CN1497065A - 防腐耐热锌扩散合金镀层 - Google Patents

防腐耐热锌扩散合金镀层 Download PDF

Info

Publication number
CN1497065A
CN1497065A CNA031649149A CN03164914A CN1497065A CN 1497065 A CN1497065 A CN 1497065A CN A031649149 A CNA031649149 A CN A031649149A CN 03164914 A CN03164914 A CN 03164914A CN 1497065 A CN1497065 A CN 1497065A
Authority
CN
China
Prior art keywords
nickel
plating
zinc
matrix
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA031649149A
Other languages
English (en)
Other versions
CN100360713C (zh
Inventor
Hm
H·M·霍金斯
¡
T·R·汉隆
P·巴蒂亚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raytheon Technologies Corp
Original Assignee
United Technologies Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Publication of CN1497065A publication Critical patent/CN1497065A/zh
Application granted granted Critical
Publication of CN100360713C publication Critical patent/CN100360713C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • 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
    • C23C22/34—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 containing fluorides or complex fluorides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Laminated Bodies (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

本发明涉及一种防腐耐热的锌扩散镍合金镀层，以及一种形成该镀层的方法。该方法主要包括以下步骤，在基体上镀覆一层纯镍或镍合金镀层，在该纯镍或镍合金镀层上镀敷一层锌层，和使锌热扩散到镍合金镀层中。该方法可进一步包括在扩散步骤之前或之后将被镀基体沉浸到磷酸盐化三价铬转化溶液中。该基体可以是一种用在气体涡轮发动机的由钢材料制成组件。

Description

防腐耐热锌扩散合金镀层
技术领域
本发明涉及一种在其表面上有一层锌扩散镍合金镀层的钢基体以及一种形成所述镀层的方法。
技术背景
钢制品经常遭到大气侵蚀的破坏，所以必须进行保护。其通常是通过镀敷有机膜(漆)或金属镀层(电镀)来实现的。钢也经常遭到在高温下的热氧化，如果其要经受这种环境，则它必须通过适当的镀层进行保护。电镀或喷涂金属涂层或金属漆经常被用来在高温环境中提供保护，诸如在气体涡流发动机中的高温环境。当同时需要耐热防腐时，问题就出现了。耐高温镀层通常不能有效的提供大气侵蚀保护，而普通的能够防止大气侵蚀镀层在高于420℃(大约790°F)时提供很少的热防护作用。
发明概述
因此，本发明的一个目的就是提供一种能够耐热防大气侵蚀的镀层。
本发明的另一个目的是提供一种形成上述镀层的方法。
前述目的通过本发明的镀层和方法实现。
根据本发明的第一方面内容，提供一种在基体上镀覆防腐耐热镀层的方法。该方法主要包括以下步骤，在基体上镀覆一层镍基镀层，在该镍合金镀层上镀敷一层锌，和使锌扩散到镍合金镀层中。如果需要可以将所述待镀基体在所述扩散步骤之前或之后沉浸到磷酸盐化三价铬转化溶液中。
根据本发明的第二方面内容，提供一种具有至少一个表面和在其至少一个表面上的一层锌扩散镍合金镀层的钢基体。
关于本发明的方法和镀层的其他细节，和其他相应的目的和优点将在以下详细描述部分和附图部分中阐述，其中同样的附图标记代表相同的内容。
附图简述
图1是锌扩散镍合金镀层形成过程示意图；
图2是图示说明在钢基体上的锌扩散镍钴镀层的浓度分布的曲线图；
图3A和B图示说明一种暴露在ASTM B117盐雾中20小时后的镀有NiCo-Zn镀层的钢板。
图4是一种备选的锌扩散镍合金镀层形成过程示意图；
图5A和5B图示说明一种暴露在ASTM盐雾中199小时之前和之后的局部转化镀覆的样品。
优选实施方案详述
本发明包括将锌扩散到在先沉积在基体上的镍基镀层中。本发明的锌扩散镍合金镀层可以被镀覆在由较宽范围的材料制成的基体上，但在由钢材料制成的基体上如被命名为C1010的还原低炭钢合金尤其有效。
图1图示说明根据本发明的镀覆锌扩散镍合金镀层10的过程。该过程从准备一个洁净的基体12开始，该基体优选由钢材料制成。基体12可以是用于气体涡流发动机内的组件。纯镍或镍合金镀层14沉积在基体12的至少一个表面16上。任何适合的已知现有技术都可用于沉积镍或镍合金层14。优选地，该镍或镍合金镀层14的沉积速度为大约12.0μm/小时，其中电镀液的操作温度为室温(大约68°F(大约20℃)到130°F(大约55℃))。电镀液组成由电镀镍材料而定。典型的镍钴合金电镀液组成包括48-76g/l Ni，1.7-2.9g/l Co，15-40g/l硼酸，4.0-10g/l氯化物(来自NiCl2-6H2O)，其pH值为3.0至6.0，优选4.5至5.5。其他适合的可镀覆的镍合金包括NiFe，NiMo和NiSn。当镀覆镍钴合金时，钴在镀层中的含量应为7.0到40wt％。镀覆过程应当在电流密度0.5amps/dm2到4.304amps/dm2之间进行，其中电镀液的pH值保持在2.0至6.0。镍层14的厚度为2.0-20μm，优选1.0-14μm，最优选8.0-11μm。
在将镍层14沉积到基体12上后，锌层18将沉积到镍或镍合金层14上。锌层沉积可使用任何适当的现有已知技术。优选地，锌层沉积应用电镀技术，其中锌沉积在室温下以大约1μm/分钟的速度进行。锌电镀化学成分主要由锌硫酸盐加入乙酸钠和氯化盐组成。锌金属浓度为8.8g/l-45g/l。钠盐被用来提供适当的电镀液导电性。锌层在中度搅拌到轻度搅拌的室温溶液中沉积。适当的锌电镀液化学成分包括442.5g/l ZnSO4-7H2O，26.5g/l NaSOP4，13.8g/l CH3COONa-3H2O和1.0g/l NaCl。电镀液的pH值为4.8至6.2，其中pH值由NaOH或H2SO4调节。3.228amps/dm2至8.608amps/dm2范围内的电流密度可用来镀覆所述锌层。锌层18的厚度为0.8-14μm，优选2.0-14μm，最优选4.0-7.0μm。
锌层18中的锌可以应用任何适当的已知技术扩散到镍合金层14中。优选应用热扩散技术。热扩散可在空气炉或惰性气体炉内进行，其中扩散温度为600-800°F(315-427℃)，扩散时间至少为100分钟。若需要，热扩散可分两步进行，首先将镀有镍合金14和锌层18的基体12在80-100分钟内加热到上述温度范围的第一温度，然后在20到60分钟内加热到上述温度范围的第二温度，优选高于第一温度。
以下所作的测试用来表示本发明的镀层的作用。
试验用的测试面板由洁净的还原低炭钢取样管制成，所述面板在500ml室温搅拌的测试电镀液中镀敷一层镍钴合金镀层。所述合金镀层是在电流密度为0.5-4.0amp/dm2范围内进行沉积的。镍钴合金电镀液组成包括62g/l Ni，2.3g/l Co，27.5g/l硼酸，7g/l氯化物，其pH值为5，由NaOH或H2SO4调节。锌电镀液的锌金属浓度为8.0-45g/l。氯化钾和氯化铵盐用来提供想要的电镀液的导电率。在测验取样管上的锌层是在室温中度搅拌的溶液中沉积形成的。扩散分两个阶段完成，最典型的是先将样品控制在630°F(332℃)90分钟，然后控制在730°F(388℃)一个小时。
样品的X-射线图表明锌原子穿过镍钴镀层扩散到NiCo-Fe界面上，在较小的程度上镍和钴原子都扩散到锌镀层中，图2的浓度分布图表示不同种类的元素浓度梯度，该浓度梯度是由最初在大约2.0μm厚的锌和在其下3.0μm厚的镍钴合金扩散成5.4μm厚的镀层的扩散过程形成的。该图表明80％的镀层表面的金属原子是锌，锌的含量在NiCo-Fe界面上下降到几乎为0。
图3A和3B表示所加的锌是如何在腐蚀环境中提高本发明的镀层的性能的。图3A表示在热扩散循环之前(右)和之后(左)形成的镀层。图3B描述了暴露在ASTM B117盐雾中20个小时后的情况。样品的边缘用电镀带遮蔽。裸露的钢部分上的严重的红锈表示出暴露的电镀带的宽度。含63％的镍和37％的钴的镍钴合金单独起到了一些防腐作用，但被破坏的部分显示出很高的易腐蚀性(在样品镀层上冲压穿孔)。只有在沉积了一层薄的锌层随后又进行了热扩散的顶部表现出增强了的防腐蚀能力。
现在参看图4，如果需要，可以将所述带镀层的基体沉浸到一种磷酸盐化三价铬转化溶液中。沉浸步骤可以在最后扩散步骤之前或之后进行。
所述磷酸盐化三价铬转化溶液含有一种水溶性三价铬化合物，一种水溶性氟化物和一种可以减少三价铬的沉淀的增进防腐添加剂。该添加剂包括螯合剂或两个或三个配位基配体。通常，该添加剂的含量基于整个溶液是5ppm到100ppm，优选的基于整个溶液的含量为15ppm到30ppmm。优选的抑制腐蚀的添加剂包括氨基磷酸的衍生物，例如盐和酯衍生物像三磷酸三亚甲基胺(NTMP)，氨基烷基磷酸(hydroxy-amino-alkyl phosphoric acids)，乙基亚甲基亚氨磷酸(ethylimido(methylene)phosphoric acids)，二乙基氨甲基磷酸(diethyl aminomethyl phosphoricacid)等，可以是其中的一种或另一种或几种的组合，只要这种组合得到的添加剂是充分溶于水的。一种特别适当的用作腐蚀抑制剂和溶液稳定剂的添加剂是三磷酸三亚甲基胺(NTMP)。
稀释的酸性水溶液包括一种水溶性三价铬化合物，一种水溶性氟化物和一种氨基磷酸。溶液中三价铬化合物的含量为0.2g/l到10.0g/l(优选0.5g/l到8.0g/l)，氟化物的含量为0.2g/l到20.0g/l(优选0.5g/l到18.0g/l)。稀释的三价铬化合物电镀液的PH值为2.5到4.0。
通过使用三价铬含量为100ppm到300ppm、氟化物含量为200ppm到400ppm、抑制腐蚀氨基磷酸含量为10ppm到30ppm的电镀液得到了非常好的防腐作用且逐渐减少了三价铬的沉淀。
电镀后的基体沉浸到磷酸盐化三价铬转化溶液中5秒到15分钟，优选至少30秒。
图5A和5B表示本发明的经转化镀覆的作画线标记的镍锌镀覆取样管只有左半部分暴露在盐雾中。图5B表示的是同样的取样管暴露在ASTM B117盐雾中199个小时。比较图5A和5B显示转化镀覆部分尤其是作划线标记的部分是如何拥有更好的防腐能力的。镀有转化镀层的样品那半部分与基础电镀部分相比总体上也有更好的表现。最右部分是没有镀覆的钢，因此遭到了严重的红锈腐蚀。
本发明的锌扩散镍合金镀层，可提供给基体尤其是应用在气体涡流发动机的基体非常出色的防腐能力和高于900°F(482℃)的耐热能力。
很明显根据本发明提供了一个防腐耐热的锌扩散镍合金镀层，该镀层能够满足在前文中已经阐明的目的、手段和优点。而本发明根据上下文已经描述的具体实施方式中的其他选择、修改和变化对已经了解在前的描述的本领域普通技术人员来说是显而易见的。因此，本发明包含的其他选择、修改和变化都将落入附加权利要求的广泛的范围内。

Claims (23)

1.一种在基体上镀覆一种防腐耐热镀层的方法，包括以下步骤：
在所述基体上镀覆一层镍基镀层；
在所述镍基镀层上镀敷一层锌；和
将锌扩散到所述镍基镀层中。
2.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括在所述基体表面电镀一层镍或镍合金。
3.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括镀覆一层厚度为2.0-20μm的镍或镍合金。
4.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括镀覆一层厚度为2.0-14μm的镍或镍合金。
5.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括镀覆一层厚度为8.0-11μm的镍或镍合金。
6.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括在用于气体涡轮发动机的组件上镀覆一层镍或镍合金。
7.如权利要求1所述的方法，其中所述镀覆镍基镀层步骤包括在钢基质上镀覆一层镍合金层，所述镍合金选自：镍钴合金、镍铁合金、镍锰合金、镍钼合金和镍锡合金。
8.如权利要求1所述的方法，其中所述锌层镀敷步骤包括制备一种锌金属浓度为8.0-45.0g/l的电镀溶液和将所述锌层电镀到所述镍合金层上。
9.如权利要求1所述的方法，其中所述锌层镀敷步骤包括镀敷一层厚度为0.8-14μm的锌层。
10.如权利要求1所述的方法，其中所述锌层镀敷步骤包括镀敷一层厚度为2.0-14μm的锌层。
11.如权利要求1所述的方法，其中所述锌层镀敷步骤包括镀敷一层厚度为4.0-7μm的锌层。
12.如权利要求1所述的方法，其中所述扩散步骤包括在空气炉和惰性气体炉中的至少一种炉内形成一个热扩散循环，该循环在600-800°F下运行至少100分钟。
13.如权利要求12所述的方法，其中所述热扩散循环包括在80-100分钟内加热所述镀有锌层的镍基基体到上述温度范围的第一温度，然后在20-60分钟内加热到一个比第一温度更高的第二温度。
14.如权利要求1所述的方法，进一步包括将所述基体沉浸到磷酸盐化三价铬转化溶液中。
15.如权利要求14所述的方法，其中所述沉浸步骤在所述锌镀覆步骤之后和所述扩散步骤之前进行。
16.如权利要求14所述的方法，其中所述沉浸步骤在所述扩散步骤之后进行。
17.如权利要求14所述的方法，其中所述沉浸步骤包括将所述基体沉浸到一种溶液中，所述溶液含有一种水溶性三价铬化合物，一种水溶性氟化物和一种提高防腐性能的添加剂。
18.一种具有至少一个表面和在其至少一个表面上的一层锌扩散镍合金镀层的基体。
19.一种如权利要求18所述的基体，其中所述基体由钢制成。
20.一种如权利要求18所述的基体，其中所述基体包括一种用于气体涡流发动机的组件。
21.一种如权利要求18所述的基体，其中所述锌扩散镍合金镀层在温度高于900°F时具有防腐耐热性，其中所述镀层具有锌原子扩散进入其中的镍或镍合金层和镍原子扩散进入其中的锌层。
22.一种如权利要求21所述的基体，其中所述镍合金镀层由选自镍钴合金、镍铁合金、镍锰合金、镍钼合金和镍锡合金中的一种合金形成的。
23.一种如权利要求21所述的基体，其中所述镍合金由钴含量为7.0-40wt％的镍钴合金形成。
CNB031649149A 2002-09-23 2003-09-22 形成防腐耐热镀层的方法及具有所述镀层的基体 Expired - Fee Related CN100360713C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/252867 2002-09-23
US10/252,867 US6756134B2 (en) 2002-09-23 2002-09-23 Zinc-diffused alloy coating for corrosion/heat protection

Publications (2)

Publication Number Publication Date
CN1497065A true CN1497065A (zh) 2004-05-19
CN100360713C CN100360713C (zh) 2008-01-09

Family

ID=31993033

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB031649149A Expired - Fee Related CN100360713C (zh) 2002-09-23 2003-09-22 形成防腐耐热镀层的方法及具有所述镀层的基体

Country Status (12)

Country Link
US (2) US6756134B2 (zh)
EP (1) EP1405934B1 (zh)
JP (1) JP2004115914A (zh)
KR (1) KR100584059B1 (zh)
CN (1) CN100360713C (zh)
AT (1) ATE397683T1 (zh)
BR (1) BR0304193A (zh)
CA (1) CA2441718A1 (zh)
DE (1) DE60321435D1 (zh)
MX (1) MXPA03008544A (zh)
SG (1) SG134989A1 (zh)
TW (1) TWI276707B (zh)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103038398A (zh) * 2010-08-04 2013-04-10 杰富意钢铁株式会社 热压用钢板及使用了热压用钢板的热压部件的制造方法
CN103103589A (zh) * 2013-01-16 2013-05-15 南京工业大学 一种锰铜合金材料的制备方法
CN105917029A (zh) * 2014-01-15 2016-08-31 萨夫罗克有限公司 用于生产铬涂层的方法和涂覆的物体
CN106493309A (zh) * 2016-11-24 2017-03-15 张红卫 一种水泵涡轮铸造和退火工艺
CN109252196A (zh) * 2018-09-30 2019-01-22 四川理工学院 一种制备MnCo2O4微纳米纤维的方法
US10443142B2 (en) 2014-01-15 2019-10-15 Savroc Ltd Method for producing chromium-containing multilayer coating and a coated object
US10487412B2 (en) 2014-07-11 2019-11-26 Savroc Ltd Chromium-containing coating, a method for its production and a coated object
CN111566410A (zh) * 2017-09-22 2020-08-21 托普索公司 对金属粉尘具有高耐受性的具有浆料涂层的燃烧器
CN112247487A (zh) * 2020-10-14 2021-01-22 山东聊城富锋汽车部件有限公司 一种耐高温的发动机支架制造方法
CN113073324A (zh) * 2021-03-26 2021-07-06 苏州航宇九天动力技术有限公司 一种真空电机表面特殊处理工艺
CN113544882A (zh) * 2019-03-29 2021-10-22 东洋钢钣株式会社 碱性二次电池用表面处理板及其制造方法
CN115679304A (zh) * 2022-08-24 2023-02-03 湖南人文科技学院 一种用纳米颗粒增强的锌镍复合渗层的制备方法与应用

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7018486B2 (en) * 2002-05-13 2006-03-28 United Technologies Corporation Corrosion resistant trivalent chromium phosphated chemical conversion coatings
US20050181137A1 (en) * 2004-02-17 2005-08-18 Straus Martin L. Corrosion resistant, zinc coated articles
US20060222880A1 (en) * 2005-04-04 2006-10-05 United Technologies Corporation Nickel coating
US7812703B2 (en) * 2006-03-23 2010-10-12 Innovative Micro Technology MEMS device using NiMn alloy and method of manufacture
WO2008034282A1 (fr) * 2006-09-14 2008-03-27 Guohua Wang Marmite
US20110005287A1 (en) * 2008-09-30 2011-01-13 Bibber Sr John Method for improving light gauge building materials
WO2010075998A2 (en) * 2008-12-29 2010-07-08 Hille & Müller GMBH Coated product for use in an electrochemical device and a method for producing such a product
US8574396B2 (en) 2010-08-30 2013-11-05 United Technologies Corporation Hydration inhibitor coating for adhesive bonds
JP5555146B2 (ja) * 2010-12-01 2014-07-23 株式会社日立製作所 金属樹脂複合構造体及びその製造方法、並びにバスバ、モジュールケース及び樹脂製コネクタ部品
RU2457287C1 (ru) * 2011-04-06 2012-07-27 Государственное образовательное учреждение высшего профессионального образования "Тюменский государственный университет" Электролит для осаждения сплава никель-висмут
CN103320739A (zh) * 2013-05-30 2013-09-25 中国船舶重工集团公司第七二五研究所 一种海洋环境防腐镍基涂层的制备方法
JP5949680B2 (ja) 2013-06-25 2016-07-13 Ｊｆｅスチール株式会社 熱間プレス部材の製造方法
CN103710692A (zh) * 2013-12-20 2014-04-09 苏州市邦成电子科技有限公司 耐腐蚀sus301不锈钢带的制备方法
US10266958B2 (en) 2013-12-24 2019-04-23 United Technologies Corporation Hot corrosion-protected articles and manufacture methods
EP3090075B1 (en) 2013-12-24 2018-12-05 United Technologies Corporation Hot corrosion-protected article and manufacture method therefor
CN105239064A (zh) * 2015-10-29 2016-01-13 无锡市嘉邦电力管道厂 一种耐腐蚀金属材料
WO2017201418A1 (en) 2016-05-20 2017-11-23 Arcanum Alloys, Inc. Methods and systems for coating a steel substrate
KR101839783B1 (ko) * 2016-12-21 2018-04-26 이종소 유기성폐기물의 분해 소멸처리가 가능한 연속식 촉매분해처리장치
JP7399080B2 (ja) * 2017-05-12 2023-12-15 ケメオン サーフェス テクノロジー， エルエルシー ｐＨ安定な三価クロムコーティング液
US11854007B2 (en) * 2018-04-16 2023-12-26 Visa International Service Association Method and system for pre-authorizing a delivery transaction

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808031A (en) * 1968-05-31 1974-04-30 Chromalloy American Corp Multi-metal corrosion-resistant diffusion coatings
JPS6049715B2 (ja) * 1979-04-09 1985-11-05 新日本製鐵株式会社 亜鉛系合金被覆鋼板
US4416737A (en) * 1982-02-11 1983-11-22 National Steel Corporation Process of electroplating a nickel-zinc alloy on steel strip
JPS6056790B2 (ja) * 1982-07-28 1985-12-11 川崎製鉄株式会社 片面のみ合金化処理した溶融亜鉛めつき鋼板の製造方法
JPS61119679A (ja) * 1984-11-16 1986-06-06 Nippon Steel Corp 高耐食性亜鉛系合金メツキ鋼板
IT1184289B (it) * 1985-07-19 1987-10-22 Consiglio Nazionale Ricerche Procedimento per il rivestimento di fili di acciaio e relativi prodotti utilizzabile nella fabbricazione di corde per strutture di rinforzo di manufatti in materiale elastomerico in particolare pneumatici
US4859289A (en) * 1986-05-26 1989-08-22 Sumitomo Electric Industries, Ltd. Process for producing a metal wire useful as rubber product reinforcement
JPS63312960A (ja) * 1987-06-17 1988-12-21 Nippon Steel Corp 加工性の良い溶融亜鉛合金めっき鋼板の製造法
US5246786A (en) * 1988-10-29 1993-09-21 Usui Kokusai Sangyo Kaisha Ltd. Steel product with heat-resistant, corrosion-resistant plating layers
US5176812A (en) * 1988-12-27 1993-01-05 The Furukawa Electric Co., Ltd. Copper fin material for heat-exchanger and method of producing the same
JPH03215693A (ja) * 1990-01-18 1991-09-20 Furukawa Electric Co Ltd:The 耐塩水性複合材料
JPH0651903B2 (ja) * 1990-01-30 1994-07-06 新日本製鐵株式会社 摺動抵抗の高い亜鉛又は亜鉛系合金溶融めっき鋼板の製造方法
EP0453374B1 (en) * 1990-04-20 1995-05-24 Sumitomo Metal Industries, Ltd. Improved corrosion-resistant surface coated steel sheet
JPH0753913B2 (ja) * 1990-11-14 1995-06-07 新日本製鐵株式会社 有機複合めっき鋼板の製造方法
KR970000190B1 (ko) * 1993-06-02 1997-01-06 니홍고오깡 가부시키가이샤 아연도금강판의 제조방법
JPH0711479A (ja) * 1993-06-28 1995-01-13 Nkk Corp 亜鉛系合金めっき鋼板及びその製造方法
US5500290A (en) * 1993-06-29 1996-03-19 Nkk Corporation Surface treated steel sheet
US5494706A (en) * 1993-06-29 1996-02-27 Nkk Corporation Method for producing zinc coated steel sheet
JPH07145469A (ja) * 1993-09-28 1995-06-06 Nippon Steel Corp 耐食性・プレス成形性に優れた合金化溶融亜鉛めっき鋼板の製造方法
US5595831A (en) * 1994-01-28 1997-01-21 Clark; Eugene V. Cadium-free corrosion protection for turbines
US6500565B2 (en) * 1994-08-30 2002-12-31 Usui Kokusai Sangyo Kaisha Limited Corrosion resistant resin coating structure in a metal tube
US6040054A (en) * 1996-02-01 2000-03-21 Toyo Boseki Kabushiki Kaisha Chromium-free, metal surface-treating composition and surface-treated metal sheet
US6527841B2 (en) * 2000-10-31 2003-03-04 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103038398A (zh) * 2010-08-04 2013-04-10 杰富意钢铁株式会社 热压用钢板及使用了热压用钢板的热压部件的制造方法
CN103038398B (zh) * 2010-08-04 2014-12-03 杰富意钢铁株式会社 热压用钢板及使用了热压用钢板的热压部件的制造方法
US9023488B2 (en) 2010-08-04 2015-05-05 Jfe Steel Corporation Steel sheet for hot pressing and method of manufacturing hot-pressed part using steel sheet for hot pressing
CN103103589A (zh) * 2013-01-16 2013-05-15 南京工业大学 一种锰铜合金材料的制备方法
CN103103589B (zh) * 2013-01-16 2015-06-10 南京工业大学 一种锰铜合金材料的制备方法
US10443143B2 (en) 2014-01-15 2019-10-15 Savroc Ltd Method for producing a chromium coating and a coated object
CN105917029A (zh) * 2014-01-15 2016-08-31 萨夫罗克有限公司 用于生产铬涂层的方法和涂覆的物体
US10443142B2 (en) 2014-01-15 2019-10-15 Savroc Ltd Method for producing chromium-containing multilayer coating and a coated object
US10487412B2 (en) 2014-07-11 2019-11-26 Savroc Ltd Chromium-containing coating, a method for its production and a coated object
CN106493309A (zh) * 2016-11-24 2017-03-15 张红卫 一种水泵涡轮铸造和退火工艺
US11739932B2 (en) 2017-09-22 2023-08-29 Topsoe A/S Burner with a slurry coating, with high resistance to metal dusting
CN111566410A (zh) * 2017-09-22 2020-08-21 托普索公司 对金属粉尘具有高耐受性的具有浆料涂层的燃烧器
CN109252196A (zh) * 2018-09-30 2019-01-22 四川理工学院 一种制备MnCo2O4微纳米纤维的方法
CN113544882B (zh) * 2019-03-29 2024-07-30 东洋钢钣株式会社 碱性二次电池用表面处理板及其制造方法
CN113544882A (zh) * 2019-03-29 2021-10-22 东洋钢钣株式会社 碱性二次电池用表面处理板及其制造方法
CN112247487A (zh) * 2020-10-14 2021-01-22 山东聊城富锋汽车部件有限公司 一种耐高温的发动机支架制造方法
CN113073324B (zh) * 2021-03-26 2023-02-28 苏州航宇九天动力技术有限公司 一种真空电机表面处理装置及其处理工艺
CN113073324A (zh) * 2021-03-26 2021-07-06 苏州航宇九天动力技术有限公司 一种真空电机表面特殊处理工艺
CN115679304A (zh) * 2022-08-24 2023-02-03 湖南人文科技学院 一种用纳米颗粒增强的锌镍复合渗层的制备方法与应用

Also Published As

Publication number Publication date
US20050058848A1 (en) 2005-03-17
MXPA03008544A (es) 2005-09-08
TWI276707B (en) 2007-03-21
KR20040026618A (ko) 2004-03-31
US6869690B1 (en) 2005-03-22
CN100360713C (zh) 2008-01-09
TW200413580A (en) 2004-08-01
ATE397683T1 (de) 2008-06-15
CA2441718A1 (en) 2004-03-23
US6756134B2 (en) 2004-06-29
JP2004115914A (ja) 2004-04-15
SG134989A1 (en) 2007-09-28
US20040058189A1 (en) 2004-03-25
EP1405934A2 (en) 2004-04-07
BR0304193A (pt) 2004-09-08
EP1405934A3 (en) 2006-02-01
KR100584059B1 (ko) 2006-05-29
DE60321435D1 (de) 2008-07-17
EP1405934B1 (en) 2008-06-04

Similar Documents

Publication Publication Date Title
CN100360713C (zh) 形成防腐耐热镀层的方法及具有所述镀层的基体
US5057196A (en) Method of forming platinum-silicon-enriched diffused aluminide coating on a superalloy substrate
US20120189868A1 (en) Process for the preparation of a coated substrate, coated substrate, and use thereof
US5494704A (en) Low temperature chemical vapor deposition of protective coating containing platinum
US6228510B1 (en) Coating and method for minimizing consumption of base material during high temperature service
JPS5815554B2 (ja) カチオン電着塗装用のメッキ鋼材
US4241147A (en) Diffusion aluminized age-hardenable stainless steel
US20120088121A1 (en) Bilayer protection coating and related method
JPS5845382A (ja) 電気合金メツキ鋼板の表面処理方法
CN1208493C (zh) 铝合金镀覆钢板的镀覆方法
JPS6343479B2 (zh)
JP2963806B2 (ja) リン酸塩処理性、塗装後耐食性に優れたアルミニウム合金板
JPH10121267A (ja) 耐熱・耐食性重層めっき鋼材
JP2978074B2 (ja) 均一表面外観に優れた電気Ｚｎめっき鋼板の製造方法
CN1318645C (zh) 具有良好的抗蚀性和色调的磷酸锌处理的镀锌钢板
JPS5920491A (ja) 亜鉛系めつき鋼板の塗膜二次密着性の改良方法
JPS63213650A (ja) Ｚｎ−Ａｌ合金溶融めっき鋼材の製造方法
Fratesi et al. Corrosion Resistance of Zinc Alloy Coatings
JPS63153262A (ja) Ｚｎ系蒸着めつきの施されたＡ１又はＡ１合金板
JPH0331495A (ja) 高耐食性表面処理金属材
JPH01159398A (ja) リン酸塩化成処理性に優れた表面処理鋼板
JPS63250489A (ja) 耐食性、電着塗装性に優れた表面処理鋼板
JPH073436A (ja) めっき密着性及び耐食性に優れた亜鉛合金めっき鋼板
JPS62267497A (ja) カチオン電着塗装用防錆鋼板およびその製造方法
Yanping et al. Protective mechanism of chromate conversion coatings on electrodeposited Zn-Ni alloy

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

Address after: Farmington Road No. 10 Connecticut state farms

Patentee after: United Technologies

Address before: American Connecticut

Patentee before: United Technologies

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080109

Termination date: 20170922

CF01 Termination of patent right due to non-payment of annual fee