirring to obtain a mixture 2;

(3) and after the mixture 2 is cooled, processing the mixture 2 by using a solution casting method under the vacuum degree of 100-200Pa to obtain the intelligent dynamic dimming film.

10. An application of the intelligent dynamic dimming film is characterized in that the intelligent dynamic dimming film of any one of claims 1 to 8 is used for manufacturing laminated glass, and comprises a first glass layer, the intelligent dynamic dimming film and a second glass layer which are sequentially stacked, wherein the first glass layer and the second glass layer are bonded with the intelligent dynamic dimming film through EVA (ethylene vinyl acetate) adhesive films.

Background

The electrochromic glass is a novel functional material and is generally assembled by a glass substrate and an electrochromic layer, wherein the main component of the electrochromic layer is an electrochromic material (generally, a transition metal oxide). The electrochromic material has the characteristic of changing color under the action of current, and by means of the characteristic, the electrochromic glass can adjust the light transmittance and the light absorption rate of the electrochromic glass under the control of the current, so that the effect of adjusting indoor brightness is realized.

Chinese patent with publication No. CN103365017B discloses an inorganic all-solid-state electrochromic device, which comprises a glass substrate, and a transparent conductive layer A, an electrochromic layer, an ion conductive layer and a transparent conductive layer B which are sequentially deposited on the glass substrate, wherein the transparent conductive layer A and the transparent conductive layer B are both aluminum-doped zinc oxide films, the electrochromic layer is a tungsten oxide film, and the ion conductive layer is a Li₄Ti₅O₁₂A film; the preparation method comprises the following steps: (1) preparing an aluminum-doped zinc oxide film on a cleaned glass substrate by adopting a direct-current magnetron sputtering method; (2) preparing a tungsten oxide film on the aluminum-doped zinc oxide film by adopting a direct-current magnetron sputtering method; (3) preparation of Li on tungsten oxide film by radio frequency magnetron sputtering method₄Ti₅O₁₂A film; (4) by using a direct current magnetron sputtering method on Li₄Ti₅O₁₂Preparing the aluminum-doped zinc oxide film on the film. When the light transmittance of the color-changing device needs to be reduced, current passes between the transparent conducting layer A and the transparent conducting layer B, meanwhile, lithium ions in the ion conducting layer migrate into the electrochromic layer, and tungsten oxide in the electrochromic layer absorbs free electrons and lithium ions and then is converted into a dark color; when the transparency of the color-changing device needs to be improved, the current is interrupted, and the tungsten oxide releases electrons and lithium ions and is converted into a transparent state.

With respect to the related art in the above, the inventors believe that, as the number of migration times of lithium ions between the ion conductive layer and the electrochromic layer increases, a part of the lithium ions will gradually block the ion transport channel between the ion conductive layer and the electrochromic layer, weakening the ability of the tungsten oxide to absorb the lithium ions, resulting in a decrease in the color-change adjustment range of the color-changing device with an increase in the use time.

Disclosure of Invention

In the related art, as the number of lithium ion transfers increases, the discoloration adjustment range of the color changing device gradually decreases. In order to overcome the defect, the application provides an intelligent dynamic light adjusting film and a preparation method and application thereof.

First aspect, this application provides an intelligence developments membrane of adjusting luminance, adopts following technical scheme: an intelligent dynamic light adjusting film is prepared from the following raw materials in parts by weight: 30-50 parts of porous glass beads, 10-18 parts of lithium hydroxide, 20-40 parts of nano tungsten trioxide, 6-12 parts of polypyrrole, 40-60 parts of silica sol and 5-10 parts of silane coupling agent

By adopting the technical scheme, the lithium hydroxide modifies the porous glass beads, lithium ions in the lithium hydroxide exchange with cations in the porous glass beads, so that lithium ions in the porous glass beads contain, and then the porous glass beads absorb the nano tungsten trioxide, so that the porous glass beads simultaneously become carriers of the nano tungsten trioxide and the lithium ions. The polypyrrole has conductivity, the polypyrrole is grafted on the surface of the lithium-based glass bead under the action of a silane coupling agent, and the porous glass bead forms an intelligent dynamic dimming film with conductivity under the action of silica sol. Because lithium ions and tungsten trioxide in the intelligent dynamic dimming film are carried in the porous glass beads, the migration distance of the lithium ions is short in the electrifying process, an ion transmission channel is not easy to block, and after the porous glass beads are treated by lithium hydroxide, all pores inside the porous glass beads are communicated with one another, even if part of pores are blocked, the lithium ions can be compounded with the tungsten trioxide through the unblocked pores, so that the effect of absorbing the lithium ions by the tungsten trioxide is improved, and the stability of the discoloration adjusting range of the intelligent dynamic dimming film is improved. In addition, the silane coupling agent also improves the surface property of the intelligent dynamic dimming film, so that the cohesiveness between the intelligent dynamic dimming film and the EVA adhesive film is improved.

Preferably, the intelligent dynamic dimming film is prepared from the following raw materials in parts by weight: 35-45 parts of porous glass beads, 12-16 parts of lithium hydroxide, 25-35 parts of nano tungsten trioxide, 7.5-10.5 parts of polypyrrole, 45-55 parts of silica sol and 6-9 parts of silane coupling agent.

By adopting the technical scheme, the proportion of the intelligent dynamic dimming film is optimized, and the color change adjusting range of the intelligent dynamic dimming film is more stable.

Preferably, the average porosity of the porous glass beads is 45% to 55%.

By adopting the technical scheme, when the porosity of the porous glass beads is too small, the absorption capacity of the porous glass beads to tungsten trioxide and lithium ions is limited, and the color change adjusting range of the intelligent dynamic light adjusting film is relatively small; when the porosity of the porous glass beads is too large, the tungsten trioxide and the lithium ions absorbed by the porous glass beads are easy to lose, the probability of compounding the tungsten trioxide and the lithium ions is reduced, and the color change adjusting range of the intelligent dynamic light adjusting film is small. When the porosity is 45% -55%, the color change adjusting range of the intelligent dynamic light adjusting film is large.

Preferably, the formula of the intelligent dynamic dimming film further comprises 2-8 parts by weight of an exciting agent, and the exciting agent is at least one of persulfate and trimethylchlorosilane.

By adopting the technical scheme, persulfate and trimethylchlorosilane can break a part of silicon-oxygen bonds in the porous glass beads and hydrolyze to form silanol groups. After the porous glass beads adsorb the nano tungsten trioxide, the nano tungsten trioxide is combined with silanol groups and fixed on the hole walls and the surfaces of the porous glass beads, so that the capacity of carrying the nano tungsten trioxide by the glass beads is improved, the possibility of loss of the nano tungsten trioxide is reduced, and the stability of the color change adjusting range of the intelligent dynamic light adjusting film is favorably improved.

Preferably, the formula of the intelligent dynamic dimming film further comprises 18-24 parts by weight of microcrystalline cellulose.

By adopting the technical scheme, the microcrystalline cellulose contains a large amount of active hydroxyl, and in the process of silica sol dehydration, the microcrystalline cellulose can form hydrogen bonds with water in the silica sol, so that the viscosity of the silica sol is increased, and the intelligent dynamic light modulation film is favorably formed. After the shaping of intelligence developments membrane of adjusting luminance, microcrystalline cellulose evenly distributed is in intelligence developments membrane of adjusting luminance, and microcrystalline cellulose can enough shield remaining hydrophilic group in the membrane of adjusting luminance to intelligence developments through the hydrogen bond, reduces the moisture absorption of intelligence developments membrane of adjusting luminance, can cushion the inside stress of intelligence developments membrane of adjusting luminance again, reduces the possibility that intelligence developments membrane of adjusting luminance takes place to warp.

Preferably, the microcrystalline cellulose has an average degree of polymerization of 120-180.

By adopting the technical scheme, when the molecular weight of the microcrystalline cellulose is smaller, the mobility of microcrystalline cellulose molecules is stronger, and the viscosity of the silica sol cannot be sufficiently adjusted; when the molecular weight of the microcrystalline cellulose is too large, the microcrystalline cellulose is easy to be polymerized into clusters and settled, and the viscosity of the silica sol cannot be sufficiently regulated, and when the average polymerization degree of the microcrystalline cellulose is 120-180, the viscosity of the silica sol is high, and the intelligent dynamic light-adjusting film is easy to form.

Preferably, the silane coupling agent is selected from methyl tri (trimethylsiloxy) silane and silane coupling agent KH-550.

By adopting the technical scheme, the methyl tri (trimethylsiloxy) silane and the silane coupling agent KH-550 have coupling effects, and compared with the silane coupling agent KH-550, the methyl tri (trimethylsiloxy) silane has higher efficiency of silanol groups generated by hydrolysis, so the coupling effect is better.

Preferably, the porous glass beads are prepared according to the following steps:

(1) heating the glass beads at the temperature of 450-600 ℃ for 30-45h, and cooling the glass beads after heating; (2) 2 mol.L of glass beads cooled to room temperature are put into the glass beads^-1And (3) carrying out acid washing in a hydrochloric acid solution, taking out the glass beads after 1.5-2h of acid washing, washing and drying to obtain the porous glass beads.

By adopting the technical scheme, in the step (1), the soluble phase and the insoluble phase of the glass beads are separated under the heating condition, and after the soluble phase of the glass beads is washed away by hydrochloric acid in the step (2), pores are formed in the remaining insoluble phase, so that the porous glass beads can be prepared.

Preferably, when the porous glass beads are prepared, the temperature of the glass beads is reduced at a rate of 20-35 ℃/min in the step (1).

By adopting the technical scheme, when the cooling speed is too high, the glass beads are easy to break, and complete porous glass beads cannot be obtained; when the temperature decrease rate is too slow, the portion of the porous glass beads in a molten state blocks the pores, and thus the porosity of the porous glass beads decreases. When the temperature reduction rate is between 20 and 35 ℃/min, the porous glass beads are not easy to break, and the porosity of the porous glass beads is increased along with the increase of the temperature reduction rate.

In a second aspect, the present application provides a method for preparing an intelligent dynamic dimming film, which adopts the following technical scheme:

(1) the porous glass beads and lithium hydroxide are uniformly mixed and heated at the temperature of 240 ℃ and 280 ℃ for 8-14h to obtain a mixture 1.

(2) Dissolving the mixture 1, nano tungsten trioxide, polypyrrole and a silane coupling agent in silica sol, heating for 1.5-2.5h at 40-60 ℃ and continuously stirring to obtain a mixture 2;

(3) after the mixture 2 is cooled, the mixture 2 is dehydrated by using a solution casting method under the vacuum degree of 100-200Pa, and the intelligent dynamic dimming film is obtained.

By adopting the technical scheme, the intelligent dynamic dimming film is prepared by taking the porous glass beads as the main material and under the assistance of silica sol.

The third aspect provides an application of intelligent dynamic dimming film, which adopts the following technical scheme:

the utility model provides an application of intelligence developments membrane of adjusting luminance will intelligence developments membrane of adjusting luminance is used for making laminated glass, including the first glass layer, the intelligence developments membrane of adjusting luminance and the second glass layer that stack gradually the setting, first glass layer and second glass layer all bond with intelligence developments membrane of adjusting luminance through the EVA glued membrane.

By adopting the technical scheme, the laminated glass with the electrochromic effect is prepared by using the intelligent dynamic dimming film.

In summary, the present application has the following beneficial effects:

1. because this application adopts porous glass microballon as tungsten trioxide and lithium ion's carrier, consequently shortened lithium ion's migration distance, and lithium hydroxide makes intercommunication each other between the different holes when handling porous glass microballon, has improved more transmission channel for lithium ion to improve the effect that tungsten trioxide absorbs lithium ion, improved the stability of the adjusting range that discolours of intelligent dynamic membrane of adjusting luminance.

2. It is one of the raw materials as intelligent dynamic membrane of adjusting luminance to prefer the exciting agent in this application to prefer persulfate and trimethylchlorosilane to be as the exciting agent, persulfate and trimethylchlorosilane all make the silica bond fracture on porous glass bead surface, and generate silanol group, silanol group combines with nanometer tungsten trioxide again, and nanometer tungsten trioxide receives the fixed of chemical bond and adsorption simultaneously, consequently is difficult to run off, thereby has improved the stability of the adjusting range that discolours of intelligent dynamic membrane of adjusting luminance.

3. According to the method, the porous glass beads are used as the main material and are molded under the assistance of silica sol, and the intelligent dynamic dimming film is finally obtained.

4. This application is applied to making laminated glass with intelligence developments membrane of adjusting luminance, and the laminated glass who makes has electrochromic effect.

Detailed Description

The present application will be described in further detail with reference to examples.

Preparation example of porous glass beads

The following will explain preparation example 1 as an example.

Preparation example 1

The raw materials used in the preparation example can be obtained commercially, wherein the glass beads are SOVITEC solid glass beads produced by Kunzahuan Linwei trade company, Inc.; the hydrochloric acid is prepared from concentrated hydrochloric acid (CP grade) with 37% of chemical purity, which is produced by Huafu chemical Limited company in Yangzhou city. The porous glass beads were prepared according to the following method:

(1) placing the glass beads into a crucible, heating for 40h at the temperature of 450-600 ℃, and cooling the glass beads at the cooling rate of 20 ℃/min after heating;

(2) 2 mol.L of glass beads cooled to room temperature are put into the glass beads^-1Pickling in hydrochloric acid solution for 1.8h, taking out the glass beads for washingAnd drying to obtain the porous glass beads.

Preparation examples 2 to 6

As shown in Table 1, production examples 2 to 6 differ from production example 1 in the temperature decreasing rate.

TABLE 1

Sample(s)	Preparation example 1	Preparation example 2	Preparation example 4	Preparation example 4	Preparation example 5	Preparation example 6
							Cooling Rate/(. degree. C./min)	15	20	25	30	35	40

After the porous glass beads were prepared, the average porosity of the porous glass beads of preparation examples 1 to 6 was examined by the Beijing research institute of cleaning and technology, and the examination results are shown in Table 2.

TABLE 2

Sample(s)

Preparation example 1

Preparation example 2

Preparation example 4

Preparation example 4

Preparation example 5

Preparation example 6

Average porosity

42％

45％

48％

52％

55％

58％

Examples

The raw materials used in the examples of the present application are all commercially available, and if not specified otherwise, the lithium hydroxide is anhydrous lithium hydroxide produced by shanghai chemical ran ltd; the nano tungsten trioxide is prepared from nano tungsten trioxide for photochromic glass produced by Hangzhou Hengge nano science and technology limited; polypyrrole was purchased from Sigma-Ald3 ich; the silica sol is HP3010 high-purity silica sol produced by Shandong Baite new material company Limited; persulfate is sodium peroxodisulfate produced by Shandong war biological science and technology limited; the trimethylchlorosilane is trimethylchlorosilane (CAS No. 75-77-4) produced by Asahi Kasei chemical science and technology Limited in Shandong; the microcrystalline cellulose is food-grade microcrystalline cellulose produced by Hebei Koron Multi-Biotech limited; methyltris (trimethylsiloxy) silane was purchased from Sigma-Ald3ich company; the silane coupling agent KH-550 is prepared from KH-550 produced by Nanjing warp weft chemical Co.Ltd; the EVA resin is a DuPont EVA resin sold by Jiangsu Yinlun Special plastics GmbH; the glass raw material is purchased from Shenzhen Chenglong glass Co.

Examples 1 to 5

The following description will be given by taking example 1 as an example.

Example 1

The intelligent dynamic dimming film in example 1 was prepared according to the following steps:

(1) the porous glass beads prepared in preparation example 1 and lithium hydroxide were uniformly mixed in a crucible and heated at 260 ℃ for 12 hours to obtain a mixture 1.

(2) Dissolving nano tungsten trioxide, a conductive assistant, a silane coupling agent and the cooled mixture 1 in silica sol, heating for 2 hours at 50 ℃ and continuously stirring to obtain a mixture 2;

(3) and after the mixture 2 is cooled, spreading the mixture 2 on a flat metal plate coated with polytetrafluoroethylene, and then placing the metal plate under the vacuum degree of 150pa until free water in the mixture 2 is completely evaporated, thus obtaining the intelligent dynamic dimming film.

The intelligent dynamic dimming glass is prepared according to the following steps:

treating the glass raw material: cutting, polishing and cleaning a large glass raw material to obtain a first glass layer and a second glass layer;

assembling intelligent dynamic dimming glass:

(1) processing EVA resin into an EVA adhesive film in a casting machine;

(2) and placing two layers of EVA (ethylene vinyl acetate) adhesive films between the first glass layer and the second glass layer, placing an intelligent dynamic dimming film between the two layers of EVA adhesive films, carrying out hot-pressing treatment to obtain the intelligent dynamic dimming glass, and measuring to obtain the thickness of 12 mm.

As shown in Table 3, examples 1 to 5 differ mainly in the ratio of raw materials

TABLE 3

Example 7

This example is different from example 6 in that the porous glass beads prepared in preparation example 2 were selected as the porous glass beads.

Example 8

This example is different from example 7 in that the porous glass beads prepared in preparation example 3 were selected as the porous glass beads.

Example 9

This example is different from example 8 in that the porous glass beads prepared in preparation example 4 were selected as the porous glass beads.

Example 10

This example is different from example 9 in that the porous glass beads prepared in preparation example 5 were selected as the porous glass beads.

Example 11

This example is different from example 10 in that the porous glass beads prepared in preparation example 6 were selected as the porous glass beads.

Example 12

The difference between this embodiment and embodiment 9 is that the formula of the intelligent dynamic dimming film further includes 2kg of an activator, and the activator is sodium persulfate.

Example 13

This example is different from example 12 in that sodium persulfate was added in an amount of 4 kg.

Example 14

This example is different from example 13 in that sodium persulfate was added in an amount of 6 kg.

Example 15

This example is different from example 14 in that sodium persulfate was added in an amount of 8 kg.

Example 16

This example differs from example 14 in that the activator is trimethylchlorosilane.

Example 17

The difference between this example and example 3 is that the formula of the intelligent dynamic dimming film further includes 18kg of microcrystalline cellulose, the average degree of polymerization of the microcrystalline cellulose is 120, and the microcrystalline cellulose is added to the silica sol in the step (2) of preparing the intelligent dynamic dimming film.

Example 18

This example is different from example 17 in that the amount of microcrystalline cellulose added was 20 kg.

Example 19

This example is different from example 18 in that the amount of microcrystalline cellulose added was 22 kg.

Example 20

This example is different from example 19 in that the amount of microcrystalline cellulose added was 24 kg.

Example 21

This example is different from example 19 in that the microcrystalline cellulose has an average degree of polymerization of 140.

Example 22

This example is different from example 21 in that the microcrystalline cellulose has an average degree of polymerization of 160.

Example 23

This example is different from example 22 in that the microcrystalline cellulose has an average degree of polymerization of 180.

Example 24

This example is different from example 23 in that the microcrystalline cellulose has an average degree of polymerization of 100.

Example 25

This example is different from example 24 in that the microcrystalline cellulose has an average degree of polymerization of 200.

Comparative example

Comparative example 1

The electro-dimming glass is prepared according to the preparation method of Chinese patent publication No. CN 103365017B.

Comparative example 2

This comparative example differs from example 3 in that a silane coupling agent is not included.

Performance detection test method

The visible light transmittance is used for representing the discoloration regulating range, and the detection method of the visible light transmittance refers to GB/T2680-1994-determination of visible light transmittance of architectural glass, ultraviolet light transmittance and related window glass parameters. After the detection is finished, calculating the difference value between the initial visible light transmittance and the minimum visible light transmittance, wherein the result is the color change adjusting range of the dimming glass; then, energization was repeated 1000 times for each group of light control glasses, and the difference between the initial visible light transmittance and the minimum visible light transmittance was calculated again, and the discoloration adjustment range at the time of initial detection, the discoloration adjustment range after repeated energization for 1000 times, and the amount of decrease in the discoloration adjustment range are shown in table 4.

The film-forming property is characterized by the viscosity of the silica sol, the viscosity detection method refers to GB/T10247-2008 viscosity measurement method, and the viscosity detection result is shown in Table 5.

TABLE 4

TABLE 5

Sample(s)	viscosity/(mPa. S)
		Example 3	7.2
Example 17	10.3
		Example 18	11.4
Example 19	12.8
		Example 20	11.0
Example 21	13.2
		Example 22	14.5
Example 23	12.9
		Example 24	8.4
Example 25	8.2

Combining examples 1-5 and comparative example 1 and combining table 4, it can be seen that the discoloration adjustment ranges of examples 1-5 are all larger than comparative example 1, and after 1000 times of cyclic energization, the discoloration adjustment ranges of examples 1-5 are reduced far less than comparative example 1, indicating that the dimming glasses of examples 1-5 are easier to maintain the discoloration adjustment ranges. In examples 1 to 5, the discoloration adjustment range of example 3 was the largest, and the decrease in the discoloration adjustment range was the lowest.

When example 3 and comparative example 2 were combined and table 4 was combined, it was found that the discoloration control range of the light control glass was significantly reduced without adding the coupling agent, but the decrease in the discoloration control range was also small after 1000 times of energization.

Combining example 3 and example 6 and combining table 4, it can be seen that the color-change adjustment range of example 6 is larger and the amount of decrease in the color-change adjustment range is consistent with example 3.

As can be seen by combining examples 6-11 with Table 4, example 9 has a larger color change adjustment range in examples 6-11. Although the amount of decrease in the discoloration-adjustment range in examples 7 to 10 was larger than that in example 6, the discoloration-adjustment range in examples 7 to 10 was still larger than that in example 6 after 1000 times of energization because the initial discoloration-adjustment range in examples 7 to 10 was larger. It can be seen from the combination of example 6 and example 11 that the discoloration adjustment range of the privacy glass is relatively small when the average porosity of the porous glass beads is outside the range of 45% to 55%.

As can be seen from example 9, examples 12 to 15, and table 4, the discoloration adjustment ranges before and after 1000 times of energization were large in example 14. It can be seen from the combination of example 14 and example 16 and from Table 4 that the trimethylchlorosilane used in example 16 has a better effect on the discoloration-control range.

As can be seen from examples 3 and 17 to 20 in combination with table 5, the silica sol in example 19 has a high viscosity, which indicates that the addition of microcrystalline cellulose of 22kg is more advantageous for forming the intelligent dynamic dimming film.

It can be seen from the combination of example 19 and examples 21-23 and from table 5 that the viscosity of the silica sol in example 22 is relatively high, which means that the average degree of polymerization of microcrystalline cellulose is 160, which is more beneficial for the formation of the intelligent dynamic light-adjusting film, and from examples 24-25, the viscosity of the silica sol is relatively low when the average degree of polymerization of microcrystalline cellulose is out of the range of 120-180, which is not beneficial for the formation of the intelligent dynamic light-adjusting film.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.