阅读说明：本技术 一种修复基体的碳氮化钛/氧化铝复合涂层的制备方法 (Preparation method of titanium carbonitride/aluminum oxide composite coating for repairing substrate ) 是由 游钱炳 熊计 郭智兴 杨天恩 霍云亮 于 2021-03-26 设计创作，主要内容包括：本发明公开了一种修复基体的碳氮化钛/氧化铝复合涂层及其制备方法,复合涂层沿基体表面向外依次为：TiN,MT-TiCN,细颗粒α-Al-(2)O-(3)表层,复合涂层的制备方法为：先将待处理基体表面抛光处理后清洗；然后将待处理基体烘干后进行涂层沉积,依次沉积涂层为TiN,MT-TiCN,α-Al-(2)O-(3),最后通过后处理降低涂层粗糙度即得复合涂层,与现有涂层相比,最内层TiN可以保证基体与涂层的结合力,第二层MT-TiCN硬度高,可作为耐磨层,同时对α-Al-(2)O-(3)涂层起到支撑作用,最外层细颗粒α-Al-(2)O-(3)硬度较高,且优异的耐高温氧化性作为隔热层,多层复合涂层协同作用,使得带有缺陷的硬质合金、陶瓷及金属陶瓷等样品使用性能提升200-300％,极大的节约成本,在高速车/铣削钢、不锈钢等领域具有广阔的应用前景。(The invention discloses a titanium carbonitride/alumina composite coating for repairing a substrate and a preparation method thereof, wherein the composite coating comprises the following components in sequence along the surface of the substrate: TiN, MT-TiCN, fine-grained alpha-Al 2 O 3 The preparation method of the surface layer and the composite coating comprises the following steps: firstly, polishing the surface of a substrate to be processed and then cleaning; then drying the substrate to be treated and depositing a coating, wherein the sequentially deposited coating is TiN, MT-TiCN and alpha-Al 2 O 3 Finally, the roughness of the coating is reduced through post-treatment to obtain the composite coating, and compared with the existing coating, the innermost TiN layer can ensureThe binding force between the substrate and the coating, the second MT-TiCN layer has high hardness, can be used as a wear-resistant layer and is opposite to alpha-Al 2 O 3 The coating plays a supporting role, and the outermost layer of fine particles of alpha-Al 2 O 3 The hardness is higher, the excellent high-temperature oxidation resistance is used as a heat insulation layer, and the multi-layer composite coating layer has synergistic effect, so that the service performance of samples such as hard alloy, ceramic and metal ceramic with defects is improved by 200-300%, the cost is greatly saved, and the method has wide application prospect in the fields of high-speed vehicle/milling steel, stainless steel and the like.)

1. The titanium carbonitride/aluminum oxide composite coating for repairing the substrate is characterized in that the composite coating sequentially comprises the following components along the surface of the substrate to be treated from outside: TiN, MT-TiCN, fine-grained alpha-Al₂O₃A surface layer.

2. A titanium carbonitride/alumina composite coating layer for repairing substrates according to claim 1 wherein the TiN coating thickness is 0.05 to 0.1 μm.

3. The titanium carbonitride/alumina composite coating for repairing a substrate according to claim 1 wherein the MT-TiCN coating has a thickness of 2 to 4 μm.

4. The titanium carbonitride/alumina composite coating layer for repairing a substrate according to claim 1 wherein the fine particles are α -Al₂O₃The coating thickness is 2-4 μm and the particle size is0.2-1.0μm。

5. A preparation method of a titanium carbonitride/aluminum oxide composite coating for repairing a substrate is characterized by comprising the following steps:

s1: firstly, polishing the surface of a substrate to be processed;

s2: washing the substrate obtained in S1 with a hot water bath;

s3: drying the substrate obtained in the step S2, and then putting the substrate into a coating furnace;

s4: the sequentially deposited coating is TiN, MT-TiCN and fine-grain alpha-Al₂O₃；

S5: and reducing the roughness of the coating through post-treatment to obtain the composite coating.

6. The method for preparing a titanium carbonitride/alumina composite coating layer for repairing a substrate according to claim 5, wherein the substrate to be treated in the step S1 is a WC-based cemented carbide substrate, ZrO, or the like₂Substrate, sialon substrate, Si₃N₄Substrate, TiCN substrate, Al₂O₃And a substrate, wherein in the step S1, polishing treatment is carried out by using a No. 1500 diamond grinding disc, so that the surface roughness Ra is 0.2 μm, and the cleaning mode in the step S2 is ultrasonic cleaning for 30 min.

7. The method as claimed in claim 5, wherein the TiN/alumina composite coating layer is deposited at S4 at a deposition temperature of 880-900 deg.C and a deposition pressure of 15-35KPa, and TiCl is used as the gas₄、H₂、N₂Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45-48 ℃, and the heat preservation time is 0.5-2 h.

8. The method as claimed in claim 5, wherein the deposition conditions of the MT-TiCN coating in S4 are 880-900 deg.C, 6-50 KPa, and gas is usedThe body is TiCl₄、H₂、N₂、CH₄Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45-48 ℃, and the heat preservation time is 4-8 h.

9. The method of claim 5, wherein the fine α -Al particles of S4 are selected from the group consisting of₂O₃The deposition conditions are deposition temperature of 1000-1010 ℃, deposition pressure of 6-20 KPa, and AlCl is used as the gas₃、H₂、CO₂Ar, wherein AlCl₃By H₂Carrying the mixture into a reaction furnace, and carrying AlCl₃The water temperature is 45-55 ℃, and the heat preservation time is 5-8 h.

10. The method of claim 5, wherein the post-treatment in S5 is brush or sand blasting, wherein the brush is made of SiC or bristles, the treatment time is 5-10S, the sand blasting is made by one or more of carborundum, silica sand and resin sand, the treatment time is 5-10S, the surface of the coating is sand blasted for a short time under the pressure of 2-4Bar, and the roughness of the surface of the treated coating is less than 0.5 um.

Technical Field

The invention relates to the field of preparation of multilayer composite coatings, in particular to a titanium carbonitride/aluminum oxide composite hard cutter ceramic coating prepared by a high-temperature chemical vapor deposition method, which is used for cutter coatings in the fields of high-speed turning/milling steel and stainless steel.

Background

Carburization, decarburization and high porosity are defects of cemented carbide articles, and their occurrence affects the mechanical and physical properties of the cemented carbide, so that the carburization defect must be eliminated in order to produce a good quality cemented carbide article. At present, a plurality of methods for eliminating the carburization defect of hard alloy products by adopting a molybdenum wire hydrogen sintering furnace are basically eliminated, the main method for eliminating the carburization defect of the hard alloy products at present is to finish carburization and back burning in a vacuum furnace by adopting a filling method, and the method has poor carburization elimination adaptability to large-size hard alloy products because a specific boat box is needed to load filling and alloy products, and cannot be suitable for the back burning of the large-size hard alloy products. Meanwhile, the filler method needs to use a screen to sort the alloy product and the decarburization filler after sintering is finished, so that the process is longer and the cost is higher. The presence of these defects, either through other process performance improvements or re-melting, would result in significant economic losses.

The hard coating is one of important surface engineering technologies, and with the continuous improvement of cutting quality and cutting efficiency, the simple cutter material is difficult to meet the cutting processing challenge. The coating of the tool surface greatly improves the cutting properties of the tool, while advances in modern manufacturing techniques place increasingly higher demands on the tool coating. The cutting tool bears great mechanical load and thermal load in the cutting process, and is easy to generate abrasion and wear damage, so that the service life of the cutting tool is sharply reduced. Therefore, it is very important to improve the surface properties of the cutting tool by modifying the surface of the cutting tool, and to improve the life of the cutting tool.

Chemical vapor deposition is classified into high temperature chemical vapor deposition (HT-CVD) and medium temperature chemical vapor deposition (MT-CVD). The HT-CVD deposition temperature is more than 900 ℃, and the main deposition types are single-layer or multi-layer composite coatings of metal carbide, nitride, oxide, boride, silicide and the like. The deposition temperature of MT-CVD is lower than 900 ℃, the MT-CVD is developed and matured in the middle of the 20 th century, the main purpose is to replace HT-CVD, because organic compounds containing C-N atomic groups are adopted during deposition, TiCN is prepared at a higher speed at a relatively lower temperature, MT-CVD has a denser tissue structure and smaller residual thermal stress compared with HT-CVD, and therefore the MT-CVD has better wear resistance and toughness, and simultaneously because of the lower temperature, a decarburized layer which has negative influence on a coated cutter is avoided, the adhesive strength is improved, the brittleness of the coated cutter is reduced, and the cutter is prevented from being broken in the cutting process. The MT-CVD method can also deposit coatings such as TiCrN, TiSiN and the like.

In the aspect of the kind of hard coating, with the rapid development of coating processes, coating equipment and coating materials, the coating is converted from the existing single compound and multi-compound, such as TiC, TiN, TiCN and the like, which cannot meet the harsh requirements of high-speed, high-efficiency and green cutting modes on the hard coating of the tool, and the hard coating is required to be further improved in various performances such as hardness, bonding force, high-temperature oxidation resistance and the like. To meet these requirements, the countries in the united states and europe have conducted a great deal of research on coating materials, processes, and equipment, and have achieved a lot of results and entered the market. In the aspect of CVD coating, various coatings are mainly combined to form composite coatings, such as early TiC/TiN, TiC/TiCN/TiN and the like, but with the continuous development of processing technology and material technology, higher requirements are put on various properties of the coating, such as hardness, toughness, wear resistance, high-temperature oxidation resistance and the like, so that Al-containing coating appears₂O₃Composite coatings of, e.g. TiCN/Al₂O₃、 TiCN/TiC/Al₂O₃、TiCN/Al₂O₃/TiN、TiCN/TiC/Al₂O₃/TiN、TiCN/Al₂O₃TiCN and the like, and the coatings are widely applied to the processing field of materials such as steel, stainless steel, cast iron and the like at present. In the process of high-speed turning/milling of easy-to-machine materials such as steel, stainless steel and the like, because the heat productivity is relatively low, the temperature of the blade is relatively low, and Al is contained₂O₃The excellent high-temperature oxidation resistance can not be reflected, the common TiN and TiCN coatings can play excellent oxidation resistance at low temperature, the effect is even better, and meanwhile, the Al is controlled₂O₃The stable nucleation and growth of the coating and the good bonding force are required to HCl and H₂S、CO₂And various reaction gases such as CO and the like are quantitatively controlled, so that the time consumption is long, the process is complex, and the process gas cost is high.

The invention carries out surface treatment on a defect sample by a special process, firstly repairs the defect, improves the mechanical property of a matrix, and then carries out coating, so that the property of the matrix is improved by 200-300%. The method has the advantages of simple process, low consumption and long service life, and is used for repairing high-speed turning/milling steel and stainless steel substrates.

Disclosure of Invention

In view of the above, the present invention provides a titanium carbonitride/alumina composite coating for repairing a substrate and a preparation method thereof, wherein the composite coating comprises, in order along a surface of the substrate: TiN, MT-TiCN, fine-grained alpha-Al₂O₃Compared with the existing coating, the surface layer has the advantages that the innermost TiN layer can ensure the binding force between the substrate and the coating, the second MT-TiCN layer has high hardness, can be used as a wear-resistant layer and is simultaneously resistant to alpha-Al₂O₃The coating plays a supporting role, and the outermost layer of fine particles of alpha-Al₂O₃The hardness is higher, the excellent high-temperature oxidation resistance is used as a heat insulation layer, and the multi-layer composite coating layer has synergistic effect, so that the service performance of samples such as hard alloy, ceramic and metal ceramic with defects is improved by 200-300%, the cost is greatly saved, and the method has wide application prospect in the fields of high-speed vehicle/milling steel, stainless steel and the like.

In order to achieve the purpose, the technical scheme is as follows:

titanium carbonitride/alumina for repairing matrixThe composite coating is characterized by comprising the following components in sequence along the surface of a substrate to be treated: TiN, MT-TiCN, fine-grained alpha-Al₂O₃A surface layer.

Further, the TiN coating thickness is 0.05-0.1 μm.

Further, the thickness of the MT-TiCN coating is 2-4 mu m.

Further, the fine particles of alpha-Al₂O₃The coating thickness is 2-4 μm and the particle size is 0.2-1.0. mu.m.

A preparation method of a titanium carbonitride/aluminum oxide composite coating for repairing a substrate is characterized by comprising the following steps:

s1: firstly, polishing the surface of a substrate to be processed;

s2: washing the substrate obtained in S1 with a hot water bath;

s3: drying the substrate obtained in the step S2, and then putting the substrate into a coating furnace;

s4: the sequentially deposited coating is TiN, MT-TiCN and fine-grain alpha-Al₂O₃；

S5: and reducing the roughness of the coating through post-treatment to obtain the composite coating.

Further, the substrate to be processed in the step S1 is a WC-based cemented carbide substrate, ZrO₂Substrate, sialon substrate, Si₃N₄Substrate, TiCN substrate, Al₂O₃And a substrate, wherein in the step S1, polishing treatment is carried out by using a No. 1500 diamond grinding disc, so that the surface roughness Ra is 0.2 μm, and the cleaning mode in the step S2 is ultrasonic cleaning for 30 min.

Further, the deposition conditions of the TiN coating in the S4 are that the deposition temperature is 880-900 ℃, the deposition pressure is 15-35KPa, and TiCl is used as the gas₄、H₂、N₂Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45-48 ℃, and the heat preservation time is 0.5-2 h.

Further, the deposition conditions of the MT-TiCN coating in the S4 are that the deposition temperature is 880-900 ℃, the deposition pressure is 6-50 KPa, and TiCl is used as the gas₄、H₂、N₂、CH₄Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45-48 ℃, and the heat preservation time is 4-8 h.

Further, the fine particles of α -Al in S4₂O₃The deposition conditions are deposition temperature of 1000-1010 ℃, deposition pressure of 6-20 KPa, and AlCl is used as the gas₃、H₂、CO₂Ar, wherein AlCl₃By H₂Carrying the mixture into a reaction furnace, and carrying AlCl₃The water temperature is 45-55 ℃, and the heat preservation time is 5-8 h.

Further, the post-treatment method in the step S5 is brush or sand blasting treatment, wherein the brush method selects a brush consisting of SiC and bristles, the treatment time is 5-10 seconds according to the thickness of the coating, the sand blasting method selects one or more of carborundum, silica sand and resin sand, the sand blasting treatment is carried out on the surface of the coating for a short time under the pressure of 2-4Bar, the treatment time is 5-10 seconds, and the roughness of the surface of the treated coating is less than 0.5 um.

The reaction principle of the first coating layer is as follows:

2TiCl₄(g)+N₂(g)+4H₂(g)→2TiN(s)+8HCl(g)；

the reaction principle of the second coating layer of the present application is:

4TiCl₄(g)+N₂(g)+2CH₄(g)+4H₂(g)→2(TiN(s)+TiC(g))+16HCl(g)；

the reaction principle of the third coating layer of the application is as follows:

CO₂(g)+H₂(g)→CO(g)+H₂O(g)；

2AlCl₃(g)+3H₂O(g)→Al₂O₃(s)+6HCl(g)。

has the advantages that:

the invention has the beneficial effects that:

the invention discloses a titanium carbonitride/alumina composite coating for repairing a substrate and a preparation method thereof, wherein the composite coating comprises the following components in sequence along the surface of the substrate: TiN, MT-TiCN, fine-grained alpha-Al₂O₃The preparation method of the surface layer and the composite coating comprises the following steps: firstly, polishing the surface of a substrate to be processed and then cleaning; then drying the substrate to be treated and depositing a coating, wherein the sequentially deposited coating is TiN, MT-TiCN and alpha-Al₂O₃Finally, the roughness of the coating is reduced through post-treatment to obtain the composite coating, compared with the existing coating, the innermost TiN layer can ensure the binding force between the substrate and the coating, the second MT-TiCN layer has high hardness and can be used as a wear-resistant layer and simultaneously is used for alpha-Al₂O₃The coating plays a supporting role, and the outermost layer of fine particles of alpha-Al₂O₃The hardness is high, the excellent high-temperature oxidation resistance is used as a heat insulation layer, the multi-layer composite coating layer has synergistic effect, the service performance of samples such as hard alloy, ceramic and metal ceramic with defects is improved by 200-300%, and the stress condition in the coating layer can be effectively improved, the surface roughness of the coating layer is reduced, and the service life of a cutter is prolonged through subsequent sand blasting treatment. The cost is greatly saved, and the method has wide application prospect in the fields of high-speed turning/milling steel, stainless steel and the like.

Drawings

In order to more clearly illustrate the embodiments of the present application 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 of the present application, 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 of the coating in example 1 of the present application;

FIG. 2 is a cross-sectional profile of the coating after deposition of coating A in example 1 of the present application;

FIG. 3 is a coating profile after deposition of coating B in example 2 of the present application;

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1: preparation of composite coating A

Deposition furnace: chemical vapor deposition furnace capable of carrying out medium and high temperature continuous deposition;

base material: SiC ceramic material.

The coating layer contacts with a substrate to form a first layer, and a second layer is deposited to form an outermost layer in sequence. The structure of the coating is shown in figure 1, the cross-sectional morphology of the deposited coating is shown in figure 2, and the deposited coating is sequentially TiN, MT-TiCN and alpha-Al₂O₃。

1. Firstly, polishing a SiC ceramic material substrate by using a 1500# diamond grinding disc to enable the surface smoothness Ra to be 0.2 μm, and then ultrasonically cleaning the polished substrate material for 30 min;

2. then, drying the base material and then loading the base material into a coating furnace;

3. firstly, TiN coating is deposited, the thickness of the coating is 0.05 mu m, the deposition temperature is 880 ℃, the deposition pressure is 25KPa, the deposition time is 0.5h, and TiCl is used as gas₄、H₂、N₂Ar, wherein TiCl₄Carrying the reaction mixture into a reaction furnace by using H2, and TiCl₄The water temperature is 48 ℃;

4. then depositing an MT-TiCN coating with the thickness of 2 mu m, the deposition temperature of 880 ℃, the deposition pressure of 6KPa and the deposition time of 4h, wherein TiCl is used as the gas₄、H₂、N₂、CH₄Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 48 ℃;

5. finally depositing alpha-Al₂O₃Coating with a thickness of 2 μm, a deposition temperature of 1000 deg.C, a deposition pressure of 6KPa, a deposition time of 5h, and AlCl as the gas₃、H₂、N₂、CO₂Ar, wherein AlCl₃By H₂Carrying the mixture into a reaction furnace, and carrying AlCl₃The water temperature is 55 ℃;

the post-treatment method is brush treatment, a brush consisting of SiC and bristles is selected by the brush method, the treatment time is 5 seconds, and the surface roughness of the treated coating is less than 0.5um, so that the titanium carbonitride/aluminum oxide composite coating A for repairing the matrix is obtained.

The thickness of the composite coating A is 4.05 mu m, the structure is relatively compact, wherein the TiN and TiCN coatings are in columnar crystal structures and have preferred orientation of (111) crystal planes. The bonding force between the coating and the substrate is 127 +/-5N, the nano-hardness of the coating is 7.2 +/-0.3 GPa, the coated sample has good wear resistance, the surface roughness is 240 +/-10 nm, and the wear rate is 3.5 multiplied by 10^-6mm³N.m, the friction coefficient of the coating is about 0.33.

Example 2: preparation of composite coating B

Deposition furnace: chemical vapor deposition furnace capable of carrying out medium and high temperature continuous deposition;

base material: WC-Co based hard alloy material.

The coating layer contacts with a substrate to form a first layer, and a second layer is deposited to form an outermost layer in sequence. The structure of the coating is shown in figure 1, the cross-sectional morphology of the deposited coating is shown in figure 3, and the deposited coating is sequentially TiN, MT-TiCN and alpha-Al₂O₃。

1. Firstly, polishing a WC-Co-based hard alloy material substrate by using a 1500# diamond grinding disc to enable the surface smoothness Ra to be 0.2 mu m, and then ultrasonically cleaning the polished substrate material for 30 min;

2. then, drying the base material and then loading the base material into a coating furnace;

3. firstly, depositing a TiN coating with the thickness of 0.1 mu m, the deposition temperature of 900 ℃, the deposition pressure of 30KPa and the deposition time of 2h by using TiCl as gas₄、H₂、N₂Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45 ℃;

4. then depositing an MT-TiCN coating with the thickness of 4 mu m, the deposition temperature of 900 ℃, the deposition pressure of 50KPa and the deposition time of 8h by using TiCl as gas₄、H₂、N₂、CH₄Ar, wherein TiCl₄By H₂Carrying the mixture into a reaction furnace, TiCl₄The water temperature is 45 ℃;

5. finally depositing alpha-Al₂O₃The coating layer is coated on the surface of the substrate,the thickness of the coating is 4 mu m, the deposition temperature is 1010 ℃, the deposition pressure is 20KPa, the deposition time is 8h, and AlCl is used as the used gas₃、H₂、N₂、CO₂Ar, wherein AlCl₃By H₂Carrying the mixture into a reaction furnace, and carrying AlCl₃The water temperature is 45 ℃;

the post-treatment method is sand blasting treatment, wherein 400-500-mesh carborundum is used as the sand, the sand blasting pressure is 2bar, the sand blasting time is 10 seconds, and the surface roughness of the treated coating is less than 0.5 mu m, so that the titanium carbonitride/aluminum oxide composite coating B for repairing the matrix is obtained.

The thickness of the composite coating B is 8.1 mu m, the structure is relatively compact, wherein the TiN and TiCN coatings are in columnar crystal structures and have preferred orientation of (111) crystal planes. The bonding force between the coating and the substrate is 144 +/-5N, the nano-hardness of the coating is 8.2 +/-0.2 GPa, the wear resistance of a coated sample is good, the surface roughness is 240 +/-10 nm, and the wear rate is 3.3 multiplied by 10^-6mm³N.m, the friction coefficient of the coating is about 0.32.

The coating prepared by the method has a structure shown in figure 1, and the alpha-Al of the surface layer is deposited₂O₃After the coating is worn off, compared with the coating A and the coating B, the service life and the bonding force are lower than those of the coating A and the coating B. In addition, only the first two layers are coated by adopting the process, and the coating can also be used, because the early pretreatment and the first layer of TiN ensure that the coating can be well combined with the matrix, but the bonding force and the friction performance are far inferior to those of the coating prepared by adopting the complete process, and particularly, the oxidation resistance has larger difference during high-speed milling.

In summary, the invention discloses a titanium carbonitride/aluminum oxide composite coating for repairing a substrate and a preparation method thereof, wherein the composite coating comprises the following components in sequence along the surface of the substrate: TiN, MT-TiCN, fine-grained alpha-Al₂O₃The preparation method of the surface layer and the composite coating comprises the following steps: firstly, polishing the surface of a substrate to be processed and then cleaning; then drying the substrate to be treated and depositing a coating, wherein the sequentially deposited coating is TiN, MT-TiCN and alpha-Al₂O₃Finally, the roughness of the coating is reduced through post-treatment to obtain the composite coating, and compared with the existing coating, the innermost TiN layer can ensure that the substrate and the coating can ensureThe second layer MT-TiCN has high hardness, can be used as a wear-resistant layer and is opposite to alpha-Al₂O₃The coating plays a supporting role, and the outermost layer of fine particles of alpha-Al₂O₃The hardness is higher, the excellent high-temperature oxidation resistance is used as a heat insulation layer, and the multi-layer composite coating layer has synergistic effect, so that the service performance of samples such as hard alloy, ceramic and metal ceramic with defects is improved by 200-300%, the cost is greatly saved, and the method has wide application prospect in the fields of high-speed vehicle/milling steel, stainless steel and the like.

Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited to the above embodiments, and those skilled in the art can make various changes and modifications without departing from the scope of the present invention.