TWI685280B - Air plasma surface treatment apparatus for surface modification of tube inner wall by grafting - Google Patents
Air plasma surface treatment apparatus for surface modification of tube inner wall by grafting Download PDFInfo
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- TWI685280B TWI685280B TW108100734A TW108100734A TWI685280B TW I685280 B TWI685280 B TW I685280B TW 108100734 A TW108100734 A TW 108100734A TW 108100734 A TW108100734 A TW 108100734A TW I685280 B TWI685280 B TW I685280B
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 54
- 230000004048 modification Effects 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims description 67
- 229920000642 polymer Polymers 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000002473 artificial blood Substances 0.000 claims description 4
- 210000004204 blood vessel Anatomy 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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Abstract
Description
本發明係關於電漿表面處理設備,尤其是關於用於管內壁接枝改質之大氣電漿表面處理設備。 The invention relates to plasma surface treatment equipment, in particular to atmospheric plasma surface treatment equipment used for graft modification of inner wall of pipes.
近年來,人工合成材料在生醫應用上的進展十分迅速。許多人工材料在物理性質上幾乎可以媲美自然組織。但是,因為材料表面特性與人體生化構造不相容,在實際應用上會面臨一些棘手的問題,例如血栓、發炎及感染等。因此,許多表面處理技術已經開發出來,以提升材料之生物相容性。 In recent years, the progress of synthetic materials in the application of biomedicine is very rapid. Many artificial materials are almost comparable to natural tissues in physical properties. However, because the surface characteristics of the material are incompatible with the biochemical structure of the human body, it will face some difficult problems in practical application, such as thrombosis, inflammation and infection. Therefore, many surface treatment technologies have been developed to enhance the biocompatibility of materials.
在這些表面處理技術中,電漿表面處理技術可以針對材料表面10微米深度內之範圍進行作用,不會損及材料主體之特性。此外,電漿表面處理亦可透過改變其進氣種類、處理功率、處理時間等參數,得到多樣化之材料表面特性,以符合實際需求。因此,電漿表面處理之技術,在生醫材料表面改質方面,已獲得廣泛使用。 Among these surface treatment technologies, plasma surface treatment technology can act on the surface of the material within a depth of 10 microns, without compromising the characteristics of the material body. In addition, plasma surface treatment can also obtain diverse material surface characteristics by changing its air intake type, processing power, processing time and other parameters to meet actual needs. Therefore, the technology of plasma surface treatment has been widely used in the surface modification of biomedical materials.
不過,受限於所產生之電漿距離與範圍,傳統之電漿表面處理技術無法有效針對管材(如人工血管、導管等)之內壁進行表面處理。 However, due to the distance and range of the generated plasma, the traditional plasma surface treatment technology cannot effectively perform surface treatment on the inner wall of the pipe (such as artificial blood vessels, catheters, etc.).
有鑑於此,本發明提供一種用於管內壁接枝改質之大氣電漿表面處理設備,可針對管材內壁進行表面處理。 In view of this, the present invention provides an atmospheric plasma surface treatment device for graft modification of the inner wall of a pipe, which can perform surface treatment on the inner wall of the pipe.
本發明之一實施例提供一種用於管內壁接枝改質之大氣電漿表面處理設備,用以對一管材內壁進行表面處理。此大氣電漿表面處理設備包括一脈衝產生器、一第一氣體源、一第二氣體源、一高分子單體(monomer)源、一噴嘴、一第一氣體流路、一第二氣體流路與一導電板。其中,脈衝產生器包括一正極與一負極,以產生一高壓脈衝。第一氣體源係用以提供一第一氣體。第二氣體源係用以提供一第二氣體作為一載氣。高分子單體源係用以提供一高分子單體。載氣係用以攜帶高分子單體。噴嘴係用以連接管材。第一氣體流路係由第一氣體源連接至噴嘴,並且,脈衝產生器所產生之高壓脈衝係施加於此第一氣體流路,以產生大氣電漿由噴嘴噴發。第二氣體流路係由第二氣體源透過高分子單體源連接至噴嘴,以提供高分子單體至管材內部。導電板係對準噴嘴之一噴發方向。管材係設置於噴嘴與導電板之間。 An embodiment of the present invention provides an atmospheric plasma surface treatment device for graft modification of an inner wall of a pipe, which is used for surface treatment of an inner wall of a pipe. The atmospheric plasma surface treatment equipment includes a pulse generator, a first gas source, a second gas source, a monomer source, a nozzle, a first gas flow path, and a second gas flow Road and a conductive board. The pulse generator includes a positive electrode and a negative electrode to generate a high-voltage pulse. The first gas source is used to provide a first gas. The second gas source is used to provide a second gas as a carrier gas. The polymer monomer source is used to provide a polymer monomer. The carrier gas is used to carry high molecular monomers. The nozzle is used to connect the pipe. The first gas flow path is connected to the nozzle by the first gas source, and the high-pressure pulse generated by the pulse generator is applied to the first gas flow path to generate atmospheric plasma to be emitted from the nozzle. The second gas flow path is connected to the nozzle by the second gas source through the polymer monomer source to provide the polymer monomer to the inside of the pipe. The conductive plate is aligned with one of the nozzles. The pipe is arranged between the nozzle and the conductive plate.
相較於傳統之電漿表面處理技術,本發明 所提供之大氣電漿表面處理設備,可以在大氣環境內生成長距離之電漿,以利於對管材內壁進行清潔、交聯(cross-linking)、機能化(functionalization)、聚合化(polymerization)等表面處理。 Compared with the traditional plasma surface treatment technology, the present invention The provided atmospheric plasma surface treatment equipment can generate a long distance plasma in the atmospheric environment to facilitate the cleaning, cross-linking, functionalization and polymerization of the inner wall of the pipe Wait for surface treatment.
本發明所採用的具體實施例,將藉由以下之實施例及圖式作進一步之說明。 The specific embodiments adopted by the present invention will be further described by the following embodiments and drawings.
10,20‧‧‧管材 10,20‧‧‧tube
100,200‧‧‧大氣電漿表面處理設備 100,200‧‧‧Atmospheric plasma surface treatment equipment
120,220‧‧‧脈衝產生器 120,220‧‧‧Pulse generator
130,230‧‧‧第一氣體源 130,230‧‧‧First gas source
140‧‧‧第二氣體源 140‧‧‧Second gas source
150‧‧‧高分子單體源 150‧‧‧polymer monomer source
160,260‧‧‧噴嘴 160,260‧‧‧ nozzle
170,270‧‧‧第一氣體流路 170,270‧‧‧ First gas flow path
180‧‧‧第二氣體流路 180‧‧‧ Second gas flow path
172,182,272‧‧‧流量控制器 172,182,272‧‧‧Flow controller
190,290‧‧‧導電板 190,290‧‧‧ conductive plate
122,222‧‧‧正極 122,222‧‧‧Positive
124,224‧‧‧負極 124,224‧‧‧Negative
D1‧‧‧預設距離 D1‧‧‧Preset distance
第一圖係本發明之用於管內壁接枝改質之大氣電漿表面處理設備第一實施例之配置示意圖。 The first figure is the configuration diagram of the first embodiment of the atmospheric plasma surface treatment equipment for graft modification of the inner wall of the present invention.
第二圖係本發明之大氣電漿表面處理設備第二實施例之配置示意圖。 The second figure is a schematic configuration diagram of a second embodiment of the atmospheric plasma surface treatment device of the present invention.
下面將結合示意圖對本發明的具體實施方式進行更詳細的描述。根據下列描述和申請專利範圍,本發明的優點和特徵將更清楚。需說明的是,圖式均採用非常簡化的形式且均使用非精準的比例,僅用以方便、明晰地輔助說明本發明實施例的目的。 The specific embodiments of the present invention will be described in more detail below with reference to schematic diagrams. The advantages and features of the present invention will be clearer from the following description and patent application scope. It should be noted that the drawings are in a very simplified form and all use inaccurate proportions, which are only used to conveniently and clearly assist the purpose of explaining the embodiments of the present invention.
第一圖係本發明之用於管內壁接枝改質之大氣電漿表面處理設備第一實施例之配置示意圖。此大氣電漿表面處理設備100係用以對一管材10內壁進行表面處理。此管材10可以是人工血管、導管等應用於生醫領域之人工裝置。管材10可由聚對苯二甲酸乙二酯
(PET或PETE),聚四氟乙烯(PTFE),聚乙烯(PE),矽橡膠(silicon rubber),聚氯乙烯(PVC)、聚氨酯(PU)等高分子材料所構成。不過,亦不限於此。任何可透過電漿處理進行高分子接枝之材質,均可適用於本發明。
The first figure is the configuration diagram of the first embodiment of the atmospheric plasma surface treatment equipment for graft modification of the inner wall of the present invention. The atmospheric plasma
如圖中所示,此大氣電漿表面處理設備100包括一脈衝產生器120、一第一氣體源130、一第二氣體源140、一高分子單體(monomer)源150、一噴嘴160、一第一氣體流路170、一第二氣體流路180與一導電板190。
As shown in the figure, the atmospheric plasma
其中,脈衝產生器120包括一正極122與一負極124,以產生一高壓脈衝。就一實施例而言,此脈衝產生器可以是一直流脈衝產生器(DC pulse generator),其正極122係一鎢電極,負極124係接地。不過,本發明並不限於此。此脈衝產生器120亦可以是一交流脈衝產生器(AC pulse generator)或射頻脈衝產生器(RF pulse generator)。
The
第一氣體源130係用以提供一第一氣體。此第一氣體係用以產生大氣電漿。就一實施例而言,此第一氣體係氦氣(He)、氖氣(Ne)或氬氣(Ar)等惰性氣體。
The
第二氣體源140係用以提供一第二氣體。此第二氣體係作為一載氣,以攜帶高分子單體至管材10。就一實施例而言,第二氣體也是氦氣(He)、氖氣(Ne)或氬氣(Ar)等惰性氣體。在一實施例中,第二氣體與第一氣體相同。又,在一實施例中,第一氣體之流量大於第二氣體之流量。
The
高分子單體源150係用以提供一高分子單體至管材10內壁,以進行沉積(deposition)、聚合等表面處理。就一實施例而言,此高分子單體具有至少一官能基。此官能基係選自由胺基(-NH2)、羧酸基(-COOH)、羥基(-OH)、醛基(-CHO)構成之一群組。在一實施例中,此高分子單體係環丙胺(Cyclopropylamine)、烯丙胺(Allylamine)、環己二胺(diaminocyclohexane)、正庚胺(heptylamine)、乙二胺(ethylenediamine)、正丁胺(butylamine)、丙炔胺(propargylamine)或正丙胺(propylamine)。此高分子單體源150可提供氣態或液態之高分子單體。
The
第一氣體流路170係由第一氣體源130連接至噴嘴160。第一氣體流路170上設置有一流量控制器172以控制第一氣體之流量。管材10則是連接至噴嘴160。脈衝產生器120之正極與負極係緊靠於第一氣體流路170,以將高壓脈衝施加於第一氣體流路170,藉以產生大氣電漿由噴嘴160噴發至管材10內部。
The first
第二氣體流路180係由第二氣體源140透過高分子單體源150連接至噴嘴160。第二氣體流路180上設置有一流量控制器182以控制第二氣體之流量。第二氣體源140所提供之第二氣體流經高分子單體源150後,會攜帶高分子單體至管材10內壁進行反應,以形成高分子鍍層或是改變管材內壁之高分子材料的特性。
The second
導電板190係對準噴嘴160之噴發方向,以提升電漿之噴發距離。管材10係設置於噴嘴160與導電板
190之間。在一實施例中,此導電板190係一接地之銅板。在一實施例中,導電板190係設置於管材10之一末端後方一預設距離D1,而未與管材10相接觸。就一實施例而言,此預設距離D1係小於1公分。
The
下表(表一)列出本發明之大氣電漿表面處理設備100實際進行管內壁接枝改質處理之實驗數據,以說明此大氣電漿表面處理設備100之特性與優點。值得注意的是,此實驗數據僅為輔助說明本發明之目的與優點,並不對本發明之範圍進行任何限制。
The following table (Table 1) lists the experimental data of the atmospheric plasma
本發明大氣電漿表面處理設備100進行表面處理之管材內徑為3mm,長度為11.5cm。依據此實驗數據實際產生用於管內壁接枝改質之環丙胺接枝濃度為9.514*10-7mol/cm2。
The inner diameter of the pipe for surface treatment by the atmospheric plasma
第二圖係本發明之大氣電漿表面處理設備第二實施例之配置示意圖。此大氣電漿表面處理設備200係用以對一管材20內壁進行表面處理。此管材20可以是人工血管、導管等應用於生醫領域之人工裝置。管材20可包含聚對苯二甲酸乙二酯(PET或PETE),聚四氟乙烯(PTFE),聚乙烯(PE),矽橡膠(silicon rubber),聚氯乙烯(PVC)、聚氨酯(PU)等高分子材料。
The second figure is a schematic configuration diagram of a second embodiment of the atmospheric plasma surface treatment device of the present invention. The atmospheric plasma
相較於第一圖之大氣電漿表面處理設備100,本實施例之大氣電漿表面處理設備200並不具有第二氣體源140與高分子單體源150。本實施例之大氣電漿表面處理設備200所具有之脈衝產生器220、正極222、負極224、第一氣體源230、噴嘴260、第一氣體流路270、流量控制器272與導電板290類似於第一圖之實施例中之對應元件,在此不予贅述。
Compared with the atmospheric plasma
此大氣電漿表面處理設備200並不提供高分子單體至管材20內壁進行沉積、聚合等表面處理,而是著重於利用長距離之電漿對管材20內壁進行表面清潔、表面強化,或是搭配反應氣體之使用以達到活化管材內壁之效果。
The atmospheric plasma
相較於傳統之電漿表面處理技術,本發明所提供之大氣電漿表面處理設備,可以在大氣環境內生成長距離之電漿,以利於對管材內壁進行清潔、交聯、機能化、聚合化等表面處理。 Compared with the traditional plasma surface treatment technology, the atmospheric plasma surface treatment equipment provided by the present invention can generate long-distance plasma in the atmospheric environment to facilitate the cleaning, cross-linking, and functionalization of the inner wall of the pipe. Surface treatment such as polymerization.
上述僅為本發明較佳之實施例而已,並不對本發明進行任何限制。任何所屬技術領域的技術人 員,在不脫離本發明的技術手段的範圍內,對本發明揭露的技術手段和技術內容做任何形式的等同替換或修改等變動,均屬未脫離本發明的技術手段的內容,仍屬於本發明的保護範圍之內。 The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. Anyone skilled in the technical field Members, within the scope of not departing from the technical means of the present invention, any equivalent replacement or modification of the technical means and technical contents disclosed in the present invention is any form of content that does not deviate from the technical means of the present invention and still belongs to the present invention Within the scope of protection.
10‧‧‧管材 10‧‧‧tube
100‧‧‧大氣電漿表面處理設備 100‧‧‧Atmospheric plasma surface treatment equipment
120‧‧‧脈衝產生器 120‧‧‧Pulse generator
130‧‧‧第一氣體源 130‧‧‧First gas source
140‧‧‧第二氣體源 140‧‧‧Second gas source
150‧‧‧高分子單體源 150‧‧‧polymer monomer source
160‧‧‧噴嘴 160‧‧‧ nozzle
170‧‧‧第一氣體流路 170‧‧‧ First gas flow path
180‧‧‧第二氣體流路 180‧‧‧ Second gas flow path
172,182‧‧‧流量控制器 172,182‧‧‧Flow controller
190‧‧‧導電板 190‧‧‧conductive plate
122‧‧‧正極 122‧‧‧Positive
124‧‧‧負極 124‧‧‧Negative
D1‧‧‧預設距離 D1‧‧‧Preset distance
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CN101013797A (en) * | 2007-02-02 | 2007-08-08 | 西安交通大学 | Method and apparatus for generating glow discharge plasma under atmospheric pressure in air |
US20080145553A1 (en) * | 2006-07-31 | 2008-06-19 | Tekna Plasma Systems Inc. | Plasma surface treatment using dielectric barrier discharges |
TW200927994A (en) * | 2007-12-25 | 2009-07-01 | Univ Chung Yuan Christian | Method for forming composite membrane having porous coating layer and apparatus thereof |
US20100236684A1 (en) * | 2009-03-18 | 2010-09-23 | Greg Garlough | Plasma deposition to increase adhesion |
TW201326508A (en) * | 2011-12-23 | 2013-07-01 | Taiwan Textile Res Inst | Continuous modification apparatus for organic stripe material |
TW201538339A (en) * | 2014-01-28 | 2015-10-16 | Taiyo Chemical Industry Co Ltd | Structure including carbon film and method of forming carbon film |
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US20080145553A1 (en) * | 2006-07-31 | 2008-06-19 | Tekna Plasma Systems Inc. | Plasma surface treatment using dielectric barrier discharges |
CN101013797A (en) * | 2007-02-02 | 2007-08-08 | 西安交通大学 | Method and apparatus for generating glow discharge plasma under atmospheric pressure in air |
TW200927994A (en) * | 2007-12-25 | 2009-07-01 | Univ Chung Yuan Christian | Method for forming composite membrane having porous coating layer and apparatus thereof |
US20100236684A1 (en) * | 2009-03-18 | 2010-09-23 | Greg Garlough | Plasma deposition to increase adhesion |
TW201326508A (en) * | 2011-12-23 | 2013-07-01 | Taiwan Textile Res Inst | Continuous modification apparatus for organic stripe material |
TW201538339A (en) * | 2014-01-28 | 2015-10-16 | Taiyo Chemical Industry Co Ltd | Structure including carbon film and method of forming carbon film |
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