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CN1338008A - 具有减少形成沉积物趋势的传热设备及其制造方法 - Google Patents

具有减少形成沉积物趋势的传热设备及其制造方法 Download PDF

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CN1338008A
CN1338008A CN99816373A CN99816373A CN1338008A CN 1338008 A CN1338008 A CN 1338008A CN 99816373 A CN99816373 A CN 99816373A CN 99816373 A CN99816373 A CN 99816373A CN 1338008 A CN1338008 A CN 1338008A
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dispersion layer
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S·许菲
A·弗兰克
S·肖尔
H·米勒－斯坦哈根
Q·赵
B·迪波尔德
P·迪尔曼
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Abstract

本发明涉及一种制造传热设备的方法,其特征在于通过无电化学沉积一层金属－聚合物－分散体层到传热设备表面,其中聚合物是卤化的。本发明另一目的是一种提供制造传热设备的方法,其特征在于,在涂敷金属－聚合物－分散体层之前,先通过无电化学沉积一层厚1－15μm的金属－磷－层。本发明的再一目的是一种可通过本发明的方法制造的传热设备,以及通过金属－聚合物－分散体层的无电化学沉积的涂层的应用,其中聚合物是卤化的,其目的是降低流体中固体物在涂敷表面上形成沉积物的趋势。

Description

具有减少形成沉积物趋势的传热设备及其制造方法
本发明涉及一种用于制造载热体的方法，该法包括金属-聚合物-分散体层的无电化学沉积。其次，本发明还涉及按本发明制造的传热设备。再次，本发明涉及金属-聚合物-分散体层作为永久性结壳抑制剂的应用。
最近十年期间几乎所有的工业部门皆遇到换热器中的沉积问题(Steinhagen et al.(1982)，Problem and Cost Due to HeatExehanger Fouling in New Zealand Industries，(新西兰工业界中由于换热器结垢产生的问题及花费)，Heat Transfer Eng.(传热工程)，14(1)，19-30页)。在计算换热器时应该考虑沉积(结垢)引起的摩擦压力损失和载热剂的阻力。这将使换热器的尺寸增大10-200％。
因此，抗结垢-方法的研究成为一个相当重要的问题。
机械解决方法具有缺点，即它被限制在较大的换热器，而且会带来巨大的附加费用。化学添加剂可能使产品受到不希望的沾污，而且部分会加重环境的负担。
出于这些原因，近年在寻找一种方法，该方法能通过传热表面的改性以降低结垢趋势。带有有机聚合物如聚四氟乙烯(PTFE)的表面涂层虽然能降低形成沉积物的趋势，但是某些已知涂层本身会明显增加导热阻力。同时由于可耐用性的缘故，其涂层厚度有一下限。类似的问题亦表现在拟保护的表面涂敷单层-硅烷涂层的方法中(Polym.Mater.Sci.and Engineering(聚合物材料科学与工程)，Proceedings of the ACS Division of Polymeric Meterials Scienceand Engineering(聚合物材料科学与工程美国化学学会分部会刊)(1990)，卷62，259-263页)。
应用聚合物涂层引起的问题在WO97/16692描述的方法中并未出现。在这个方法中通过离子植入或通过阴极溅射技术提高表面的憎水性。这虽然降低结垢趋势，但是总是要求真空技术的方法的应用是很昂贵的。加上所描述的方法不适宜在难以接近或者复杂形状的表面或部件上涂敷均匀的涂层。
应防止的沉积物涉及无机盐如硫酸钙和硫酸钡、碳酸钙和碳酸镁、无机磷酸盐、硅酸和硅酸盐、腐蚀产物、颗粒状沉积物如冲积砂(河水和海水)、以及有机沉积物如细菌、藻、蛋白质、贝壳或贝壳类幼虫、聚合物、油和树脂及上述物质组成的生物矿化复合物。
本发明的目的在于提出一种制造传热设备的方法，该方法一方面降低传热面上沉积固体物的趋势，另一方面在较高强度(抗热抗腐蚀和抗冲刷)下导致可忽略程度的导热阻力。而且按本发明处理过的表面具有令人满意的可耐用性。这种方法亦可以合理的费用应用于难于接近的表面。
本发明的目的通过一种用于制造传热设备的方法来达到，其特征在于，在传热设备的表面上，采用无电化学沉积金属-聚合物-分散体层，而且该聚合物是经过卤化的。
传热设备在本发明的范围内系指一种具有为热交换而设计的表面(传热表面)的装置。优选是与流体，特别是液体进行热交换的换热器。
加热部件和换热器，特别是板式换热器和螺旋式换热器是换热器的优选实施方案。
卤化聚合物是一种氟化的或氯化的聚合物；优选氟化聚合物，尤其是全氟化聚合物。全氟化聚合物的例子为聚四氟乙烯(PTFE)和全氟-烷氧-聚合物(PFA，按DIN7778，部分1，1988年6月)。
达到本发明目的一种方法是基于以无电化学沉积金属-聚合物-分散体层，这种方法已有报导(W.Riedel：功能性镀镍，Eugen Leize出版社，Saulgau，1989231-236页，ISBN3-750480-044-x)。金属-聚合物-分散相包括聚合物，在本明的范围内为一种卤化聚合物，该聚合物分散在金属-合金之中。金属-合金主要涉及金属-磷-合金。
迄今为降低结壳趋势所采用的方法导致比电抛光钢还粗糙的表面(参见表1)。曾经发现，能使粗糙度降低的涂层能同样满足要求。此外还发现，对降低结壳趋势起决定作用的是聚合物含量，虽然分散体层中的聚合物含量是低的，为5-30％(体积)。
此外，曾经确定，按本发明处理过的表面能很好导热，虽然1-100μm的涂层厚不能认为不大。按照本发明处理过的表面还具有满意的耐用性，涂层厚度为1-100μm时是恰当的；优选3-20μm，尤其是5-16μm。分散体涂层的聚合物含量为5-30％(体积)，优选15-25％(体积)，特别是19-21％(体积)。其次，本发明工艺条件下采用的涂层价格相对合理，并能涂敷以于接近的表面。这类表面涉及任何一种传热设备表面如管内表面、电加热部件的表面、和板式换热器表面等，这些表面可用作工业装置中流体的加热与冷却，住宅的加热与冷却，食品加工或在发电或水处理装置中的加热与冷却。
“导热”系指从传热设备内部传到面向流体的涂层的传热、涂层内部的导热和从涂层到流体(例如盐溶液)的传热。
本发明方法的一个优选实施方案中，金属-聚合物-分散体层的金属-磷-合金涉及铜-磷或镍-磷；优选镍-磷。
本发明方法的另一优选实施方案中，镍-聚合物-分散体层涉及镍-磷-聚四氟乙烯组成的分散体层。但是其它的氟化聚合物亦是适宜的，如全氟烷氧-聚合物(PFA，由四氟乙烯和全氟烷氧乙烯基醚，如全氟乙烯基丙基醚的共聚物)。如果传热设备在较低的温度运行，则同样可设想采用氯化的聚合物。
在本发明的另一实施方案中，金属-聚合物-分散体层具有球状聚合物颗粒，其平均直径(中值)为0.1μm-1.0μm，尤其是0.1-0.3μm。
与电流沉积相反，在镍-磷的化学或自催化沉积中为此所需的电子不是通过外电流源提供，而是通过化学反应在电解质本身中产生(还原剂的氧化)。涂敷是通过将工件浸于金属-电解质溶液中完成，该溶液预先与一种被稳定的聚合物分散体相混合。紧接浸没过程，宜在200-400℃下，特别在315-325℃下进行退火。退火时间通常为5分钟-3小时，优选35-45分钟。作为金属溶液可采用例如市售的镍电解质溶液，该溶液含NiII、次磷酸盐、羧酸和氟化物，有时还含沉积缓和剂如Pb2+。这类溶液例如为Riedel，Galvano-和Filtertechnik公司，Halle，Westfalen和Atotech Deutschland公司，Berlin经销。作为聚合物可采用例如市售的聚四氟乙烯分散体(PTFE-分散体)。优选固体物含量为35-60％(重量)的、平均颗粒直径(中值)为0.1-1μm，尤其是0.1μm-0.3μm的PTFE分散体，其颗粒具有球状形态，而且含有中性洗涤剂(例如聚乙二醇，烷基酚基乙氧酸盐或上述物质的混合物，80-120g中性洗涤剂/升)  和一种离子型洗涤剂(例如烷基磺酸盐和卤烷基磺酸盐、烷基苯磺酸盐、烷基酚基醚硫酸盐、四烷基铵协或上述物质的混合物，15-60g离子型洗涤剂/升)。典型的浸没浴的pH-值为5左右，并含大约27g/l的NiSO4×6H2O和大约21g/l的NaH2PO2×H2O，而PTFE的含量为1-25g/l。
分散体层的聚合物含量主要受聚合物分散体添加量和洗涤剂选择的影响。
本发明的另一目的是提供用于制造传热设备的方法，该设备具有附着性特强的、耐用的、抗热的涂层、因而以特殊的方式达到了本发明的目的。
这种方法是基于，一种制造传热设备的方法，其特征在于以无电流化学沉积将金属-聚合物-分散体层沉积到传热设备的表面，而且该聚合物是经过卤化的。
这种方法的特征在于，在涂敷金属-聚合物-分散体层之前，先以无电化学沉积厚度为1-15μm的金属-磷-层。
为改善附着性的1-15μm厚的金属-磷-层的无电化学涂敷，通过已经叙述的金属-电解液浴实现，但是在这种情况下不向电解液添加任何被稳定的聚合物-分散体。在此时不进行退火，因为它对后继的金属-聚合物-分散体层的附着性通常有负影响。在沉积金属-磷-层之后，工件浸没入上述的浸没浴中，该浴除含金属-电解质外，还包括被稳定的聚合物分散体。在此形成金属-聚合物-分散体层，接着宜在200-400，尤其在315-325℃下进行退火。退火时间通常为5分钟-3小时，优选35-45分钟。
在本发明的另一个优选实施方案中，金属-磷-层的厚度为1-5μm。
本发明方法的另一实施方案中，金属-聚合物-分散体层的金属-磷-合金和金属-磷-层涉及镍-磷或铜-磷。
本发明方法的另一实施方案中，金属-聚合物-分散体层涉及由镍-磷-聚四氟乙烯组成的分散体层。
本发明再一目的是提供通过本发明的方法制造的传热设备。本发明的传热设备宜采用本发明的方法进行制造。
在另一实施方案中，上述本发明的传热设备是为将热传给流体，尤其是液体而设计的。这里涉及全部将热传到流体的加热部件。其次为热交换器，尤其是板式热交换器和螺旋式热交换器，是这类传热设备的优选例子。
本发明再一目的是涂层的应用，该涂层是通过无电沉积金属-聚合物-分散体层而制造的，而且该聚合物是经过卤化的，其目的在于降低流体中固体物在被涂表面上形成沉积物的趋势。流体主要涉及液体。本发明要防止其生成的沉积物已有叙述。
本发明的传热设备或其涂层的某些优点将在附图中显示出来，其中，
图1表示在不同的热交换表面与沸腾的盐溶液接触时，在通过有涂层存在的边界层的导热系数随时间的变化。
图2表示在不同的热交换表面与流过的热的盐溶液接触时，在通过有涂层存在的边界层的导热系数随时间的变化。
图1表明，在表面特性各不相同的不同传热设备中，由于CaSO4-沉积物其导热系数(α[W/m2K])随时间而下降的关系。标号1表示实施例(*7)的本发明涂层的测量数据。标记2表示电抛光的钢表面的测量数据。单位面积功率为200kW/m2，CaSO4-溶液的浓度为1.6g/l，而温度相当于沸点。
图2表明，在表面特性各不相同的传热设备中由于CaSO4-沉积物，其导热系数(α[W/m2K])随时间(t[min]，横坐标)而下降的关系。标号1涉及实施例(*7)的本发明的涂层。标号3表示未经处理的钢表面。传热设备单位表面功率为100kW/m2。浓度为2.5g/l的CaSO4溶液以80cm/s的速度在80℃的温度下流过传热设备。
实施例
实验室试验曾确定按照本发明涂敷的加热表面与相应的未经涂敷的加热表面即电抛光表面和离子植入或阴极溅射表面相比较的优点。表1列出了表面粗糙度、表面能和被研究加热表面的湿润角的测量值，以及在试验过程的最初100小时内测出的导热系数的相对降低情况。结果表明，本发明的传热设备具有很低的表面能、很大的接触角以及很好的传热行为。
表1
  表面能[mJ/m2]*   接触角[°]**  粗糙度μm****  α100/α0***
未处理(钢)     84     65     0.14     0.4
抛光的钢     86     62     0.08     0.65
Si-离子植入的钢*5     39     80     0.14     0.75
钢F-离子值入的钢*5     37     82     0.14     0.9
DLC溅射的钢*6     36     85     0.13     0.85
TiNF溅射的钢*6     34     87     0.14     0.9
钢/Ni-PTFE*7     25     100     0.1     0.9
表2比较了本发明的传热设备与现有技术的传热设备的表面能、接触角、和单位面积沉积的细菌(嗜热链球菌)。
表2
  表面能[mJ/m2]*  接触角[°]**   Log10菌数/cm2*9
 未处理(钢)     84     65     5.7
 电抛光钢     86     62     5.5
 Si-离子植入的钢*5     39     80     4.9
 F-离子植入的钢*5     37     82     5.5
 DLC溅射钢*6     36     85     5.0
 CrC溅射钢*6     34     87     4.1
 钢/Ni-PTFE     25     100     3.9
*根据A.J.Kindoch，Adhesion and Adhesives测定，Chapman&Hall，University Press，Cambridge1994
**根据D.K.Owens测定，J.of Appl.Polym.Sci.(应用聚合物科学志)3(1969)1741-1747
***100小时运行时间后的相对导热系数(根据Müller-Steinhagenet al.的方法，Heat Transfer Engineering(传热工程)17(1998)，46-63)
****表面粗糙度，根据DIN ISO为1302的Ra
*5根据J.M.Mayer方法“Ion Implantation in Semiconductors，Silicon and Germanium”(半导体、硅和锗中的离子植入)，Academic Press1970(ISSBN 75107563)
*6类金钢石-碳DLC的涂敷方法，根据GB-A9006073
*7首先通过浸没入化学无电镍-电解质溶液以无电化学涂敷5μm的含8％磷的镍层。接着在浸没浴中制造Ni-磷-PTFE-分散体层，该浴由无电化学镍-电解质溶液和经洗涤剂稳定的PTFE-分散体的混合物组成。镍-磷-聚四氟乙烯的沉积在87-89℃，亦可在低于90℃和电解质溶液pH-值为4.6-5.0的条件下进行，沉积速度为l0μm/h，层厚15μm。无电化学镍-电解质-PTFE-溶液的组成列于表3。
表3
    浓度[g/l]     pH
 NiSO4x6H2ONaH2PO2xH2OCH3CHOHCOOHC2H5COOH柠檬酸钠；NaFPTFE(50％)8*     2721203512-50     4,8
无电化学镍-电解质溶液是市售得到的(Riedel，Galvano-undFiltertechnik公司，Halle，Westfalen und der AtotechDeutchland公司，Berlin)。在涂敷镍-磷-PTFE-层之后，该工件在300℃下退火20分钟。分散体层中聚合物和磷的含量为20％(体积)PTFE(相当于6％(重量)PTFE)和7％磷。
*8PTFE-分散体是市售得到的。固体物含量和平均颗粒尺寸为50％(重量)和0.2μm。分散体用中性洗涤剂(50g/l烷基酸乙氧酸盐，商标为Lutensol；50g/l烷基酚乙氧酸盐，商标为Emulan，两种洗涤剂的厂商为BASF AG，Ludwigshafen)和离子型洗涤剂(15g/l烷基磺酸盐，商标为Lutensit，BASF AG，Ludwigshalfen；8g/l全氟-C3-C8烷基磺酸盐，商标为Zonyl，DuPont，Wilmington，U.S.A)稳定。浓度数值2-50是基于所加分散体溶液量计。
*9测量根据H.Müller-Steinhagen，Q.Zao和M.Reiβ进行，“A novellow fouling metal heat trasfer surface”(一种新型的低结垢金属的传热表面)，5th UK National Conference on HeatTransfer(第五届联合王国国家传热会议)，London17-18sept，1997.细胞培养物是嗜热链球菌。

Claims (12)

1.一种传热设备的制造方法，其特征在于，将金属-聚合物-分散体层以无电化学沉积到传热表面，而且该聚合物是经过卤化的。
2.权利要求1的方法，其特征在于，金属-聚合物-分散体层的金属-磷-合金涉及铜-磷或镍-磷。
3.权利要求2的方法，其特征在于，镍-聚合物-分散体层涉及由镍-磷-聚四氟乙烯的分散体层。
4.权利要求1-3之一的方法，其特征在于，金属-聚合物-分散体层具有平均直径为0.1μm-1.0μm的球状聚合物颗粒。
5.权利要求1-3之一的方法，其特征在于，金属-聚合物-分散体层具有平均直径为0.1μm-0.3μm的球状聚合物颗粒。
6.权利要求1-5之一的方法，其特征在于，在涂敷金属-聚合物-分散体层之前，先通过无电化学沉积涂敷厚度为1-15μm的金属-磷层。
7.权利要求6的方法，其特征在于，金属-磷-层的厚度为1-5μm。
8.权利要求6或7的方法，其特征在于，金属-聚合物-分散体层的金属-磷-合金和金属-磷-层涉及镍-磷或铜-磷。
9.权利要求8的方法，其特征在于，金属-聚合物-分散体层涉及由镍-磷-聚四氟乙烯组成的分散体层。
10.一种按权利要求1-9之一的方法制造的传热设备。
11.权利要求10的传热设备，它是为与流体进行换热而设计的。
12.通过无电化学沉积制备的金属-聚合物-分散体层的涂层的应用，其中该聚合物是经过卤化的，其目的为降低流体中固体物在被涂表面上表成沉积物的趋势。
CN99816373A 1998-12-30 1999-12-24 具有减少形成沉积物趋势的传热设备及其制造方法 Pending CN1338008A (zh)

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WO2000040775A2 (de) 2000-07-13
ATE237006T1 (de) 2003-04-15
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WO2000040775A3 (de) 2000-11-09
US6617047B1 (en) 2003-09-09
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WO2000040773A3 (de) 2000-11-09
CA2358099A1 (en) 2000-07-13
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EP1144723A2 (de) 2001-10-17
CN1636305A (zh) 2005-07-06
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