阅读说明：本技术 一种纤维网状氧化镁薄膜及其制备方法与应用 (Fiber mesh-shaped magnesium oxide film and preparation method and application thereof ) 是由 张波 李武 李丽娟 董亚萍 梁建 于 2021-07-23 设计创作，主要内容包括：本发明公开了一种纤维网状氧化镁薄膜及其制备方法与应用。所述制备方法包括：至少使作为阴极的金属或单晶硅、阳极与电解液共同构建电化学反应体系,所述电解液包括包含镁离子和添加剂的水溶液,所述添加剂包括黄原胶以及葡萄糖或其衍生物的组合；使所述电化学反应体系通电进行电解,从而在所述阴极表面沉积形成纤维网状氢氧化镁前驱体薄膜,再进行高温热处理,获得纤维网状氧化镁薄膜。本发明制得的氧化镁薄膜具有更高的比表面积,其富有规律性的纤维网状结构有利于提升薄膜的缓冲性能,方便各种功能材料在薄膜表面的负载和金属元素的掺杂；同时可进一步稳固氧化镁薄膜作为中间缓冲层和介质保护层在硅基复合材料和等离子体显示器等领域的应用。(The invention discloses a fiber mesh magnesium oxide film and a preparation method and application thereof. The preparation method comprises the following steps: at least making metal or monocrystalline silicon as a cathode, an anode and an electrolyte jointly construct an electrochemical reaction system, wherein the electrolyte comprises an aqueous solution containing magnesium ions and an additive, and the additive comprises xanthan gum and a combination of glucose or a derivative thereof; electrifying the electrochemical reaction system for electrolysis, depositing a fiber mesh magnesium hydroxide precursor film on the surface of the cathode, and performing high-temperature heat treatment to obtain the fiber mesh magnesium oxide film. The magnesium oxide film prepared by the method has higher specific surface area, and the rich regular fiber net structure of the magnesium oxide film is beneficial to improving the buffer performance of the film, and is convenient for loading various functional materials on the surface of the film and doping metal elements; meanwhile, the magnesium oxide film can be further stabilized to be used as an intermediate buffer layer and a dielectric protective layer in the fields of silicon-based composite materials, plasma displays and the like.)

1. A preparation method of a fiber mesh magnesium oxide film is characterized by comprising the following steps:

at least enabling metal or monocrystalline silicon as a cathode, an anode and an electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises an aqueous solution containing magnesium ions and an additive, and the additive comprises xanthan gum and glucose or a combination of derivatives thereof; electrifying the electrochemical reaction system for electrolysis, and depositing and forming a fiber mesh-shaped magnesium hydroxide precursor film on the surface of the cathode, wherein the electrode potential of the cathode is below-1.8V;

and carrying out high-temperature heat treatment on the fiber mesh-shaped magnesium hydroxide precursor film to obtain the fiber mesh-shaped magnesium oxide film.

2. The method of claim 1, wherein: the glucose derivative comprises gluconic acid and/or gluconate, preferably, the gluconate comprises potassium gluconate and/or sodium gluconate.

3. The method of claim 1, wherein: the concentration of glucose or derivatives thereof in the electrolyte is 0.1 g/L-50 g/L; and/or the concentration of the xanthan gum in the electrolyte is 0.05 g/L-1 g/L.

4. The method of claim 1, wherein: the magnesium ions are derived from magnesium salts, and the magnesium salts comprise any one or combination of more than two of magnesium chloride, magnesium nitrate and magnesium sulfate; and/or the concentration of magnesium ions in the electrolyte is 0.01-5 mol/L.

5. The method of claim 1, wherein: the electrochemical reaction system is a double-electrode or three-electrode system, preferably, the electrochemical reaction system further comprises a reference electrode, and the reference electrode is an Ag/AgCl electrode.

6. The method of claim 5, wherein: during the electrolysis, the electrode potential of the cathode is-5.0V to-1.8V relative to the reference electrode, the electrolysis time is 1min to 60min, and the temperature of the electrolyte is 5 ℃ to 70 ℃.

7. The method of claim 1, wherein: the temperature of the high-temperature heat treatment is above 340 ℃, preferably 340-1000 ℃, and the time of the high-temperature heat treatment is 1 min-12 h.

8. The method of claim 1, wherein: the cathode is monocrystalline silicon subjected to element doping treatment; and/or the anode comprises a lead plate, a platinum sheet or a titanium plate coated with a protective coating.

9. The fiber-network magnesium oxide film prepared by the method of any one of claims 1 to 8, which has a three-dimensional fiber network structure, and which contains fibrous magnesium hydroxide having a diameter of 10nm to 500nm, preferably, a thickness of 100nm to 100 μm.

10. The use of the fiber network magnesium oxide film of claim 9 as an intermediate buffer layer and a dielectric protective layer in the field of preparation of silicon-based composite materials or plasma displays.

Technical Field

The invention relates to a preparation method of a magnesium oxide film, in particular to a fiber mesh magnesium oxide film and a preparation method and application thereof, belonging to the technical field of magnesium oxide film preparation.

Background

The magnesium oxide film is an intermediate buffer layer and a medium protective layer material with excellent performance, and is often applied to the aspects of silicon-based composite materials, such as the epitaxial growth of high-temperature superconducting oxides and ferroelectrics on a silicon substrate, and the fields of plasma display screens and the like. In addition, the magnesium oxide film can also be used as an insulated gate of a transducer in the field of biosensors.

The magnesium oxide film prepared by the existing method has common appearance, is mostly compact layered or powdery and has a gap structure, has single function and structure, and cannot realize strong functional material loading capacity and improve multidimensional mechanical property. The magnesium oxide film has no porous structure supported by a multidimensional structure, the buffering performance of the material is poor, and the performance of the magnesium oxide film is difficult to further improve when the magnesium oxide film is used as an intermediate buffer layer and a dielectric protective layer in the fields of silicon-based composite materials, plasma displays and the like.

Disclosure of Invention

The invention mainly aims to provide a fiber mesh magnesium oxide film, a preparation method and application thereof, thereby overcoming the defects of the prior art.

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

the embodiment of the invention provides a preparation method of a fiber mesh magnesium oxide film, which comprises the following steps:

at least enabling metal or monocrystalline silicon as a cathode, an anode and an electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises an aqueous solution containing magnesium ions and an additive, and the additive comprises xanthan gum and glucose or a combination of derivatives thereof;

electrifying the electrochemical reaction system for electrolysis, and depositing and forming a fiber mesh-shaped magnesium hydroxide precursor film on the surface of the cathode, wherein the electrode potential of the cathode is below-1.8V;

and carrying out high-temperature heat treatment on the fiber mesh-shaped magnesium hydroxide precursor film to obtain the fiber mesh-shaped magnesium oxide film.

In some preferred embodiments, the concentration of glucose or a derivative thereof in the electrolyte is 0.1g/L to 50 g/L.

Further, the concentration of the xanthan gum in the electrolyte is 0.05 g/L-1 g/L.

Furthermore, the concentration of magnesium ions in the electrolyte is 0.01-5 mol/L.

In some preferred embodiments, during the electrolysis, the electrode potential of the cathode is-5.0V to-1.8V, the electrolysis time is 1min to 60min, and the temperature of the electrolyte is 5 ℃ to 70 ℃.

In some preferred embodiments, the temperature of the high-temperature heat treatment is above 340 ℃, and the time of the high-temperature heat treatment is 1 min-12 h.

The embodiment of the invention also provides the fiber mesh-shaped magnesium oxide film prepared by the method, and the fiber mesh-shaped magnesium oxide film has a three-dimensional fiber mesh structure.

The embodiment of the invention also provides application of the fiber mesh magnesium oxide film as an intermediate buffer layer and a dielectric protective layer in the field of preparation of silicon-based composite materials or plasma displays and the like.

Compared with the traditional preparation method of the magnesium oxide film, the preparation method of the magnesium oxide film with the special fiber mesh structure provided by the invention has the advantages that xanthan gum and glucose or derivatives thereof are added into electrolyte, and electrolysis is carried out under higher electrode potential, so that the prepared magnesium oxide film with the special fiber mesh structure has higher specific surface area than a common magnesium oxide film, and the fiber mesh structure with rich regularity is particularly beneficial to improving the buffer performance of the film, and is convenient for loading various functional materials on the surface of the film and doping metal elements; meanwhile, because rich gaps in the magnesium oxide film have high specific surface area and three-dimensional fibrous space structure, the internal buffering performance of the magnesium oxide film is enhanced, and the application of the magnesium oxide film as an intermediate buffering layer and a medium protective layer in the fields of silicon-based composite materials, plasma displays and the like can be further stabilized.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic view showing a flow of preparing a fiber network type magnesium oxide thin film according to an exemplary embodiment of the present invention;

FIG. 2 is a scanning electron micrograph of the fiber network magnesium oxide film obtained in example 1 of the present invention.

Detailed Description

In view of the defects in the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide a technical scheme of the present invention, which mainly provides an unreported preparation method of a magnesium oxide film with a special fiber mesh structure to prepare an unreported fiber mesh magnesium oxide film material, and the novel film material has a high specific surface area and a three-dimensional spatial structure, and is beneficial to improving the buffer performance of the film, and facilitating the loading of a functional material on the surface of the film and the doping of metal elements. In the main concept scheme of the invention, xanthan gum and glucose or derivatives thereof as additives and the higher electrode potential (calculated by Ag/AgCl electrode, minus 1.8V) of the cathode surface required for preparing the magnesium hydroxide precursor film with the fiber network structure are the necessary conditions for constructing the fiber network structure.

The technical solution, its implementation and principles, etc. will be further explained as follows.

One aspect of the embodiments of the present invention provides a method for preparing a fiber mesh magnesium oxide film, which includes:

at least enabling metal or monocrystalline silicon as a cathode, an anode and an electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises an aqueous solution containing magnesium ions and an additive, and the additive comprises xanthan gum and glucose or a combination of derivatives thereof;

electrifying the electrochemical reaction system for electrolysis, and depositing and forming a fiber mesh-shaped magnesium hydroxide precursor film on the surface of the cathode, wherein the electrode potential of the cathode is below-1.8V;

and carrying out high-temperature heat treatment on the fiber mesh-shaped magnesium hydroxide precursor film to obtain the fiber mesh-shaped magnesium oxide film.

In some preferred embodiments, the glucose derivative includes gluconic acid and/or gluconate, wherein the gluconate includes potassium gluconate, sodium gluconate, etc., but is not limited thereto.

In the electrolysis process, in order to ensure that the magnesium hydroxide precursor film generated on the surface of the cathode has a fiber mesh structure, an additive, mainly xanthan gum and one or more of glucose, gluconic acid or gluconate (such as sodium gluconate and potassium gluconate) is added into the electrolyte.

The action mechanism of adding xanthan gum is as follows: the xanthan gum is a microbial extracellular polysaccharide, and the inventor of the invention unexpectedly finds that the xanthan gum has good compatibility with magnesium salts and the like and is easy to generate a synergistic effect with the magnesium salts in the process of electrodeposition of the magnesium salts. Xanthan gum has a wide pH range, and the process for electrodepositing magnesium hydroxide involved in the present invention is actually an acid-making process, and the structure of xanthan gum can be kept stable under conditions where the pH is easily changed in a wide range. Meanwhile, the xanthan gum is also an effective thickening agent, the viscosity of the solution can be obviously improved by using a small amount of xanthan gum, the state of a diffusion layer on the surface of a cathode is changed by influencing the diffusion coefficient, the growth trend of a magnesium hydroxide deposition layer is changed by the long-chain steric hindrance effect and the characteristic adsorption on the surface of the generated magnesium hydroxide crystal, and a fiber mesh structure is formed.

Furthermore, although xanthan gum has a remarkable effect in the process of electrolyzing to construct the magnesium hydroxide deposition layer with a fiber mesh structure, xanthan gum is easy to agglomerate in the preparation process, and the formed tiny undissolved agglomerated particles can influence the shape and performance of the fiber mesh magnesium hydroxide deposition layer. Therefore, the inventor of the present invention has further added glucose and derivatives thereof to the electrolyte, and has surprisingly found that the addition of one or more of glucose, gluconic acid or gluconate can significantly promote the uniform dissolution of xanthan gum in water, thereby avoiding the occurrence of agglomeration. Meanwhile, the glucose, the gluconic acid or the gluconate can improve the current distribution uniformity on the surface of the cathode in the electrolytic process, so that the thickness and the structure of the prepared fiber mesh-shaped magnesium hydroxide deposition layer are more uniform.

In some preferred schemes, the xanthan gum is added into the electrolyte so that the concentration of the xanthan gum in the finally obtained electrolyte is 0.05 g/L-1 g/L.

In some preferred schemes, the invention adds one or more of glucose, gluconic acid or gluconate (such as potassium gluconate and sodium gluconate) and the like into the electrolyte, so that the concentration of the glucose or the derivative thereof in the finally obtained electrolyte is 0.1 g/L-50 g/L calculated by glucose acid radicals.

In some preferred embodiments, the magnesium ion is derived from a magnesium salt, i.e., the electrolyte comprises an aqueous solution of a magnesium salt, wherein the solute magnesium salt may include any one or a combination of two or more of magnesium chloride, magnesium nitrate, magnesium sulfate, and the like, but is not limited thereto.

Furthermore, the concentration of magnesium ions in the electrolyte is 0.01-5 mol/L.

In some preferred embodiments, the electrochemical reaction system is a two-electrode or three-electrode system.

Further, the electrochemical reaction system also comprises a reference electrode which is an Ag/AgCl electrode, but is not limited thereto.

In addition, the inventor proves through experiments that in the electrolytic system of the invention, higher electrode potential is also a necessary condition for preparing the fiber-network-shaped magnesium hydroxide deposition layer. The process of preparing the magnesium hydroxide by the electro-deposition is substantially water electrolysis, and the hydrogen evolution on the surface of a cathode and the enriched OH^-Can be used as precipitant and solventMg in liquid²⁺Reaction to form Mg (OH)₂. At higher electrode potential (the cathode surface is minus 1.8V relative to the saturated calomel electrode), OH is generated on the cathode surface^-The rate is greatly increased, and Mg (OH) on the surface of the cathode can be promoted₂The generation reaction is changed from chemical reaction to diffusion control, and the shape of the final product is directly influenced.

In some preferable schemes, during the electrolysis, the electrode potential of the cathode is-5.0V to-1.8V relative to the reference electrode, the electrolysis time is 1min to 60min, and the temperature of the electrolyte is 5 ℃ to 70 ℃.

In addition, the inventor of the present invention has proved through experiments that, on the basis of the above experiments, the fiber mesh-shaped magnesium hydroxide layer generated by electrodeposition is used as a precursor, the magnesium hydroxide layer is subjected to high-temperature treatment, when the temperature is higher than 340 ℃, the magnesium hydroxide can be dehydrated and converted into magnesium oxide, and meanwhile, the original fiber mesh structure is maintained, and finally, the preparation of the fiber mesh-shaped magnesium oxide film is completed.

In some preferable schemes, the temperature of the high-temperature heat treatment is 340-1000 ℃, and the time of the high-temperature heat treatment is 1 min-12 h.

That is to say, the preparation method of the magnesium oxide film with the special fiber net-shaped structure provided by the invention is that firstly, a magnesium hydroxide film precursor is prepared on the surface of metal or monocrystalline silicon by adopting an electrodeposition method, xanthan gum and one or more of gluconate such as glucose, gluconic acid, sodium gluconate and potassium gluconate are added in the process to ensure that the generated magnesium hydroxide film has the fiber net-shaped structure, and then the magnesium hydroxide precursor film is subjected to high-temperature treatment at 340-1000 ℃ to finally obtain the magnesium oxide film with the fiber net-shaped structure.

In some preferred embodiments, the cathode is monocrystalline silicon subjected to elemental doping treatment, i.e., the cathode used is a conductive metal substrate or monocrystalline silicon subjected to doping treatment.

Further, the anode includes a lead plate, a platinum sheet, a titanium plate coated with a protective coating, or the like, but is not limited thereto.

In some more specific embodiments, referring to fig. 1, the method for preparing the fiber-network magnesium oxide film specifically includes the following steps:

step 1, adopting a double-electrode or three-electrode system to carry out electrolysis, wherein the cathode is a conductive metal substrate or doped monocrystalline silicon, and the anode is a lead plate, a titanium plate with a protective coating covered on the surface, a platinum sheet or other inert metal products.

And 2, the electrolyte is a magnesium salt aqueous solution, the solute can be one or more of magnesium chloride, magnesium nitrate and magnesium sulfate, and the concentration of magnesium ions in the solution is between 0.01 and 5 mol/L.

Step 3, adding xanthan gum into the electrolyte, wherein the concentration of the xanthan gum is between 0.05g/L and 1 g/L; simultaneously adding one or more of glucose, gluconic acid or gluconate (such as potassium gluconate and sodium gluconate), wherein the concentration of the gluconate is 0.1 g/L-50 g/L calculated by the gluconate radical.

And 4, during electrolysis, the potential of the cathode electrode is between-5.0V and-1.8V (relative to an Ag/AgCl electrode), the electrolysis time is between 1min and 60min, the electrolysis temperature is between 5 ℃ and 70 ℃, and the fiber mesh-shaped magnesium hydroxide precursor film is obtained by electrodeposition on the surface of the cathode.

And 5, carrying out high-temperature heat treatment on the obtained magnesium hydroxide precursor film, wherein the treatment temperature is between 340 and 1000 ℃, and the treatment time is between 1min and 12 h. After heat treatment, the magnesium hydroxide is dehydrated to generate magnesium oxide, and finally the fiber mesh magnesium oxide film is formed.

Another aspect of an embodiment of the present invention also provides a fiber-network magnesium oxide film having a three-dimensional fiber network structure, prepared by the foregoing method.

Further, the fibrous magnesium hydroxide contained in the fiber-network magnesium oxide film has a diameter of 10nm to 500 nm. Further, the thickness of the fiber network magnesium oxide film is 100nm to 100 μm, and is not particularly limited.

Compared with the common magnesium oxide film, the magnesium oxide film with the special fiber net structure prepared by the invention has higher specific surface area, and the fiber net structure with rich regularity is particularly beneficial to the loading of various functional materials and the doping of metal elements. Meanwhile, due to rich gaps and a three-dimensional fibrous structure in the magnesium oxide film, the internal buffering performance of the magnesium oxide film is enhanced, and the application of the magnesium oxide film serving as an intermediate buffering layer and a medium protective layer in the fields of silicon-based composite materials, plasma displays and the like can be further stabilized.

The invention also provides application of the fiber mesh magnesium oxide film as an intermediate buffer layer and a dielectric protective layer in the field of preparation of silicon-based composite materials or plasma displays and the like.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in further detail below with reference to the accompanying drawings and several preferred embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying the specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The reagents used in the following examples were all of analytical purity.

Example 1

Conducting metal is used as a cathode, a lead plate is used as an anode, and a double-electrode system is adopted for electrolysis. The electrolyte is magnesium nitrate aqueous solution, wherein the concentration of magnesium ions is 0.5 mol/L. Adding xanthan gum and glucose into the electrolyte to ensure that the concentration of the xanthan gum in the electrolyte is 0.5g/L and the concentration of the glucose is 50 g/L. The potential of the cathode surface electrode is-2.4V relative to the Ag/AgCl electrode during electrolysis, the temperature of the electrolyte is 45 ℃, and the electrolysis time is 30 min. The obtained fiber-network magnesium hydroxide precursor film is subjected to high-temperature heat treatment at 340 ℃ for 12h to obtain a magnesium oxide film with good fiber-network shape, wherein the diameter of the fiber-network magnesium hydroxide is between 10nm and 500nm, and a scanning electron micrograph thereof is shown in FIG. 2.

Example 2

The monocrystalline silicon subjected to doping treatment is used as a cathode, a titanium plate covered with a protective coating on the surface is used as an anode, a three-electrode system is adopted for electrolysis, and the reference electrode is an Ag/AgCl electrode. The electrolyte is mixed aqueous solution of magnesium sulfate and magnesium chloride, wherein the total concentration of magnesium ions is 0.01 mol/L. Adding xanthan gum and gluconic acid into the electrolyte to ensure that the concentration of the xanthan gum in the electrolyte is 0.05g/L, and adding the gluconic acid to ensure that the concentration is 0.1g/L in terms of gluconate. The potential of the cathode surface electrode is-1.8V relative to the Ag/AgCl electrode during electrolysis, the temperature of the electrolyte is 5 ℃, and the electrolysis time is 60 min. The obtained fiber-network magnesium hydroxide precursor film is subjected to high-temperature heat treatment at 800 ℃ for 5 hours to obtain a magnesium oxide film with good fiber-network shape, and the scanning electron microscope photo of the magnesium oxide film is similar to that in FIG. 2.

Example 3

The conductive metal is used as a cathode, a platinum sheet is used as an anode, and a double-electrode system is adopted for electrolysis. The electrolyte is an aqueous solution of magnesium chloride, wherein the concentration of magnesium ions is 5 mol/L. Adding xanthan gum, sodium gluconate and potassium gluconate into the electrolyte to enable the concentration of the xanthan gum in the electrolyte to be 1g/L, and adding the sodium gluconate and the potassium gluconate to enable the concentration to be 15g/L by a gluconate radical. The potential of the cathode surface electrode is-5.0V relative to the Ag/AgCl electrode during electrolysis, the temperature of the electrolyte is 70 ℃, and the electrolysis time is 1 min. The obtained fiber-network magnesium hydroxide precursor film is subjected to high-temperature heat treatment at 1000 ℃ for 1min to obtain a magnesium oxide film with good fiber-network shape, and the scanning electron microscope photo of the magnesium oxide film is similar to that in FIG. 2.

Comparative example 1

This comparative example is substantially the same as example 1 except that: no xanthan gum and glucose were added to the electrolyte.

Finally, the magnesium hydroxide deposited on the surface of the electrode falls off in a large area, and a complete film layer is difficult to form.

Comparative example 2

This comparative example is substantially the same as example 1 except that: xanthan gum was added only to the electrolyte, no glucose was added. The results show that xanthan gum is difficult to dissolve uniformly in the absence of glucose, and is mostly present in solution as small particles. Finally, the magnesium hydroxide deposited on the surface of the electrode falls off in a large area, and a complete film layer is difficult to form.

Comparative example 3

This comparative example is substantially the same as example 1 except that: only glucose was added to the electrolyte, no xanthan gum was added.

Finally, the magnesium hydroxide deposited on the surface of the electrode falls off in a large area, and a complete film layer is difficult to form.

Comparative example 4

This comparative example is substantially the same as example 1 except that: the surface electrode potential of the cathode during electrolysis is-0.5V.

The magnesium hydroxide finally deposited on the surface of the electrode is of a sheet structure, and a fiber net structure does not exist.

Comparative example 5

This comparative example is substantially the same as example 1 except that: the temperature of the high-temperature heat treatment is lower than 340 ℃.

However, the results show that at temperatures below 340 ℃, magnesium hydroxide cannot be converted to magnesium oxide.

Comparative example 6

This comparative example is substantially the same as example 1 except that: the concentration range of xanthan gum is lower than 0.05g/L, or higher than 1 g/L.

The results show that the magnesium hydroxide film layer finally deposited on the surface of the electrode is flaky and not fiber net-shaped.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.