阅读说明：本技术 一种氧化镁氮化硼复合微球的制备方法 (Preparation method of magnesium oxide and boron nitride composite microspheres ) 是由 陈煌 尹志坚 李海静 肖展业 于 2021-09-16 设计创作，主要内容包括：本发明涉及一种氧化镁氮化硼复合微球的制备方法,以氧化镁粉体和氮化硼粉体为原料制备浆料,依次经过造粒、排胶处理和煅烧后,得到氧化镁氮化硼复合微球。本发明制备的氧化镁氮化硼复合微球结构致密,机械强度好,球形度高,可达96％以上,兼具很好的流动性,可实现在导热体系中高填充,同时大大降低氮化硼的用量,可节约导热粉体综合成本60％以上。本发明以碳酸钙-氧化钇为烧结助剂,有效地促进了氮化硼晶体生长并呈现连续的架桥搭接方式,从而使整个氧化镁氮化硼复合微球导热粉表现出热传导各向同性。整个工艺简单,在制备过程中不使用危险化学品,不产生“三废”,对环境友好,适合大规模工业化推广,具有良好的经济效益和应用前景。(The invention relates to a preparation method of magnesium oxide boron nitride composite microspheres, which comprises the steps of preparing slurry by using magnesium oxide powder and boron nitride powder as raw materials, and carrying out granulation, degumming treatment and calcination in sequence to obtain the magnesium oxide boron nitride composite microspheres. The magnesium oxide boron nitride composite microsphere prepared by the invention has the advantages of compact structure, good mechanical strength, high sphericity which can reach more than 96%, good fluidity, realization of high filling in a heat conduction system, great reduction of the using amount of boron nitride, and saving of the comprehensive cost of heat conduction powder by more than 60%. The invention takes calcium carbonate-yttrium oxide as a sintering aid, effectively promotes the growth of boron nitride crystals and presents a continuous bridging and lapping mode, thereby enabling the whole magnesium oxide-boron nitride composite microsphere heat-conducting powder to present isotropic heat conduction. The whole process is simple, no dangerous chemicals are used in the preparation process, no three wastes are generated, the environment is protected, the method is suitable for large-scale industrial popularization, and the method has good economic benefit and application prospect.)

1. A preparation method of magnesium oxide and boron nitride composite microspheres is characterized by comprising the following steps:

(1) preparing slurry by using magnesium oxide powder and boron nitride powder as raw materials, and granulating to obtain composite microspheres;

(2) carrying out degumming treatment on the composite microspheres obtained in the step (1);

(3) and (3) calcining the composite microspheres treated in the step (2) to obtain the magnesium oxide boron nitride composite microspheres.

2. The method for preparing the magnesium oxide boron nitride composite microspheres according to claim 1, wherein the specific method for preparing the slurry in the step 1 is as follows: mixing magnesium oxide powder, calcium carbonate powder and yttrium oxide powder, adding polyvinyl alcohol solution and water, mixing and stirring, then adding boron nitride powder, and stirring to obtain slurry.

3. The method for preparing magnesium oxide boron nitride composite microspheres according to claim 2, wherein the mass ratio of the magnesium oxide powder to the calcium carbonate powder to the yttrium oxide powder to the polyvinyl alcohol solution to the water is 1 (0.02-0.05) to 0.01-0.02 to 0.05-0.15 to 1-1.2.

4. The preparation method of the magnesium oxide boron nitride composite microspheres according to claim 2, wherein the mass ratio of the magnesium oxide powder to the boron nitride powder is 1 (0.1-0.6).

5. The method for preparing magnesium oxide boron nitride composite microspheres according to claim 2, wherein the concentration of the polyvinyl alcohol solution is 5-15 wt%.

6. The method for preparing magnesium oxide boron nitride composite microspheres according to claim 1, wherein the step (1) is performed by spray drying at 180-300 ℃.

7. The preparation method of the magnesium oxide boron nitride composite microspheres according to claim 1, wherein the degumming treatment process in the step (2) is as follows: and (2) respectively carrying out heating and heat preservation treatment in the first stage, heating and heat preservation treatment in the second stage, heating and heat preservation treatment in the third stage and heating and heat preservation treatment in the fourth stage on the composite microspheres obtained in the step (1).

8. The preparation method of the magnesium oxide boron nitride composite microspheres according to claim 7, wherein the first-stage heating and heat-preserving treatment comprises: heating the composite microspheres from room temperature to the temperature of 220 ℃ and 250 ℃ at the speed of 8-10 ℃/min, and preserving the heat for 2-3 h;

the second stage of heating and heat preservation treatment comprises the following steps: heating to 420-460 ℃ at the speed of 10-15 ℃/min and preserving the heat for 1-3 h;

the third-stage heating and heat preservation treatment comprises the following steps: heating to 610-650 ℃ at the speed of 4-8 ℃/min and preserving the heat for 4-6 h;

the fourth stage comprises the following steps: heating to 750 ℃ and 850 ℃ and keeping the temperature for 1-6 h.

9. The method for preparing magnesium oxide boron nitride composite microspheres according to claim 1, wherein the calcination temperature in step (3) is 1400-1900 ℃.

10. The method for preparing magnesium oxide boron nitride composite microspheres according to claim 1, wherein the method comprises the following steps:

(1) mixing and stirring magnesium oxide powder, calcium carbonate powder, yttrium oxide powder, 5-15 wt% polyvinyl alcohol solution and water uniformly according to the mass ratio of (0.02-0.05) to (0.01-0.02) to (0.05-0.15) to (1-1.2), then adding boron nitride powder with the mass of 0.1-0.6 time of that of the magnesium oxide powder, stirring uniformly to obtain slurry, and granulating the slurry at 300 ℃ by using a spray drying method to obtain composite microspheres;

(2) carrying out degumming treatment on the composite microspheres obtained in the step (1), wherein the specific process comprises the following steps: the composite microspheres are heated from room temperature to 250 ℃ for 2-3h at the rate of 8-10 ℃/min, then heated to 460 ℃ for 1-3h at the rate of 10-15 ℃/min, then heated to 650 ℃ for 4-6h at the rate of 4-8 ℃/min, and finally heated to 850 ℃ for 1-6h at the rate of 750℃.

(3) And (3) calcining the composite microspheres treated in the step (2) at the temperature of 1400 ℃ and 1900 ℃ to obtain the magnesium oxide boron nitride composite microspheres.

Technical Field

The invention belongs to the field of multifunctional ceramic powder, and relates to a preparation method of magnesium oxide and boron nitride composite microspheres, which is mainly applied to the fields of heat-conducting fillers and thermal spraying coatings in the electronic industry.

Background

With the coming of the 5G era, the application of the 5G new technology can promote the rapid promotion of the requirements of heat conduction materials and devices. While the wide use of high-performance communication equipment, computers, smart phones, automobiles and other terminal products has driven the rapid expansion of heat-conducting devices and related industrial applications, electronic components have become increasingly miniaturized and integrated, thereby placing increasing demands on the heat dissipation performance of the equipment. The development trend of middle-high-end heat-conducting insulating materials is gradually developed due to high heat conductivity, low specific gravity, low dielectric constant, high temperature resistance and high product design degree. Hexagonal boron nitride is gradually the best choice for heat-conducting fillers due to its unique electrical insulation properties, excellent thermal and chemical stability, ultra-low dielectric constant and thermal expansion coefficient.

At present, spherical alumina powder is mainly used as an insulating and heat-conducting filler in the electronic heat dissipation industry, and the traditional spherical alumina filler has good insulating property and fluidity and can be densely filled in gaps, but the thermal conductivity coefficient of alumina is low (30 wm)^-1K^-1) High density (3.9 g/cm)³) And high hardness. Thermal conductivity of boron nitride (125 wm)^-1K^-1) Compared with alumina, boron nitride is hexagonal and flaky, the density is light, the viscosity of the system is obviously increased after a large amount of boron nitride is filled, more gaps are generated as fillers, and the excellent heat-conducting property of the boron nitride cannot be fully exerted. Secondly, the structure of the hexagonal boron nitride is similar to that of graphite, and the hexagonal boron nitride has a hexagonal layered structure and anisotropic heat conduction property, and is self-ownedThe structural features make it easy to create tropism in the system application and difficult to achieve high filling. In addition, compared with alumina, the cost of the raw material of boron nitride is much higher, and the cost is continuously and greatly increased if the boron nitride is prepared into micron-sized spherical boron nitride powder, which greatly limits the popularization of the application of the boron nitride.

Disclosure of Invention

In view of the problems in the prior art, the invention discloses a preparation process of a novel magnesium oxide boron nitride composite microsphere, which is prepared by mixing hexagonal boron nitride and magnesium oxide (the density is 3.58 g/cm) which is a cheaper heat conduction material³Thermal conductivity coefficient of 36wm^{- 1}K^-1) The composite material is compounded, so that the using amount of boron nitride is reduced, the cost is saved, the problems of thermal conductivity anisotropy and low filling amount of hexagonal flaky boron nitride can be effectively solved, and the composite material has good economic benefit and application prospect.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of magnesium oxide boron nitride composite microspheres, which comprises the following steps:

(1) preparing slurry by using magnesium oxide powder and boron nitride powder as raw materials, and granulating to obtain composite microspheres;

(2) carrying out degumming treatment on the composite microspheres obtained in the step (1);

(3) and (3) calcining the composite microspheres treated in the step (2) to obtain the magnesium oxide boron nitride composite microspheres.

The invention utilizes the methods of slurry preparation, granulation, binder removal and high-temperature calcination to compound magnesium oxide and boron nitride to obtain the compact magnesium oxide boron nitride composite microsphere, which has compact structure, the median particle size distribution of 30-200 microns and good mechanical strength.

The boron nitride material adopted by the invention is preferably hexagonal boron nitride.

The specific method for preparing the slurry in the step 1 of the invention comprises the following steps: mixing magnesium oxide powder, calcium carbonate powder and yttrium oxide powder, adding polyvinyl alcohol solution and water, mixing and stirring, then adding boron nitride powder, and stirring to obtain the high-solid-phase low-viscosity slurry.

In the invention, a certain amount of calcium carbonate powder and yttrium oxide powder are added as sintering aids in the process of preparing the slurry, so that the growth of hexagonal boron nitride crystals can be effectively promoted and a continuous bridging and lapping mode is presented, and the whole magnesium oxide boron nitride composite microsphere heat-conducting powder presents isotropic heat conduction. In addition, the addition of the calcium carbonate and the yttrium oxide can be beneficial to forming composite microspheres with uniform sizes in the spray drying granulation stage, and the spheroidization degree of the microspheres is increased.

The mass ratio of the magnesium oxide powder, the calcium carbonate powder, the yttrium oxide powder, the polyvinyl alcohol solution and the water is 1 (0.02-0.05): (0.01-0.02): (0.05-0.15): 1-1.2.

The mass ratio of the magnesium oxide powder to the boron nitride powder is 1 (0.1-0.6). The specific proportion can be adjusted according to actual requirements.

The concentration of the polyvinyl alcohol solution in the invention is 5-15 wt%.

In the invention, the granulation is carried out by adopting a spray drying method in the step (1), and the temperature of the spray drying is 180-300 ℃.

The process for the glue discharging treatment in the step (2) comprises the following steps: and (2) respectively carrying out heating and heat preservation treatment in the first stage, heating and heat preservation treatment in the second stage, heating and heat preservation treatment in the third stage and heating and heat preservation treatment in the fourth stage on the composite microspheres obtained in the step (1).

The first stage of the temperature rise and heat preservation treatment comprises the following steps: heating the composite microspheres from room temperature to the temperature of 220 ℃ and 250 ℃ at the speed of 8-10 ℃/min, and preserving the heat for 2-3 h;

the second stage of heating and heat preservation treatment comprises the following steps: heating from 220 ℃ to 250 ℃ at the speed of 10-15 ℃/min to 420 ℃ to 460 ℃ and preserving the heat for 1-3 h;

the third-stage heating and heat preservation treatment comprises the following steps: raising the temperature from 420 ℃ to 460 ℃ at the rate of 4-8 ℃/min to 610 ℃ and 650 ℃ and preserving the temperature for 4-6 h;

the fourth stage comprises the following steps: finally, the temperature is raised to 750 ℃ and 850 ℃ and the temperature is kept for 1 to 6 hours.

The four stages are continuously carried out, namely after the temperature rise and the heat preservation in the first stage, the temperature rise and the heat preservation in the second stage are carried out on the basis, and the like.

The binder removal treatment is to decompose and oxidize excessive organic matters in the material, if the binder removal is insufficient, a certain amount of organic matter residues are left in the material, and during sintering, the organic matters are melted, decomposed and volatilized to cause defects such as deformation and cracks. Meanwhile, because the organic matter contains a large amount of carbon, when oxygen is insufficient to form a reducing atmosphere, the sintering quality is affected. Therefore, the organic substances in the green body need to be completely removed before the green body is fired, so as to ensure the requirements of the shape and quality of the product.

The conventional binder removal treatment at present is generally carried out at a certain temperature (about 100 ℃ C. and 400 ℃ C.) for a period of time, but organic matters cannot be completely removed, about 10-20% of the organic matters are usually left, and the quality of materials is influenced during subsequent calcination.

According to the invention, the continuous four-stage heating and heat preservation treatment is adopted in the degumming treatment process, and organic matters in the composite microspheres can be removed to the greatest extent by controlling the temperature gradient, the heating rate and the heat preservation time in different stages, and the removal rate of the organic matters can reach about 99.5%.

As a preferable scheme of the present invention, the preparation method of the magnesium oxide boron nitride composite microspheres comprises the following steps:

(1) mixing and stirring magnesium oxide powder, calcium carbonate powder, yttrium oxide powder, 5-15 wt% polyvinyl alcohol solution and water uniformly according to the mass ratio of (0.02-0.05) to (0.01-0.02) to (0.05-0.15) to (1-1.2), then adding boron nitride powder with the mass of 0.1-0.6 time of that of the magnesium oxide powder, stirring uniformly to obtain slurry, and granulating the slurry at 300 ℃ by using a spray drying method to obtain composite microspheres;

(2) carrying out degumming treatment on the composite microspheres obtained in the step (1), wherein the specific process comprises the following steps: the composite microspheres are heated from room temperature to 250 ℃ for 2-3h at the rate of 8-10 ℃/min, then heated to 460 ℃ for 1-3h at the rate of 10-15 ℃/min, then heated to 650 ℃ for 4-6h at the rate of 4-8 ℃/min, and finally heated to 850 ℃ for 1-6h at the rate of 750℃.

(3) And (3) calcining the composite microspheres treated in the step (2) at the temperature of 1400 ℃ and 1900 ℃ to obtain the magnesium oxide boron nitride composite microspheres.

The invention combines hexagonal boron nitride and magnesium oxide (density 3.58 g/cm) which is cheaper and heat-conducting material³Thermal conductivity coefficient of 36wm^-1K^-1) The composite material is compounded, so that the using amount of boron nitride is reduced, the cost is saved, the problems of thermal anisotropy and low filling amount of hexagonal flaky boron nitride are effectively solved, and the composite material is very suitable for being used as a thermal conductive filler.

The preparation method provided by the invention is also suitable for preparing the alumina, silicon oxide, silicon carbide and silicon nitride and boron nitride composite microspheres, and in order to prepare a finished product which can be finally sold, a method for controlling the particle size of the magnesia boron nitride microspheres by controlling the spray drying process conditions can be adopted, and the prepared magnesia boron nitride microspheres can be subjected to airflow classification according to the particle size requirement of the heat-conducting powder.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) the magnesium oxide boron nitride composite microsphere heat-conducting powder prepared by the invention has a compact structure, high sphericity which can reach over 96 percent, good fluidity and can realize high filling in a heat-conducting system.

(2) The magnesium oxide boron nitride composite microspheres prepared by the invention have good mechanical strength.

(3) The invention takes calcium carbonate-yttrium oxide as a sintering aid, effectively promotes the growth of hexagonal boron nitride crystals and presents a continuous bridging and lapping mode, thereby enabling the whole magnesium oxide boron nitride composite microsphere heat-conducting powder to present isotropic heat conduction.

(4) According to the invention, the hexagonal boron nitride is compounded with the magnesium oxide microspheres which are cheaper in heat conduction materials, so that the consumption of the boron nitride is greatly reduced, and the comprehensive cost of the heat conduction powder can be saved by more than 60%.

(5) The invention optimizes the degumming treatment process, adopts the continuous four-stage heating and heat preservation treatment in the degumming treatment process, and eliminates organic matters in the material to the maximum extent by controlling the temperature gradient, the heating rate and the heat preservation time of different stages, and the elimination rate can reach about 99.5 percent.

(6) The magnesium oxide and boron nitride composite microsphere heat-conducting powder has simple process and is suitable for industrial production. No dangerous chemicals are used in the preparation process, no three wastes are generated, and the method is environment-friendly and suitable for large-scale industrial popularization and application.

Detailed Description

To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:

example 1

The embodiment provides a preparation method of magnesium oxide boron nitride composite microspheres, which comprises the following process steps:

the first step is as follows: uniformly mixing 800g of magnesium oxide powder, 30g of calcium carbonate powder, 8g of yttrium oxide powder, 10 wt% of PVA (polyvinyl alcohol) aqueous solution and 1000g of ultrapure water to prepare slurry, and stirring at high speed for 30 min;

the second step is that: adding 240g of boron nitride powder into the slurry mixed in the first step, and continuously stirring at a high speed in the adding process;

the third step: granulating the slurry obtained in the step (1) at 220 ℃ by using a spray drying process to form composite microspheres with median particle size ranging from 30 to 200 microns;

the fourth step: performing gel discharging treatment on the composite microspheres obtained by spray drying in the third step, wherein the specific gel discharging process comprises the following steps: heating from room temperature to 230 ℃ at the speed of 9 ℃/min and preserving heat for 2.5 h; heating from 230 ℃ to 450 ℃ at the speed of 12 ℃/min and preserving heat for 2 h; heating from 450 ℃ to 650 ℃ at the speed of 6 ℃/min and preserving heat for 5 h; finally, the temperature is raised to 800 ℃ and the temperature is kept for 4 hours, and the removal rate of organic matters is 99.7 percent;

the fifth step: and (3) calcining the composite microspheres obtained in the fourth step at 1500 ℃ for 2 hours to obtain the magnesium oxide boron nitride composite microsphere heat-conducting powder with a compact structure, wherein the spheroidization rate is up to 97%, but the hexagonal boron nitride sheets do not have obvious crystal growth.

Example 2

The preparation process of this example is substantially the same as that of example 1, except that the high-temperature calcination temperature is increased to 1850 ℃ to obtain the magnesium oxide boron nitride composite microsphere heat-conducting powder with a compact structure, the spheroidization rate is as high as 97%, the hexagonal boron nitride sheet body has crystal growth, and the crystal shape becomes more complete.

Example 3

The preparation method of the magnesium oxide boron nitride composite microspheres comprises the following process steps:

the first step is as follows: uniformly mixing 1000g of magnesium oxide powder, 35g of calcium carbonate powder, 10g of yttrium oxide powder, 10 wt% of PVA (polyvinyl alcohol) aqueous solution and 1000g of ultrapure water to prepare slurry; stirring at high speed for 30 min;

the second step is that: adding 300g of boron nitride powder into the slurry mixed in the first step, and continuously stirring at a high speed in the adding process;

the third step: granulating the slurry obtained in the step (1) at 220 ℃ by using a spray drying process to form composite microspheres with median particle size ranging from 30 to 200 microns;

the fourth step: performing gel discharging treatment on the composite microspheres obtained by spray drying in the third step, wherein the specific gel discharging process comprises the following steps: heating from room temperature to 220 ℃ at the speed of 8 ℃/min and preserving heat for 3 h; heating from 220 ℃ to 420 ℃ at the speed of 10 ℃/min and preserving heat for 3 h; heating from 420 ℃ to 610 ℃ at the speed of 4 ℃/min and preserving heat for 6 h; finally, the temperature is raised to 750 ℃ and the temperature is kept for 6 hours, and the removal rate of organic matters is 99.5 percent;

the fifth step: and (3) calcining the composite microspheres obtained in the fourth step at 1800 ℃ for 2 hours to obtain the magnesium oxide boron nitride composite microsphere heat-conducting powder with a compact structure, wherein the spheroidization rate is up to 97%. By improving the concentration of the slurry and the proportion of the sintering aid, the crystal form of the hexagonal flaky boron nitride is complete, and the structure of the magnesium oxide boron nitride composite microsphere becomes more compact.

Example 4

The preparation method of the magnesium oxide boron nitride composite microspheres comprises the following process steps:

the first step is as follows: uniformly mixing 1000g of magnesium oxide powder, 35g of calcium carbonate powder, 10g of yttrium oxide powder, 10 wt% of PVA (polyvinyl alcohol) aqueous solution and 1000g of ultrapure water to prepare slurry; stirring at high speed for 30 min;

the second step is that: adding 300g of boron nitride powder into the slurry mixed in the first step, adding 50g of second small-particle-size boron nitride powder serving as a raw material for flaky growth, and continuously stirring at a high speed in the adding process;

the third step: granulating the slurry obtained in the step (1) at 250 ℃ by using a spray drying process to form composite microspheres with median particle size of 30-200 microns;

the fourth step: performing gel discharging treatment on the composite microspheres obtained by spray drying in the third step, wherein the specific gel discharging process comprises the following steps: heating from room temperature to 250 ℃ at the speed of 10 ℃/min and preserving heat for 2 h; heating from 250 ℃ to 460 ℃ at the speed of 15 ℃/min and preserving heat for 1 h; heating from 460 ℃ to 650 ℃ at the speed of 8 ℃/min and preserving heat for 4 h; finally, the temperature is raised to 850 ℃ and the temperature is kept for 1.5h, and the removal rate of organic matters is 99.7 percent;

the fifth step: and (3) calcining the composite microspheres obtained in the fourth step at 1900 ℃ for 2 hours to obtain the magnesium oxide boron nitride composite microsphere heat-conducting powder with a compact structure, wherein the spheroidization rate is up to 98%. By further increasing the calcination temperature, the crystal form of the hexagonal flaky boron nitride is more complete, the small-particle-size boron nitride is fused and disappears by the large-particle-size particles, and meanwhile, the thickness of the boron nitride flake in the microsphere is obviously thickened.

Comparative example 1

This comparative example is essentially the same as example 4 except that calcium carbonate powder and yttrium oxide powder were not added at the stage of preparing the slurry, i.e., no sintering aid was added. The spheroidization rate of the obtained magnesium oxide boron nitride composite microspheres is 75 percent.

Comparative example 2

The comparative example is basically the same as the preparation process of example 4, and is different in that only one temperature rising and heat preservation stage is adopted in the degumming process, namely the temperature of the spray-dried composite microspheres is raised from room temperature to 250 ℃ and is preserved for 8.5 hours, the removal rate of organic matters after degumming treatment is 81.3%, and cracks appear in partial regions of the obtained magnesium oxide boron nitride composite microspheres.

Comparative example 3

The comparative example is basically the same as the preparation process of example 4, and is different in that only one temperature rise and preservation stage is adopted in the degumming process, namely the temperature of the spray-dried composite microspheres is raised from room temperature to 460 ℃ for preservation for 8.5 hours, the removal rate of organic matters after degumming treatment is 85.7%, the obtained magnesium oxide boron nitride composite microspheres are non-uniform in spheres, and small cracks are generated locally.

Comparative example 4

The comparative example is basically the same as the preparation process of example 4, and is different in that only one temperature rise and preservation stage is adopted in the degumming process, namely the temperature of the spray-dried composite microspheres is raised from room temperature to 650 ℃ for preservation for 8.5 hours, the removal rate of organic matters after degumming treatment is 86.9%, the obtained magnesium oxide boron nitride composite microspheres are uneven in sphere, and large pits are generated in partial areas.

Comparative example 5

The comparative example is basically the same as the preparation process of the example 4, and is different in that only one temperature rise and preservation stage is adopted in the degumming process, namely the temperature of the spray-dried composite microspheres is raised from room temperature to 850 ℃ for preservation for 8.5 hours, the organic matter removal rate after degumming treatment is 92.0%, the obtained magnesium oxide boron nitride composite microsphere is uneven in sphere and generates a certain deformation integrally.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.