CN101443230B - 用于水下结构的防污纤维包覆层 - Google Patents
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Abstract
本发明提供一种具有防污特性的纤维包覆的水下材料，不需要包含生物活性剂。至少部分所述水下材料被具有至少50μm的厚度和至少3mm的纤维长度的纤维绒覆盖。所述纤维的厚度与长度的比例至少为0.010，所述纤维绒具有低于40纤维/mm2的密度。所述纤维包覆可以直接施加在水下材料上，例如绳索和结构部件上，或可以施加在能够用于水下设备的薄板上。
Description
技术领域
本发明涉及一种纤维包覆的水下材料，其防止有害污损生物在与水、尤其是海水接触的水下结构上附着和生长。本发明还涉及这种纤维包覆的水下材料的制备以及一种适用于制造防污水下结构的纤维包覆的薄板。
背景技术
在暴露于海水和/或淡水的水下结构和船体上，海洋生物的附着和生长会带来严重的经济损失，这是由于增加的摩擦力和由此增加的燃油消耗、或增加的波浪或水流(对于静止结构，例如海上钻塔)阻力、以及减小的可能的操作时间。通常，大部分船主尝试通过使用包含例如铜或三丁基锡、锡-基化合物的涂料涂在船体上防止污染。这些涂料是高毒性的，这些毒性物质浸入水中杀死海洋生物。
长期以来，一些不含杀虫剂的防污涂料种类已经进入市场，以满足对环境友好的替代品的不断需要。同时还关注了纤维包覆层。通过在水下材料表面上布置绒毛和薄纤维，阻止了污损生物的沉积。柔性纤维自然地在水中摇摆，如此形成一个摆动的毛皮状的表面，而孢子、游动孢子或藻类和贝类的幼生物通常比较困难并几乎不会附着在摆动物质上。
根据B.T.Watermann等的“Bioassays and selected chemical analysis ofbiocide-free antifouling agents”Chemosphere 60(2005)1530-1541，纤维包覆层通常包含稠密型的短纤维(200-500纤维/mm2)。首先，涂敷粘合剂，其用来作为固定纤维的胶。然后所述纤维充静电并被喷射到湿的粘合剂层，使得它们在粘合剂层内保持垂直方向。
EP-A-312.600涉及一种防止藻类和贝类附着的毛皮状纤维包覆的水下材料，该材料特征在于它被许多包含有5旦尼尔或更小的细纤维的绒毛覆盖。旦尼尔单位有时用来表示纱线的细度，等同于每9km纱线的质量g。在EP-A-312.600中提及，大于5旦尼尔是不理想的，因为纤维在水里摆动小并进一步产生不平的表面，这将会引起藻类和贝类的附着。作为替代，其教导使用1.5旦尼尔或更小的纤维，因为效果、生产简单、经济原因以及使用简单的原因。这些小纤维对藻类和贝类的附着效果被认为与纤维的摆动特性相关。绒毛在潮流和波浪中的摆动能力由绒毛的长度和厚度控制。
进一步，EP-A-353.095公开了一种包含纤维成份的防污薄板，所述纤维成份的直径约10-300μm并且长约10-30mm。所述纤维成份相对较长，并且选择厚度对长度的比例例如以获得能在水里做自由摆动运动的柔性毛皮状表面。
WO-A-93/25432教导了使用具有高密度的细短纤维的纤维绒用于船体结构的防污。它提到了密度为50-300纤维/mm2，纤维厚度为小于0.1mm和绒毛长度为0.5-5mm，但是没有提到所述纤维绒的其他任何物理特性和获得这种纤维的方法。至少清楚的是，从现有技术和材料来看，不可能生产具有该文献提及的所有范围的密度和厚度的组合的纤维。最小密度为50纤维/mm2且优选最小密度为150纤维/mm2表示：建议采用非常细和短的纤维，长度最大约1mm且厚度小于10旦尼尔。
这些现有的摆动的毛皮状包覆层中没有一个能完全阻止藤壶、藻类、海草、贝类等的附着和生长。尤其是，不能以与诸如采用含有杀虫剂的涂料同样的效率来减小藻类和其他软体污损生物的生长。
发明内容
本发明的目的是提供一种具有改善的防污特性的纤维包覆的水下材料，不需要任何杀虫剂材料，并且所述纤维包覆的材料保护水面下的水下结构避免各种生物体的沉积。
现在发现通过选择具有50μm或更大、优选为60μm或更大的厚度、至少3mm的纤维长度的纤维可改善防污包覆层的有效性，其中所述包覆层包含具有低于40纤维/mm2的密度的纤维绒。为了比较，60μm的厚度对应于约30旦尼尔。选择相对短和厚的纤维所形成的表面，用“荆棘状”能更好地代表其特征，而不是现在应用的毛皮状纤维包覆层。与现有技术已经揭示的相反，观察到该技术的有效性显著偏向较硬的绒毛。
由此本发明涉及一种具有防污特性的纤维包覆的水下材料，其中至少部分水下材料被具有至少70μm的厚度和至少3mm的纤维长度的纤维绒覆盖，其中所述纤维绒具有低于40纤维/mm2的密度。
“防污”是指阻止(部分)对水下表面的物理属性有消极影响的水生物在水下表面上的附着和生长。阻止沉积的重要生物包括：贝类例如蚌类和牡蛎、藤壶等以及它们的幼虫、管虫类、海鞘类、水螅虫类和苔藓虫类。所述纤维材料也用于避免植物例如藻类、海草以及它们的孢子和游动孢子在水下结构上生长。
在本发明上下文中，“水下材料”意指包括涉及在水介质中移动遇到摩擦力产生的流体阻力的物体，以及至少部分达到水面以下的水下结构的材料。适合于纤维包覆的水下材料的非穷尽的列举包括网、绳索、浮标、航标等和船舶设备材料、船体、港口、码头以及那些相关水上设备和用品，例如布置在海、河、湖、港口和码头下的管道、配水槽和排水沟。在具体实施例中，所述纤维包覆层用来保护静止水下结构，例如平台、石油钻塔、系泊柱。在另一具体实施例中，所述纤维用于船、艇、浮标和其他浮动设备。
所述水下材料用本发明的纤维覆盖其大部分表面积，优选的至少75％，更优选的至少90％。
纤维形成材料的所有种类可以用于形成水下材料上的荆棘状表面。可采用亲水性和疏水性聚合物。所述纤维通常由聚酯、聚酰胺或聚丙烯组成，包括聚酯(如聚对苯二甲酸乙二酯和聚对苯二甲酸丁二酯)、聚酰胺(以尼龙6、11、12、66和610为代表)、聚氨酯、(改性)聚(乙烯醇)、聚亚烷基(如聚乙烯或聚丙烯或它们的改性(共聚)形式)并且也可以使用人造纤维。所述纤维也可以包括改性物、共聚物或前面提到的各种类型的混合物。所述纤维优选包括聚乙烯和/或聚丙烯、或它们的共聚物。当需要耐久性的情况下，可以优选使用聚丙烯。
因为本发明纤维增强的有效性，这些可以用于水下结构的表面而不需要杀虫剂，但是可以和(较低)浓度的生物活性化合物(例如传统的锡基、铜基、锌基或其它防污剂)组合使用。然而在优选的具体实施例中，所述水下材料的纤维层不含杀虫材料和可能具有杀虫剂性质的材料。
所述纤维厚度优选在60μm和150μm之间，更优选的在70-120μm范围内。这些厚度是平均值。这些范围之外的一定范围内(例如至多10％)不会降低纤维的有效性。纤维长度通常在3mm和30mm之间。然而，厚度和长度不能彼此独立地选择；纤维厚度和纤维长度的结合需要产生比较硬的、荆棘状的纤维。要避免过高的纤维长度，因为会引起摆动运动，并只能通过加大纤维厚度进行补偿。另一方面，太短的纤维长度可能也不具有所需要的“荆棘”效果，而会产生不能阻止生物体沉积的光滑平面。对纤维厚度的选择也要考虑纤维的长度。另外，高的纤维长度和/或厚度增加了多余的重量和费用。优选的，纤维长度小于20mm，最佳的，最大长度小于10mm。所需的纤维长度能通过诸如切割的传统方法得到。
为了保证足够的绒毛硬度，纤维的厚度与长度的比例优选的在0.010和0.040之间，更优选的在0.012和0.030之间，最优选的在0.015和0.025之间，尤其是大于0.016。如果该比值太低，绒毛会变得柔软，引起水下物质摆动。要避免水流和波浪引起的摆动运动，因为发现它不能满足阻止尤其是藻类和藤壶的附着和生长。太大的比值引起荆棘状特性的丢失，也将减小所述纤维的抑制效果。
如果水下材料覆盖有具有10-35纤维/mm2、尤其是在15-30纤维/mm2范围内的纤维密度的绒毛，将会取得最好的结果。绒毛中纤维的实际密度通过绒毛长度和纤维厚度的结合来确定。
本发明进一步涉及一种用来给水下材料提供至少部分覆盖有本发明的纤维绒的防污外层的方法。这些绒毛可以通过现有技术已知的任意制造方法来生产，可以直接应用到水下材料。在EP-A-312.600中描述了几种制造方法。
在一个具体实施例中，所述荆棘状表面的提供是通过首先把防水粘合剂(例如环氧树脂或聚氨酯)涂敷到水下材料以形成粘合剂层，其中在选定的纤维被充静电后与粘合层接触，例如使用喷雾技术。
在另一个具体实施例中，所述绒毛也可以薄板使用。因此，本发明也涉及一种薄板，其包括基本部件和附着在其上的本发明的纤维。所述基本部件可以由任何种类的材料制成，例如聚酯、聚乙烯、聚丙烯、乙烯树脂、织物和纸类材料。
另外，纱线可以做成具有纤维束形式的绒毛，该纱线可以经过织网或制绳的加工过程。接着该编织的织物可用于水下结构。
该加工方法适合于把纤维特别地用作包覆层、薄板、绳、网或织物，并能用于所有的水湿表面。该包覆层能通过适当选择其材料和形状，以适用于预期的污染颗粒的尺寸和预期的经过水下表面的水流。
当三维物体覆盖有本发明的荆棘状表面时，需要把所述物体固定在植绒机器(flocking machine)上以避免所述物体和装置接触的导向***。为物体提供粘合层的第一步可以通过例如喷雾、浸涂或辊压完成。为了节省在网喷涂情况下的粘合剂材料，浪费的粘合剂可以在网下收集。在浸涂的情况下，一定要注意避免形成不均匀的层，例如使用气喷。可以采用泡沫粘合剂。也可以调整粘合剂的流变性。
为了获得均匀分布的荆棘层，发现将流动势能和/或流出口与要覆盖物体之间的距离最优化是有用的。荆棘也可以以两个步骤布置：首先向所述物体提供低密度但是均匀分布的荆棘绒，之后通过相继的植绒步骤获得更密的覆盖。每个步骤可以具有自己最佳的速率和出口-物体距离。确定最佳条件被认为是在普通技术人员知晓的范围内。
当表面处于垂直位置时包覆荆棘是更有利的。同样，所述物体也可以反向充电，不需要相同的绝对量。通常，所述物体是接地的。
如果是网，网后面的空气流或第二(接地的或反向充电的)物体可以用来提高通过率。可以同时从两侧提供所述荆棘。
为了使藻类的依靠光合作用的生长最小化，所述水下材料可以染色。所述荆棘状表面的阻止效果可以通过选择纤维层里的颜料进一步提高，所述颜料几乎不吸收适合于容易附着到采用所述材料的水中的藻类的光合作用的波长范围内的光线。紫外线吸收剂也可以用来阻止由紫外线辐射引起的老化和/或提高纤维包覆的材料的耐久性。如果需要的话，可以通过使用添加剂(例如纳米结构颗粒)来提高所述纤维硬度。
具体实施方式
实施例1
使用防水聚氨酯胶作为粘合剂和几种不同类型的密度为20荆棘/mm2、由聚酰氨制成的荆棘(长度>3mm，厚度>60μm)，将30×20cm2的PVC板包覆荆棘。使用静电植绒施加。胶水硬化后，所述PVC板暴露在海水中10个月。普通的PVC板也暴露在海水中。具有所述荆棘的所有材料没有被污染。不具有所述荆棘的面板被蚌类、藤壶和藻类污染。
对比实施例I
使用防水聚氨酯胶作为粘合剂和几种不同类型的密度为20荆棘/mm2、由聚酰氨制成的荆棘(长度0.5mm和2mm，厚度<60μm)，将30×20cm2的PVC板包覆荆棘。使用静电植绒施加。胶水硬化后，所述PVC板暴露在海水中10个月。具有所述荆棘的所有材料被蚌类、藤壶和藻类污染。
对比实施例II
由Deutsche Bundesstiftung Umwelt资助、在2003年11月的InternationalSymposium on Biocide-fredd Antifouling Coatings performance，Prospectsand Regulations中提出的大型研究项目里，“摆动”纤维用于防止污染。纤维长度1.0mm和1.2mm，纤维密度为200纤维/mm2。在一段时间后污染的覆盖率达到100％，严重污染(例如藤壶)达到70％，表明具有“摆动”运动的细纤维对于防止附着污染不是很有效。
实施例2
使用防水聚氨酯胶作为粘合剂和由聚酰氨制成的密度为20荆棘/mm2的荆棘(长度>3mm，厚度>60μm)，将由尼龙和纤维防弹线(Dyneema)制成的六边网格的柔性无结网的大小为20×20cm2的样品、和具有方形网格的由PVC制成的硬网材料的大小为20×20cm2的样品包覆荆棘。使用静电植绒进行施加。粘合剂硬化后，所述样品网和作为参照的没有包覆所述的荆棘的样品网一起暴露在海水中8个月。所有具有荆棘的材料没有被污染，而参照网材料有轻微的藻类、水螅虫类和海鞘污染和严重的蚌类和藤壶污染。
Claims (11)
1.一种具有防污特性的纤维包覆的水下材料，其中至少部分所述水下材料被具有至少50μm的厚度和至少3mm的纤维长度的纤维绒覆盖，其中所述纤维的厚度与长度的比例为至少0.010，并且其中所述纤维绒具有低于40纤维/mm2的密度。
2.如权利要求1的纤维包覆的水下材料，其中所述厚度在70μm和150μm之间。
3.如权利要求1或2的纤维包覆的水下材料，其中所述长度在3mm和10mm之间。
4.如权利要求1或2的纤维包覆的水下材料，其中所述纤维的厚度与长度的比例在0.015和0.025之间。
5.如权利要求1或2的纤维包覆的水下材料，其中所述纤维是任选被改性的聚亚烷基。
6.如权利要求1或2的纤维包覆的水下材料，其中其不含生物活性剂。
7.如权利要求1或2的纤维包覆的水下材料，向其中加入生物活性剂。
8.一种用于提供具有防污外层的水下材料的方法，所述方法包括向水下材料提供附着在其上的具有至少50μm的厚度和至少3mm的纤维长度的纤维绒，其中所述纤维的厚度与长度的比例至少为0.010，并且所述纤维绒具有低于40纤维/mm2的密度。
9.如权利要求8的方法，其中首先将防水粘合剂涂敷到所述水下材料上以形成粘合层，所述纤维被充静电后与所述粘合层接触。
10.一种适于为水下材料提供防污特性的纤维包覆的薄板，其中所述薄板包括基本部件和附着在其上的纤维绒，所述纤维绒具有至少50μm的厚度和至少3mm的纤维长度，其中纤维的厚度和长度的比例至少为0.010，所述纤维绒具有低于40纤维/mm2的密度。
11.如权利要求10的纤维包覆的薄板，其中所述基本部件由聚合物材料的薄片制成。
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| WO2011145927A1 (en) | 2010-05-18 | 2011-11-24 | Materials Innovation Centre B.V. | Antifouling fibre coatings for curved constructions |
| DE102011012517A1 (de) * | 2011-02-25 | 2012-08-30 | Renolit Ag | Verfahren zum Schutz von Oberflächen vor Bewuchs |
| DE102012102161A1 (de) * | 2012-03-14 | 2013-09-19 | Ewald Dörken Ag | Antifouling-Bahn |
| DE102012210294A1 (de) | 2012-06-19 | 2013-12-19 | Evonik Industries Ag | Bewuchsmindernde-Additive, Verfahren zu deren Herstellung und deren Verwendung in Beschichtungen |
| NL2018082B1 (en) | 2016-12-27 | 2018-07-03 | Innovalue B V | Coating for long term flow control around marine objects |
| CN107177050B (zh) | 2017-07-10 | 2019-03-19 | 中国船舶重工集团公司第七二五研究所 | 一种微结构与防污活性物质协同防污材料及其制备方法 |
| KR102120781B1 (ko) * | 2018-11-21 | 2020-06-17 | 한국해양과학기술원 | 능동 기체 생성을 이용한 능동 방오표면의 방오성능 향상 방법 |
| CN111169606A (zh) * | 2020-01-02 | 2020-05-19 | 杭州友凯船艇有限公司 | 解决海洋附着生物的纤维布套及其制备方案 |
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| US3554154A (en) * | 1969-02-26 | 1971-01-12 | Firestone Tire & Rubber Co | Structure with antifouling surface |
| JPS5256737A (en) * | 1975-09-14 | 1977-05-10 | Mitsubishi Heavy Ind Ltd | Method of preventing oceanic life from adhering |
| JPS61164829A (ja) * | 1985-01-17 | 1986-07-25 | 住友金属工業株式会社 | 防汚被覆金属材 |
| JPS62239934A (ja) * | 1986-04-10 | 1987-10-20 | 澤下 明夫 | 防汚材料 |
| US5116655A (en) * | 1988-07-28 | 1992-05-26 | Tuguo Ezoe | Preventive method against apposition of a marine organism and a preventive sheet against apposition of a marine organism |
| JPH02274911A (ja) * | 1989-04-17 | 1990-11-09 | Tsugio Ezoe | 貝類付着防止シート |
| US4923730A (en) * | 1988-08-04 | 1990-05-08 | Dai-Ichi High Frequency Co. Ltd. | Anti-fouling surface structure, anti-fouling covering material and method of planting ribbons for producing anti-fouling surface structure and covering material |
| JP2684783B2 (ja) * | 1989-08-18 | 1997-12-03 | 東レ株式会社 | 水中フェンス |
| WO1992007037A1 (en) * | 1990-10-11 | 1992-04-30 | A.B.O.E. Pty Ltd. | Anti-fouling composition |
| SE9201736D0 (sv) * | 1992-06-05 | 1992-06-05 | Juristbyraon Indirekt Ab | Fartyg, saasom baatar, flygplan etc. |
| JPH06311831A (ja) * | 1993-04-26 | 1994-11-08 | Akira Yokoyama | 貝付着防止養殖用植毛漁網 |
| JPH08322430A (ja) * | 1995-06-01 | 1996-12-10 | Lion Corp | 水生生物付着防止方法およびその用具 |
| JP2000303423A (ja) * | 1999-04-19 | 2000-10-31 | Nisshoku Corp | 海水との接水壁面に対する貝類の付着防止方法 |
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| US8278226B2 (en) | 2012-10-02 |
| ES2356044T3 (es) | 2011-04-04 |
| JP5161201B2 (ja) | 2013-03-13 |
| NO337906B1 (no) | 2016-07-04 |
| WO2007108679A8 (en) | 2009-01-08 |
| EP1996453B1 (en) | 2010-11-10 |
| ATE487657T1 (de) | 2010-11-15 |
| WO2007108679A1 (en) | 2007-09-27 |
| JP2009530144A (ja) | 2009-08-27 |
| DE602007010432D1 (de) | 2010-12-23 |
| NO20084092L (no) | 2008-12-19 |
| EP1996453A1 (en) | 2008-12-03 |
| CA2646436A1 (en) | 2007-09-27 |
| AU2007227903B2 (en) | 2011-10-13 |
| US20100227111A1 (en) | 2010-09-09 |
| CN101443230A (zh) | 2009-05-27 |
| AU2007227903A1 (en) | 2007-09-27 |
| CA2646436C (en) | 2015-01-06 |
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