CN107457707A - A kind of titanium or titanium alloy surface aoxidize layer minimizing technology - Google Patents
A kind of titanium or titanium alloy surface aoxidize layer minimizing technology Download PDFInfo
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- CN107457707A CN107457707A CN201710708232.6A CN201710708232A CN107457707A CN 107457707 A CN107457707 A CN 107457707A CN 201710708232 A CN201710708232 A CN 201710708232A CN 107457707 A CN107457707 A CN 107457707A
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- alloy surface
- minimizing technology
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000010936 titanium Substances 0.000 title claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003082 abrasive agent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 6
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010962 carbon steel Substances 0.000 claims description 2
- 239000002223 garnet Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims 10
- 238000007605 air drying Methods 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 239000004576 sand Substances 0.000 claims 2
- 239000002002 slurry Substances 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- 238000005422 blasting Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000005270 abrasive blasting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
- B24C1/086—Descaling; Removing coating films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C11/00—Selection of abrasive materials or additives for abrasive blasts
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
Abstract
本发明提供一种钛或钛合金表面氧化层去除方法，包括：将磨料与水混合，配制得到砂浆，将砂浆经抛丸器抛射至钛或钛合金表面，抛射去除氧化层。本发明可以有效去除钛或钛合金板带表面氧化层，并且，处理过程中不产生废水、废气等污染物，环保节能。
The invention provides a method for removing an oxide layer on the surface of titanium or titanium alloy, comprising: mixing abrasives with water to prepare mortar, projecting the mortar onto the surface of titanium or titanium alloy through a shot blaster, and removing the oxide layer by projecting. The invention can effectively remove the oxide layer on the surface of the titanium or titanium alloy strip, and does not generate waste water, waste gas and other pollutants during the treatment process, and is environmentally friendly and energy-saving.
Description
技术领域technical field
本发明涉及合金材料的氧化层去除技术领域，特别是涉及一种钛或钛合金表面氧化层去除方法。The invention relates to the technical field of oxide layer removal of alloy materials, in particular to a method for removing an oxide layer on the surface of titanium or titanium alloy.
背景技术Background technique
钛/钛合金具有重量轻、强度高、耐蚀性好和耐高温等优异性能，在各工业领域尤其是航空、航天、军事等领域获得大量应用。钛/钛合金板带在热轧或冷轧退火时表面会产生氧化层，现有技术通常采用酸洗方式去除钛/钛合金板带表面氧化层，传统的酸洗工艺通常包含以下步骤：第一步，采用干式抛丸去除表面部分氧化皮，或者将钛/钛合金浸入熔融碱液对氧化层进行处理；第二步，用硝酸或氢氟酸和硝酸配成的混酸进一步去除氧化层；第三步，用氢氟酸和硝酸的混酸去除残留的氧化层，并进行表面钝化。Titanium/titanium alloy has excellent properties such as light weight, high strength, good corrosion resistance and high temperature resistance, and has been widely used in various industrial fields, especially aviation, aerospace, military and other fields. Titanium/titanium alloy strips will produce an oxide layer on the surface during hot rolling or cold rolling and annealing. In the prior art, pickling is usually used to remove the oxide layer on the surface of titanium/titanium alloy strips. The traditional pickling process usually includes the following steps: In the first step, dry shot blasting is used to remove part of the oxide scale on the surface, or the titanium/titanium alloy is immersed in molten lye to treat the oxide layer; in the second step, the oxide layer is further removed with nitric acid or a mixed acid made of hydrofluoric acid and nitric acid ; The third step is to use a mixed acid of hydrofluoric acid and nitric acid to remove the residual oxide layer and passivate the surface.
上述现有的氧化层去除方法存在如下缺陷：1)钛/钛合金化学性能活泼，抛丸过程产生的粉尘易着火爆炸；2)碱洗时，熔融碱液会与表面的氧化物发生反应，加之熔融碱液本身温度较高，碱熔融会剧烈沸腾甚至爆炸，同时钛/钛合金在熔融碱液中还易燃烧；3)硝酸和氢氟酸酸洗过程，会产生废水和废气，对环境造成污染；4)硝酸和氢氟酸酸洗过程会造成钛/钛合金吸氢并引起氢脆，后期为了除氢必须进行真空退火。There are following defects in the above-mentioned existing oxide layer removal method: 1) titanium/titanium alloy has active chemical properties, and the dust produced in the shot blasting process is easy to catch fire and explode; In addition, the temperature of the molten lye itself is high, and the alkali melting will violently boil or even explode. At the same time, titanium/titanium alloys are also flammable in the molten lye; Cause pollution; 4) Nitric acid and hydrofluoric acid pickling process will cause hydrogen absorption and hydrogen embrittlement of titanium/titanium alloy, and vacuum annealing must be carried out in order to remove hydrogen later.
发明内容Contents of the invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种钛或钛合金表面氧化层去除方法，用于解决现有技术中钛或钛合金表面氧化层去除工艺复杂、成本较高、易污染环境等问题。In view of the shortcomings of the prior art described above, the purpose of the present invention is to provide a method for removing the oxide layer on the surface of titanium or titanium alloy, which is used to solve the problem of complex removal process, high cost, and high cost of oxide layer on the surface of titanium or titanium alloy in the prior art. Easy to pollute the environment and other issues.
为实现上述目的及其他相关目的，本发明提供一种钛或钛合金表面氧化层去除方法，包括：将磨料与水混合，配制得到砂浆，将砂浆经抛丸器抛射至钛或钛合金表面，抛射去除氧化层。当然，去除氧化层的同时，也可以去除表面的其他异物。采用该方法可以避免干式抛丸过程存在的粉尘易着火爆炸和碱熔融处理过程易着火等安全隐患，处理过程中不产生废水、废气等污染物，并可以避免吸氢引起的氢脆，是一种环保高效的钛或钛合金表面处理方法。In order to achieve the above purpose and other related purposes, the present invention provides a method for removing an oxide layer on the surface of titanium or titanium alloy, comprising: mixing abrasives with water to prepare mortar, and projecting the mortar onto the surface of titanium or titanium alloy through a shot blaster, Blasting to remove oxide layer. Of course, while removing the oxide layer, other foreign matter on the surface can also be removed. Using this method can avoid safety hazards such as dust that is easy to ignite and explode in the dry shot blasting process and easy to catch fire in the alkali fusion treatment process. Waste water, waste gas and other pollutants will not be generated during the treatment process, and hydrogen embrittlement caused by hydrogen absorption can be avoided. An environmentally friendly and efficient surface treatment method for titanium or titanium alloy.
进一步地，所述磨料选自不锈钢、碳钢、棕刚玉、白刚玉、玻璃珠、石榴石、碳化硼、碳化硅中的至少一种。可以根据板面质量和处理效率选择磨料种类。Further, the abrasive is selected from at least one of stainless steel, carbon steel, brown corundum, white corundum, glass beads, garnet, boron carbide, and silicon carbide. The type of abrasive can be selected according to the surface quality and processing efficiency.
进一步地，所述磨料的粒径为10目-140目。可以根据板面表面粗糙度目标值选择磨料粒径。Further, the particle size of the abrasive is 10 mesh-140 mesh. The abrasive particle size can be selected according to the target value of the surface roughness of the board.
优选地，所述磨料的粒径为36目-50目。Preferably, the particle size of the abrasive is 36 mesh-50 mesh.
进一步地，所述砂浆中磨料的质量与水的质量之比为(0.1-3)：1。Further, the ratio of the mass of abrasive to the mass of water in the mortar is (0.1-3):1.
优选地，所述砂浆中磨料的质量与水的质量之比为(0.6-0.8)：1。Preferably, the ratio of the mass of abrasive to the mass of water in the mortar is (0.6-0.8):1.
进一步地，抛丸器抛射砂浆的速度为10m/s-100m/s。可以根据板面粗糙度和处理效率选择砂浆抛射速度。Further, the speed at which the shot blaster projects the mortar is 10m/s-100m/s. The mortar ejection speed can be selected according to the surface roughness and processing efficiency.
优选地，抛丸器抛射砂浆的速度为50m/s-60m/s。Preferably, the speed at which the shot blaster projects the mortar is 50m/s-60m/s.
进一步地，砂浆的入射方向与被处理表面所在平面的夹角为20°-90°。可以根据表面粗糙度和处理效率选择夹角。Further, the included angle between the incident direction of the mortar and the plane where the treated surface is located is 20°-90°. The included angle can be selected according to surface roughness and processing efficiency.
优选地，砂浆的入射方向与被处理表面所在平面的夹角为60°-70°。Preferably, the angle between the incident direction of the mortar and the plane of the treated surface is 60°-70°.
具体抛射速度、角度视钛/钛合金板处理后表面氧化层去除率和粗糙度情况而定。The specific ejection speed and angle depend on the removal rate and roughness of the surface oxide layer of the titanium/titanium alloy plate after treatment.
进一步地，抛射处理时间为0.1s-20s。Further, the ejection processing time is 0.1s-20s.
优选地，抛射处理时间为5s-7s。Preferably, the ejection processing time is 5s-7s.
进一步地，还包括后处理：清洗钛或钛合金表面，干燥得到去除氧化层后的钛或钛合金。Further, post-treatment is also included: cleaning the surface of the titanium or titanium alloy, and drying to obtain the titanium or titanium alloy after the oxide layer has been removed.
进一步地，干燥方式为30℃-150℃热风干燥。Further, the drying method is hot air drying at 30°C-150°C.
优选地，干燥方式为70℃-150℃热风干燥。Preferably, the drying method is hot air drying at 70°C-150°C.
如上所述，本发明的一种钛或钛合金板带表面氧化层去除方法，具有以下有益效果：本发明可以有效去除钛或钛合金板带表面氧化层，并且，处理过程中不产生废水、废气等污染物，环保节能。As mentioned above, a method for removing the oxide layer on the surface of titanium or titanium alloy strips of the present invention has the following beneficial effects: the present invention can effectively remove the oxide layer on the surface of titanium or titanium alloy strips, and does not produce waste water, Waste gas and other pollutants, environmental protection and energy saving.
附图说明Description of drawings
图1a显示为本发明实施例1中纯钛板带表面氧化层去除后的表面微观形貌图。Fig. 1a shows the surface microscopic topography of the pure titanium strip after removal of the oxide layer on the surface in Example 1 of the present invention.
图1b显示为本发明实施例1中纯钛板带表面氧化层去除后的面扫描表面能谱图。Fig. 1b shows the surface scanning surface energy spectrum of the pure titanium strip surface in Example 1 of the present invention after removal of the oxide layer.
图2a显示为本发明实施例2中TC4钛合金板带表面氧化层去除后的表面微观形貌图。Fig. 2a shows the surface microscopic topography of the TC4 titanium alloy strip surface after removal of the oxide layer in Example 2 of the present invention.
图2b显示为本发明实施例2中TC4钛合金板带表面氧化层去除后的面扫描表面能谱图。Fig. 2b shows a surface scanning surface energy spectrum after the oxide layer on the surface of the TC4 titanium alloy strip in Example 2 of the present invention is removed.
具体实施方式detailed description
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude that there may be other method steps before and after the combined steps or other method steps may be inserted between these explicitly mentioned steps, unless otherwise There are descriptions; it should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices before and after the combined devices/devices or those explicitly mentioned Other devices/apparatus can also be interposed between the two devices/apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the sequence of each method step or limit the scope of the present invention. The change or adjustment of its relative relationship is in In the case of no substantive change in the technical content, it shall also be regarded as the applicable scope of the present invention.
实施例1Example 1
纯钛板带表面处理Pure titanium strip surface treatment
工艺流程包括：磨料抛射处理-水洗-烘干。The technological process includes: abrasive blasting treatment-water washing-drying.
(1)磨料为棕刚玉和水混合形成的砂浆，棕刚玉粒径为36目，棕刚玉和水的比率为每升水中含0.8kg棕刚玉，砂浆经抛丸器加速至50m/s后抛射至纯钛板表面，砂浆入射角与纯钛板表面夹角为70°，砂浆抛射处理时间为5s。(1) The abrasive is a mortar formed by mixing brown corundum and water. The particle size of brown corundum is 36 mesh. The ratio of brown corundum to water is 0.8kg of brown corundum per liter of water. The mortar is accelerated to 50m/s by a shot blasting machine and then projected To the surface of the pure titanium plate, the angle between the incident angle of the mortar and the surface of the pure titanium plate is 70°, and the mortar blasting treatment time is 5s.
(2)处理后的纯钛板用清水冲洗干净。(2) The treated pure titanium plate is rinsed with clean water.
(3)用70℃热风将纯钛板表面烘干。(3) Dry the surface of the pure titanium plate with hot air at 70°C.
纯钛板经以上工序处理后，经扫描电镜观察和能谱分析检测，图1a显示为本实施例中纯钛板带表面氧化层去除后的表面微观形貌图，图1b显示为本实施例中纯钛板带表面氧化层去除后的面扫描表面能谱图。实验发现，处理后的纯钛板表面无氧化物残留，其表面粗糙度Ra为5.6μm。After the pure titanium plate is processed by the above process, it is observed by scanning electron microscope and energy spectrum analysis. The surface scanning surface energy spectrum of the medium-pure titanium strip after the surface oxide layer is removed. Experiments have found that there is no oxide residue on the surface of the treated pure titanium plate, and its surface roughness Ra is 5.6 μm.
实施例2Example 2
TC4钛合金板带表面处理TC4 titanium alloy strip surface treatment
工艺流程包括：磨料抛射处理-水洗-烘干。The technological process includes: abrasive blasting treatment-water washing-drying.
(1)磨料为棕刚玉和水混合形成的砂浆，棕刚玉粒径为36目，棕刚玉和水的比率为每升水中含0.8kg棕刚玉，砂浆经抛丸器加速至50m/s后抛射至TC4钛合金板表面，砂浆入射角与TC4钛合金板表面夹角为70°，砂浆抛射处理时间为5s。(1) The abrasive is a mortar formed by mixing brown corundum and water. The particle size of brown corundum is 36 mesh. The ratio of brown corundum to water is 0.8kg of brown corundum per liter of water. The mortar is accelerated to 50m/s by a shot blasting machine and then projected To the surface of the TC4 titanium alloy plate, the angle between the incident angle of the mortar and the surface of the TC4 titanium alloy plate is 70°, and the mortar blasting treatment time is 5s.
(2)处理后的TC4钛合金板用清水冲洗干净。(2) Rinse the treated TC4 titanium alloy plate with clean water.
(3)用70℃热风将TC4钛合金板表面烘干。(3) Dry the surface of the TC4 titanium alloy plate with hot air at 70°C.
TC4钛合金板经以上工序处理后，经扫描电镜观察和能谱分析检测，图2a显示为本实施例中TC4钛合金板带表面氧化层去除后的表面微观形貌图，图2b显示为本实施例中TC4钛合金板带表面氧化层去除后的面扫描表面能谱图。实验发现，处理后的TC4钛合金板表面无氧化物残留，其表面粗糙度Ra范围为2.8μm。After the TC4 titanium alloy plate is processed by the above process, it is observed by scanning electron microscope and energy spectrum analysis. The surface scanning surface energy spectrogram of the TC4 titanium alloy strip surface in the embodiment after the oxide layer is removed. Experiments have found that there is no oxide residue on the surface of the treated TC4 titanium alloy plate, and its surface roughness Ra ranges from 2.8 μm.
实施例3-12Example 3-12
表1 不同工艺的处理情况表Table 1 Table of processing conditions of different processes
钛或钛合金板带上下表面的硬质磨料尺寸、抛射速度、硬质磨料和水的比率、磨料入射角等参数可以相同或不同。Parameters such as the size of the hard abrasive on the upper and lower surfaces of the titanium or titanium alloy strip, the ejection speed, the ratio of the hard abrasive to water, and the incident angle of the abrasive can be the same or different.
综上所述，本发明主要有如下效果：(1)采用本发明，可以彻底去除钛/钛合金板表面氧化层；(2)处理过程不会造成钛或钛合金吸氢；(3)处理过程无废水、废气等污染物产生；(4)可以处理钛/钛合金板一个或两个表面，可以分别控制正面和反面的氧化层去除率和粗糙度。In summary, the present invention mainly has the following effects: (1) by adopting the present invention, the oxide layer on the surface of the titanium/titanium alloy plate can be completely removed; (2) the treatment process will not cause hydrogen absorption by titanium or titanium alloy; (3) the treatment No waste water, waste gas and other pollutants are produced in the process; (4) One or both surfaces of titanium/titanium alloy plates can be treated, and the removal rate and roughness of the oxide layer on the front and back sides can be controlled respectively.
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.
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