CN100374621C - 在由钛锌制成的平面制品上制备深色保护层的方法 - Google Patents

在由钛锌制成的平面制品上制备深色保护层的方法 Download PDF

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CN100374621C
CN100374621C CNB02822700XA CN02822700A CN100374621C CN 100374621 C CN100374621 C CN 100374621C CN B02822700X A CNB02822700X A CN B02822700XA CN 02822700 A CN02822700 A CN 02822700A CN 100374621 C CN100374621 C CN 100374621C
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titanium
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zinc
pickling
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CN1585834A (zh
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M·舒内贝克
A·斯特拉德曼
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Rheinzink GmbH and Co KG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Treatment Of Metals (AREA)
  • Physical Vapour Deposition (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

本发明涉及一种通过对经轧制的用于建筑业的钛锌平面制品的酸洗而制备深色保护层的方法，所述平面制品在含硫酸和硝酸的混合酸的水性酸洗浴中酸洗，并且在冲洗后通过覆有保护层而钝化。作为经轧制的平面制品使用由钛-锌-合金构成的平面制品。该合金主要含有高纯度的锌，和此外1.0-2.0重量%的铜含量、0.06-0.2重量%的钛含量和最大为0.015重量%的铝含量。

Description

在由钛锌制成的平面制品上制备深色保护层的方法
本发明涉及通过对由钛-锌-合金制成的用于建筑业的经轧制的平面制品的酸洗而制备深色保护层的方法，在此，平面制品在水性的含有硫酸和硝酸的混合酸中酸洗，并且在冲洗后在形成保护层的情况下被钝化。此外本发明还涉及具有保护层的平面制品。
从DE 196 36 370 A1获知一种这样的方法，在此完全地引入其内容。用该文献中公开的对由钛-锌-合金制成的钛锌板材的处理，在钛锌板材的表面得到均匀的、灰色的保护层，合金具有0.07-0.12重量％的钛、直至0.015重量％的铝、0.08-0.17重量％的铜和余量为99.995％的锌，其灰色在美观方面被认为特别优越的，因为它相应于锌的天然的铜锈色。在DE 196 36 370 A1中所公开的合金，在其组成成分上相应于TV Produkt und Umwelt GmbH，环保和能源技术研究所，Am grauenStein，51105 Kln的“质量锌”-目录的标准。
然而试验已经表明，用该已知的方法，在一些情况下所期望的板材的深色只有稍许，并且通过应用较高浓度的酸才能达到。由此存在问题，随着酸的强度升高，即酸洗浴的pH-值较低，合金物质会被侵蚀，金属厚度就会减小。特别地，使用非常低的pH-值的混合酸导致在表面上的所不期望的层结构构造，因为形成了所谓的酸洗沉积物不良附着层。从而用已知的方法将钛锌板材制成更深色受到限制。然而对于建筑业非常深色的表面层也是所期望的，以使得特别在屋顶铺层和正面覆盖面的区域保持预先安装的锌板材与其他所用建筑材料，如黑色的油页岩面板或法兰密斯瓦较小的对比度反差，或与白色的表面正好引成强烈的对比度反差。
还已知对钛锌的磷酸化处理而制备深色表面的方法(参见DIN 50942)。然而这样就以不期望的方式改变了金属表面结构，假如表面不进一步用漆涂层的话。
所以本发明的任务是，这样地进一步研发上述种类的方法，即可制备具有非常深色的直至黑色的表面的钛锌板材，在此应保持金属表面的自然结构。
该任务如此解决，即针对上述的合金成分，采用具有提高了的铜含量的钛-锌-合金，铜含量为1.0-2.0重量％，然而该合金含有上述份额的钛和铝。
令人惊奇地，用这种提高了的铜含量与其他的已知的合金组成成分一起和采用已知的处理方法得到了比使用通常的、铜含量低的合金更深色的铜锈色。根据迄今为止的知识，铜锈色特别地由具有痕量-铜的碳酸锌构成。
所得到的暗黑色允许，这种铜锈色的建筑材料可特别和谐地用于具有黑色的波形瓦或木瓦的屋顶铺层中，或在那些期望有对比度反差的地方，给出明显的黑-白色层次。优选地在合金中1.1-1.4重量％的铜含量已经足够了。下面通过实施例更清楚地解释根据本发明的方法：
应用一种钛-锌-合金，其含有0.06-0.2重量％的钛和最大为0.015重量％的铝。根据本发明铜含量为1.0-2.0重量％，优选地为1.1-1.3重量％的Cu。合金的主要成分由锌构成，也即根据合金元素钛、铝和铜的含量由约97.7-98.9重量％的锌(纯度为99.995重量％)构成。
由具有提高了的铜含量的锌合金制成的0.8mm厚和600mm宽的带材用碱性的去除脂肪的溶液在约60℃的温度下和约2.5bar的冲洗压力下冲洗去除脂肪，随后用约65℃的温度的和约2.5bar的压力的水喷射流冲洗。为了支持冲洗过程和为了表面粗糙，在最后的冲洗阶段刷擦带材。随后带材在具有酸洗浴温度为30-80℃，优选为50℃的酸洗装置中酸洗。酸洗浴含有在水中约30-60g/l的硫酸和约20-50g/l的硝酸的混合酸。附加地还有25-80g/l，优选约为50g/l的溶解的锌-离子。
酸洗反应的速度基本上取决于自由酸的含量。硝酸的还原是主要的反应并阻止了氢气的产生。另一个对酸洗结果的影响由酸含量的比例给出。
优选地应用具有2-10体积％的硫酸和2-10体积％的硝酸，在此硫酸∶硝酸的混合比例是小于或等于3∶1，且自由酸的含量为25-100g/l。
从酸洗装置中取出的带材进行如上所述的冲洗。随后优选地如下通过涂覆和干燥含铬的聚合物分散体而生成进一步的保护层。
在去除残余水后，在带材上通过轧制而涂覆上由65-98体积％，优选为95体积％的聚合物分散体与2-35体积％，优选为5体积％的水性铬溶液构成的混合物。在约80-120℃下干燥涂层。在经干燥的状态下所生成的薄膜的层厚为约0.4-3.0μm，优选为1.5μm。
在此，对于聚合物分散体例如理解为由苯乙烯-丙烯酸酯、脂肪族聚酯和聚氨基甲酸酯构成的混合物。
优选地，用本发明的方法得到这样一种由钛-锌-合金制成的平面制品，其主要具有高纯度的锌和此外1.0-2.0重量％的铜含量、0.07-0.12重量％的钛含量和最大为0.015重量％的铝含量，并且具有暗黑色的铜锈色。后者优选用具有厚度为0.4-3.0μm的保护层涂覆，其在实施例中在含铬的聚合物分散体的涂覆和干燥后得到；相应的涂层的面密度为5-40mg/m2。

Claims (6)

1.一种通过对经轧制的用于建筑业的钛锌平面制品的酸洗而制备深色的保护层的方法，所述平面制品在含硫酸和硝酸的混合酸的水性酸洗浴中酸洗，并且在冲洗后通过涂覆另一层保护层而钝化，其特征在于，应用由钛-锌-合金构成的经轧制的平面制品，根据合金元素钛、铝和铜的含量，该合金具有含量为97.7-98.9重量％、纯度为99.995重量％的锌，和此外具有1.1-2.0重量％的铜含量、0.06-0.2重量％的钛含量和最大为0.015重量％的铝含量。
2.根据权利要求1的方法，其特征在于，铜含量在1.1和1.4重量％之间。
3.根据权利要求1或2的方法，酸洗浴除了含有水外，还含有30-60g/1的硫酸和20-50g/l的硝酸。
4.根据权利要求1或2的方法，其特征在于，通过涂覆和干燥含铬的聚合物分散体而生成另一层保护层。
5.一种由钛-锌-合金制成的平面制品，其在有硫酸和硝酸的加入下酸洗且被钝化为深色保护层，根据合金元素钛、铝和铜的含量，钛-锌-合金具有含量为97.7-98.9重量％、纯度为99.995重量％的锌，此外还具有1.0-2.0重量％的铜含量、0.07-0.12重量％的钛含量和最大为0.015重量％的铝含量。
6.根据权利要求5的平面制品，其特征在于，通过涂覆和干燥含铬的聚合物分散体而生成另一层保护层来覆盖酸洗后的保护层。
CNB02822700XA 2001-11-16 2002-11-15 在由钛锌制成的平面制品上制备深色保护层的方法 Expired - Lifetime CN100374621C (zh)

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DE10156475A DE10156475A1 (de) 2001-11-16 2001-11-16 Verfahren zur Herstellung von dunklen Schutzschichten auf Flacherzeugnissen aus Titanzink
DE10156475.9 2001-11-16

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DE112007003465T5 (de) * 2007-04-27 2010-05-06 Shine Metal Hot - Galvanization Enterprise Verfahren zum bleifreien Feuerverzinken und bleifrei feuerverzinktes Produkt
US8442507B2 (en) * 2007-09-26 2013-05-14 Qualcomm Incorporated Methods and apparatus for dynamic source determination of provisioning information on a per-network service basis for open market wireless devices
US8831575B2 (en) * 2007-09-26 2014-09-09 Qualcomm Incorporated Apparatus and methods associated with open market handsets
US20090082004A1 (en) * 2007-09-26 2009-03-26 Qualcomm Incorporated Apparatus and methods of open market handset identification
CN103849868A (zh) * 2014-02-14 2014-06-11 浙江工业大学 一种钛锌板表面无铬发黑处理液及使用方法
EP3211113A1 (en) 2016-02-25 2017-08-30 Rautaruukki Oyj Galvanized product & method
CN114000136A (zh) * 2021-10-28 2022-02-01 苏州市祥冠合金研究院有限公司 一种锌合金表面涂层的制备方法
CN115433932B (zh) * 2022-08-29 2023-09-12 武汉大学 一种纯钛表面梯度微纳TiZn3-TiZnX复合涂层及其制备方法

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EP0827785A2 (de) * 1996-09-09 1998-03-11 Rheinzink Gmbh Verfahren zur Herstellung von Schutzschichten auf Flacherzeugnissen aus Titanzink

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US6916546B2 (en) 2005-07-12
AU2002352012A1 (en) 2003-06-17
ES2236604T3 (es) 2005-07-16
CN1585834A (zh) 2005-02-23
DE10156475A1 (de) 2003-06-05
EP1444381A1 (de) 2004-08-11
DE50202024D1 (de) 2005-02-17
ATE286993T1 (de) 2005-01-15
HK1072785A1 (en) 2005-09-09
EP1444381B2 (de) 2008-09-10
JP2005511896A (ja) 2005-04-28
US20050003091A1 (en) 2005-01-06
EP1444381B1 (de) 2005-01-12
ES2236604T5 (es) 2009-03-01

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