CN101608697B - 水龙头 - Google Patents

水龙头 Download PDF

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CN101608697B
CN101608697B CN200910145949XA CN200910145949A CN101608697B CN 101608697 B CN101608697 B CN 101608697B CN 200910145949X A CN200910145949X A CN 200910145949XA CN 200910145949 A CN200910145949 A CN 200910145949A CN 101608697 B CN101608697 B CN 101608697B
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layer
valve plate
amorphous diamond
reinforced layer
carbon
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CN101608697A (zh
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K·布伦杜姆
R·P·韦尔蒂
P·B·约恩特
D·S·里士满
K·托马斯
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Masco Corp
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Delta Faucet Co
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K11/00—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves
    • F16K11/02—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit
    • F16K11/06—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit comprising only sliding valves, i.e. sliding closure elements
    • F16K11/078—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit comprising only sliding valves, i.e. sliding closure elements with pivoted and linearly movable closure members
    • F16K11/0782—Single-lever operated mixing valves with closure members having flat sealing faces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K25/00—Details relating to contact between valve members and seat
    • F16K25/005—Particular materials for seats or closure elements
    • 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
    • Y10T137/00—Fluid handling
    • Y10T137/8593—Systems
    • Y10T137/86493—Multi-way valve unit
    • Y10T137/86549—Selective reciprocation or rotation
    • 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
    • Y10T137/00—Fluid handling
    • Y10T137/8593—Systems
    • Y10T137/86493—Multi-way valve unit
    • Y10T137/86815—Multiple inlet with single outlet
    • Y10T137/86823—Rotary valve

Abstract

本发明涉及具有互滑式部件的物品，具体而言，公开一种包括第一阀板的水龙头，该阀板包括基材和提供在基材上的加强层。非结晶的金刚石材料提供在加强层之上。非晶金刚石材料具有低于类钻碳的摩擦系数，并具有高于类钻碳的硬度。

Description

水龙头
相关申请的交叉引用
本申请是2007年4月5日提交的第11/732,948号美国专利申请的部分继续申请，该第11/732,948号申请是2005年8月10日提交的第11/201,395号美国专利申请的部分继续申请，该第11/201,395号申请是2003年12月18日提交的第10/741,848号美国专利申请的部分继续申请，该第10/741,848号申请是2002年12月18日提交的第10/322,871号美国专利申请的部分继续申请。本申请也是2007年4月9日提交的第11/784,765号美国专利申请的部分继续申请，该第11/784,765号申请是2005年8月10日提交的第11/201,395号美国专利申请的部分继续申请(如上所述，该第11/201,395号申请是2003年12月18日提交的第10/741,848号美国专利申请的部分继续申请，该第10/741,848号申请是2002年12月18日提交的第10/322,871号美国专利申请号为的部分继续申请)。上述专利申请中的各个，其全文内容通过引用结合于本文中。
技术领域
本发明一般地涉及用于制品的多层面覆层以及需要低摩擦、低磨损和保护性外表面的产品。更具体地，本发明涉及具有互滑式部件的物品(例如用于水混合阀的阀部件)，该物品具有包括加强层和外部非晶金刚石覆层的表面保护层。
背景技术
在某些应用中，例如用于流体控制阀的阀板，需要互滑式表面以抗磨损、抗磨蚀、抗划，并且具有低摩擦系数。用于混合冷水流和热水流的一种类型的控制阀的元件典型地包括固定盘和可移动滑动盘，尽管板元件可具有任何外形或具有密封面的几何形状，包括例如平面、球形和圆柱形表面。因此本文的用语“盘”指任何外形和具有配合面的几何形状的阀板，该配合面彼此接合并且滑动以形成不漏流体的密封。固定盘典型地具有热水入口、冷水入口和混合水排放出口，而可移动盘包括类似特征和混合室。应该了解的是，混合室无需在盘内但可能是邻近结构的一部分。可移动盘与固定盘重叠，并可在固定盘上滑动和/或旋转，以便在混合室中通过调节从热水入口导入的热水和从冷水入口导入的冷水的流动速度和比例来获得理想温度和流动速度的混合水，并且通过混合水排放出口排出。与密封面配合的盘应该以足够精密度制成以允许两个密封面配合在一起，并形成不漏流体的密封(也就是，它们必需合共形(co-conformal)且足够光滑以防止流体在密封面之间流过)。平面度(对于平板形状)或相一致性(对于非平表面)和所需要的平滑度在某种程度上依赖阀的构造和所涉及的流体，并且通常在工业上是众所周知的。其它类型的盘阀，尽管在彼此间的滑动接触中仍然使用配合密封面，但仅可控制一个流体流或可通过不同的结构或端口配置提供混合。例如，固定盘可为阀体的整体部分。
这类控制阀的先前经验表明，由于固定盘和可移动盘紧靠彼此接触和滑行的事实(例如，参见美国专利4935313和4966789)，在盘的配合面存在磨损问题。为了使磨损问题最小化，这些阀盘通常由烧结陶瓷例如铝土(例如氧化铝)制成。虽然氧化铝盘具有好的抗磨损性，但它们由于操纵力增加而具有不良的摩擦特征，并在最初被应用到盘的滑润剂油脂磨损和冲走后，它们趋向于变“粘”。氧化铝板在水流中相对于大微粒和小微粒(分别地)的抗划和抗磨蚀性是好的；然而，他们仍然容易受到含磨粒(例如沙子)的污染水流的破坏；并且在这点上的改进是有益的。此外，在长期的停用期间，由于溶解于水供应中的矿物在配合面的重合孔之间沉淀和结晶，烧结陶瓷盘的多孔性使它们倾于“锁定(lockup)”。本发明的一个目标是提供具有减少磨损、改进抗划和抗磨蚀以及减少摩擦力特征的盘。另一个目标是提供非多孔或多孔性减小的阀盘，以便减少沉淀晶体可在配合面之间形成的位置数。
在盘上使用更便宜、更易磨碎和更易磨光并且是非多孔的材料(例如金属)将是有利的。然而，裸金属盘的抗磨损和摩擦性能一般在滑动密封应用中难以接受。本发明的另一个目标是提供由金属基材制成的盘，与未覆层的陶瓷盘相比，该金属基材制成的盘具有改良的抗磨损、抗划和抗磨蚀以及改良的摩擦特征。
在现有技术(例如美国专利4707384和4734339，其通过引用结合于本文中)中已公开：通过化学汽相淀积(CVD)以800-1000℃的温度沉积在衬底上的多晶金刚石覆层可与不同材料的粘附层结合使用，以便提供抗划和抗磨损部件。然而，多晶金刚石膜因为个别金刚砂的晶体面而具有粗糙表面，这在US4707384专利中的图2和图3的照片中是显而易见的。现有技术中已知的是，对这种表面抛光以便使滑动应用中的摩擦系数最小化，或者甚至将多晶金刚石沉积在光滑衬底上，然后从衬底移去膜，并将膜的光滑面(其之前是紧靠在衬底上)而不是初始表面作为支承面。本发明通过提供许多有利特征(包括但不限于提供用于滑动应用中的光滑和非常硬的表面，同时避免多晶金刚石表面层的费力而昂贵的后加工)以克服现有技术问题。有利地是，该方法也可使用不可在多晶金刚石的CVD沉积所需的高温下进行加工的衬底材料(例如合适的金属、玻璃和合成物以及有机材料)。
在现有技术(例如美国专利6165616，其通过引用结合于本文中)中也公开：工程中间层用来减轻多晶金刚石层上的热感应力。这些热感应力在覆层沉积后的衬底冷却期间在相对高的温度下产生，并且由于衬底和金刚石覆层之间的热膨胀系数的不同而引起。相当复杂的工程计算在US6165616中得以详述以预定理想的中间层的合成物和厚度。US6165616所公开的以最小化金刚石层上的热感应力的中间层厚度根据图1至图3在20至25微米之间。这种厚的中间层由于沉积费时并且所需设备成本高，因而沉积代价昂贵。本发明也有利地包括但不限于使覆层成本最小化，但仍然通过使用比US6165616所教导的中间层薄得多的中间层来获得期望结果，并同时避免产生热感应力，该热感应力通过以比现有技术(例如US6165616专利)更低的温度沉积硬表面层而使如此复杂的工程计算成为必要。
在现有技术(例如美国专利4935313和4966789，其通过引用结合于本文中)中进一步公开：立方晶格碳(多晶金刚石)和其它硬材料可用作阀盘上的表面覆层，并且在表面组合物或表面抛光彼此不同的一对互滑式阀盘比具有相同特征的阀盘在最小化板之间的摩擦方面更为可取。本发明提供配合阀盘表面，该配合阀盘表面具有低于水-润滑或流体浸润面应用(例如水阀)中所公开的材料的摩擦系数，并允许两个配合面完全一致的处理以避免购买和操作不同类型的加工设备的需要。本发明进一步提供但不限于配合阀盘表面，该配合阀盘表面具有低于水-润滑或流体浸润面应用(例如水阀)中所公开的材料的摩擦系数。此外，盘的两个配合滑动表面可以是硬的并具有对污染水流的抗磨蚀性，并且允许两个配合面完全一致的处理以避免购买和操作不同类型的加工设备的需要。
发明内容
示例性实施例涉及包括第一阀板的水龙头，该阀板包括基材和提供在基材上的加强层。非结晶的金刚石材料提供在加强层之上。非晶金刚石材料具有低于类钻碳的摩擦系数，并具有高于类钻碳的硬度。
另一个示例性实施例涉及包括流体控制阀的水龙头，该流体控制阀包括多个阀部件。所述阀部件中的至少一个包括衬底、提供在基材之上的加强层和提供在加强层之上的非晶金刚石材料。非晶金刚石材料具有低于类钻碳的摩擦系数，并具有高于类钻碳的硬度，和至少约40％的sp3键(bonding)。
水龙头包括第一阀部件和配置用于与第一阀部件滑动接合的第二阀部件。第一阀部件和第二阀部件中的至少一个包括衬底、包括提供在衬底上的钽和铌中的至少一个的材料层以及提供在加强层之上的非晶金刚石材料层。该非晶金刚石材料具有低于类钻碳的摩擦系数，并具有高于类钻碳的硬度。
附图说明
图1是结合有多层结构的阀的一种形式，该多层结构具有覆盖在衬底之上的非晶金刚石层；
图2是本发明的多层结构的一种形式的明细；
图3图示了具有增加的额外粘合促进层的另一种多层结构；
图4为图2中的多层结构的进一步形式，其中加强层包括两种不同材料层；以及
图5是叠加衬底或层之上的外部非晶金刚石层的表面外观显微照片。
具体实施方式
本发明的实施例一般在附图中示出，其中图1示出了结合到本发明中的具有把柄12的阀10的一种形式。特别是，图2至图4图示了阀10的一部分，该阀10具有用于阀10的滑动部件20和/或固定部件22的衬底18，其可包括基材，其中基材在滑动部件20和固定部件22中可以是相同或不同的。在其它实施例中，部件20和部件22中的一个被固定。优选地，基材是烧结陶瓷或金属。基材也可包括玻璃或玻璃质材料、金属陶瓷、聚合材料、复合材料、例如是铁铝(iron aluminide)的金属间化合物和机械地适合于应用的其它材料。金属可包括，例如任何传统的金属，包括但不限于不锈钢、黄铜、锆、钛、铝和后三种材料的合金。不锈钢、钛和锆和铝是优选的金属，用语“不锈钢”指任何类型，例如304、316等，以及它们的定制变形，并且用语钛、锆和铝应理解为包括主要由那些金属所组成的合金。烧结(粉末状)不锈钢是首选的衬底材料，因为它可经济性地铸塑成适于盘的复杂形状，并且可经济性地研磨和抛光以获得配合光滑密封面。至于烧结不锈钢，“全致密”衬底和金属注射成型衬底是优选的。钛和锆是优选的基材，因为它们能被轻易地氧化或阳极电镀(anodized)以形成坚硬表面层。陶瓷可以是任何传统的陶瓷材料，包括但不限于，例如烧结铝土(氧化铝)和金刚砂，其中氧化铝是优选材料。例如，复合材料可包括任何传统的金属陶瓷、纤维增强环氧树脂和聚酰胺以及碳碳合成物。例如，玻璃或玻璃状材料可包括硼硅玻璃(比如PyrexTM)和例如是钢化层压玻璃和玻璃陶瓷的材料。玻璃、玻璃状材料和金属陶瓷是优选的衬底，因为它们能经济性地铸塑成适于盘的复杂外形，并且可经济性地研磨和抛光以获得平坦和光滑的表面。铁铝应理解成主要由铁和铝组成的材料，但也可包含少量例如是钼、锆和硼的其它元素。
如图2所示，加强层23也可直接放置在衬底表面18上。该层23可包括具有高于衬底18的硬度的材料(尽管应该了解的是，根据其它示例性实施例，加强层可不具有高于衬底的硬度)。用于加强层23的适宜材料可包括Cr、Ti、W、Zr、Ta、Nb以及传统上已知的用于硬覆层的任何其它金属的化合物。该化合物包括但不限于氮化物、碳化物、氧化物、碳氮化物以及其它结合氮、氧和碳的混合相材料。用于加强层23的一种高度优选的材料是氮化铬。本申请中的氮化铬更优选地是指含氮量在大约10％到大约50％的原子百分比的铬和氮的单一或混合相化合物。用语氮化铬也指包含除铬和氮之外的例如钇、钪和镧的掺杂元素或合金元素的材料。
适合加强层23的另一种材料是传统的DLC(类钻碳(diamond-likecarbon))，该DLC是在现有技术中众所周知的非结晶碳的一种形式，并不同于非晶金刚石。例如，DLC覆层在美国专利6165616(在这里它们被叫做(a-C)覆层)中得到描述。DLC可通过溅射或传统的CVD沉积。DLC是一种主要具有sp2碳键和很少量特征为非晶金刚石的四面体sp3键的非结晶材料。DLC的硬度大体上低于非晶金刚石的硬度，并且更类似于传统的硬覆层材料(例如氮化钛和氮化铬)的硬度。DLC覆层的内应力也比非晶金刚石覆层中的低，其在不损失黏着力的情况下，允许DLC沉积在比非晶金刚石厚的层中。本文使用的用语DLC包括材料的氢化形式。
根据另一个示例性实施例，加强层包括含钽的材料，例如碳化钽、氮化钽或碳氮化钽(tantalum carbo-nitride)。对于加强层使用钽或钽化合物的一个有利特征是钽表现出极好的耐腐蚀性，并当其作为金属使用时相对易延展。此外，钽容易形成具有相对高硬度值(9+的莫氏硬度值)的碳化物，这是加强层为衬底提供抗划和抗磨蚀所期望的。
根据又一个示例性实施例，加强层包括含铌的材料，例如碳化铌、氮化铌或碳氮化铌(niobium carbo-nitride)。
加强层23主要起提高多层覆层的抗划性和抗磨损性的作用。加强层23的硬度应至少大于衬底18的硬度，以便完成提高被涂覆盘抗划的预定功能。加强层23的厚度至少足够地厚以提高衬底18的抗划性。对于典型地用作硬覆层的材料，例如上文所描述的那些，其厚度一般在约500纳米到约10微米之间，并且优选地在约2000纳米到约5000纳米之间。在测试旋塞式水阀中，已发现具有约为5微米厚的氮化铬加强层(与薄的非晶金刚石顶层相结合)为市政水源和井水源中典型类型和典型尺寸的污染物提供适当的抗划性和抗磨损性。
在如图3所示的本发明的某些实施例中，对于图4的部件22，薄的粘附增强层21可沉积在衬底18上，然后加强层23在层21之上。该层21提高叠加加强层23到衬底18的附着力。用于粘附增强层21的适宜材料包括如下成分的材料：铬、钛、钨、钽、铌、其它难熔金属、硅以及本领域中认为适合用于粘附增强层的其它已知材料。该层21可方便地使用与用于加强层23相同的元素材料制成。层21具有至少足能提高或改善层23到衬底18的附着力的厚度。该厚度一般地在约5纳米到约200纳米之间，并且更优选地在约30纳米到60纳米之间。粘附增强层21可通过传统的气相淀积技术(包括优选的物理气相沉积(PVD))被沉积，也可通过化学气相沉积(CVD)来完成。
PVD工艺是众所周知的并是传统的，其包括阴极电弧沉积(cathodic arc evaporation)(CAE)、溅射和其它传统的沉积工艺。CVD过程包括低压化学气相沉积(LPCVD)、等离子体增强化学气相沉积(PECVD)和热分解方法。PVD和CVD技术和设备已经公开在下述文献中：由J.Vossen和W.Kern编著、美国学术出版社1991年出版的“Thin FilmProcesses II”；由R.Boxman等人编著、Noyes于1995年出版的“Handbook of Vacuum Arc Science and Technology”以及美国专利4162954和4591418，其中专利文献通过引用结合于本文中。
就烧结陶瓷材料而言，虽然形成烧结材料的单个颗粒具有高的硬度，但划痕试验所测量到的整个烧结结构的抗划性比形成颗粒的材料(例如氧化铝)的抗划性要低得多。这是因为：典型用来将氧化铝颗粒烧结或粘结在一起的材料(典型的硅酸盐)不象颗粒本身一样硬。加强层23的硬度与构成陶瓷盘的单个颗粒的硬度类似或者更小，但仍比整个烧结陶瓷结构硬。例如通过实验已经发现，由触针(半径＝100微米)在30牛顿的负载下滑动所引起的刮痕深度在未涂覆的烧结氧化铝衬底上大约为4至6微米，而在同一个涂上3微米厚的氮化铬加强层的衬底上刮痕深度仅为2至3微米。
加强层23可由传统的汽相淀积工艺形成，该技术包括但不限于溅射、阴极电弧沉积(CAE)和CVD。最优选的方法是溅射、CAE或其它可在相对低的温度下执行的方法，从而在冷却时最小化覆层堆叠中的热感应力。如果加强层23是通过CAE沉积的话，也希望使用大粒子过滤以便控制和维护衬底18表面的光滑度。加强层23也可通过用于形成硬覆层的其它已知方法形成，例如喷雾热解法(spray-pyrolysis)、溶胶一凝胶法、带后续热处理的浸液法、奈米制造(nano-fabrication)法、原子层沉积法和分子层沉积法。
加强层23可备选地由在衬底基材上产生硬化表面层的工艺形成。该工艺包括：例如热氧化、等离子体氮化、离子注入、化学和电化学表面处理(例如化学转化覆层)、包括硬质阳极氧化和传统后处理的阳极氧化处理、微弧氧化和表面硬化。该加强层23也可包括图4所示的多层24和25，其中，层24和25一起形成加强层23。例如，层24可以是在衬底基材上热生成的氧化物，而层25是沉积材料比如CrN。加强层23也可包括多于两层，例如可优选地包括具有大量非常薄的交替层的超点阵类型(superlattice type)的覆层。加强层23的这样一种多层或超点阵形式也可包括非晶金刚石的一层或多层。
在图1至图4的多层结构中，非晶金刚石层30沉积在加强层23之上以形成外部表面层。非晶金刚石层30的目的是在滑动部件上提供非常硬的抗磨耐蚀和光滑的顶面。非晶金刚石是技术领域中众所周知的非晶碳的一种形式，并且有时也指四面体键合非晶碳(taC)。它的特征是具有至少40％的sp3碳键、至少45吉帕斯卡的硬度和至少400吉帕斯卡的弹性模数。非晶金刚石材料在美国专利5799549和5992268中得以描述，两者通过参考结合于本文中。非晶金刚石材料层30可应用的工艺包括：例如传统的过滤阴极电弧沉积和激光烧蚀(ablation)。本文使用的用语“非晶金刚石”包括所有形式的taC类型碳，并且也可包含掺杂元素和合金元素(例如氮和金属)，并且也包括含非晶金刚石的纳米结构材料。纳米结构材料在本文中是指：具有按纳米或数十纳米级的结构特征的材料，包括但不限于超点阵。
非晶金刚石层30的厚度至少为能有效地提供滑动部件的改良抗磨损和抗磨蚀性的厚度。该厚度一般至少为约100纳米，优选地为至少约200纳米，并且更优选地是至少约300纳米。层30的上部厚度范围由材料特征、经济考虑和使层30中依赖厚度的内应力最小化的需求确定，这将在下文进行讨论。同样，参考图5中的照片能够看到，非晶金刚石层30有利地表现非常光滑的表面拓扑，其主要是因为在非结晶覆层中没有独立的金刚砂。此外，薄的非晶金刚石层30的表面形貌实质上是复制了沉积在其上的下层表面(subsurface)的表面形貌，因此非晶金刚石层30大体上具有与下层表面一样的平均表面粗糙度。石墨内含物(如图5中亮点所示)不是有助于表面粗糙度，如同此用语用在此处的那样，因为它们非常软并当滑动面开始接触时其化为润滑粉。非晶金刚石具有进一步优点，那就是它可在比多晶金刚石低很多的温度(一般低于大约250℃)下沉积，因而消除厚度的需求以及现有技术(参见美国专利6165616)中所公开的用于消除金刚石层中的热感应力的工程中间层的需求。这些热感应力在沉积后的冷却期间由CVD的高温特征引起，并且由衬底和金刚石覆层之间热膨胀系数不同引起。我们已经发现，US616561中所公开的用于确定热感应力消除中间层的厚度的计算类型由于低的沉积温度而没有必要用于非晶金刚石薄膜。
非晶金刚石的一个特征是它产生高的固有(非热感应的)内应力，当覆层厚度增加时内应力增加，并且内应力主要与原子键变形相关并不与热膨胀/收缩相关。尽管此固有应力被认为是有助于材料的高硬度，但也由于应力诱导的力倾向于引起覆层在一定厚度之上从衬底18(或加强层23)脱离，这也限制了覆层厚度。虽然非晶金刚石可直接沉积在金属、玻璃或铁铝盘(可选择地具有粘附层)上，但也难于沉积足够厚的层以为水阀应用提供足够的抗划性能。由于管道破裂、构造等使水源供应有时包含磨料污染物，因而抗划性是重要的。本发明的附加加强层23提供比较软衬底材料更好的非晶金刚石层30的支撑，有利地是允许使用更薄的非晶金刚石层，而仍然获得改良的抗划性和抗磨蚀性。为了在保持性能的同时使整个覆层成本最小化，加强层23也可选为比非晶金刚石层30具有更大沉积速率和/或更便宜沉积的材料。在最优实施例中，用于大约1至2微米的非晶金刚石层30的上部厚度极限可用来避免应力感应脱层，同时，约800纳米的上部厚度，更优选地约300-500纳米的上部厚度在经济上是理想的，同时仍能获得期望的性能特征。
非晶金刚石非常适于水阀应用中的湿滑动应用。尤其是，已经示出它具有非常低的摩擦系数，并且在水润滑滑动试验中也具有极低的磨损，其中两个滑动表面都涂覆了非晶金刚石。相比之下，已知DLC覆层具有更高的摩擦系数、更高的磨损率，并且随着湿度的增加摩擦性能恶化。非晶金刚石的另一个优点是：相对低的沉积温度允许衬底材料的更广泛选择，并且最小化或消除了衬底的永久性热感应变形。
至于水润滑滑动试验中所报道的用于非晶金刚石覆层的低摩擦系统，认为至少部分地是归因于通过某些方法引入到非晶金刚石覆层内的石墨内含物(inclusion)(通常称为大粒子(macroparticle))。这种石墨内含物在通过阴极电弧沉积法沉积的碳覆层中有许多，取决于所选的目标材料和如下文所讨论的大粒子过滤设备的使用。这些石墨内含物由于它们的柔软度以及它们所占整个表面积的很小一部分而不降低非晶金刚石覆层的性能。恰恰相反，认为它们通过在滑动板之间增加润滑剂持留性可提高性能。
在美国专利5401543(通过引用结合于本文)中已公开：本质上不具有(free of)大粒子的非晶金刚石覆层可通过阴极电弧沉积法从玻璃碳或热解石墨阴极中沉积出。在这种覆层中大粒子(石墨内含物)的最大密度大约是每平方毫米大约200个大粒子，这可通过摄制图像的面积尺寸和公开的大粒子数量计算出。这种不具有大粒子的非晶金刚石覆层可在本发明中用作层30，但这比从普通的石墨阴极中沉积出并包括大量石墨内含物(例如至少每平方毫米500个)的那些次优选一些。由于玻璃碳或热解石墨阴极相比普通石墨而言贵得多，因而它们也是次优选的。
根据本发明，通过选择过滤设计和运行参数，可控制引入到通过过滤电弧沉积从普通石墨阴极沉积出的覆层(参见图4示意图)中的石墨内含物40的数量，以便允许理想数目的大粒子传输通过源极(source)。影响大粒子传输通过过滤器的因素在例如美国专利5840163中得到了讨论，该专利通过引用结合于本文中。传统地选择过滤器设计和运行参数以使传输通过源极的大粒子数目最小化，然而这种选择也通常减少碳离子的(理想)输出，因而减少沉积速度。与此通常实施相反，我们发现：为了最小化覆层成本，优选地是选择过滤设计和运行参数，以便使源极的碳离子输出(也就是沉积速度)最大化，而不超过结合到覆层中的石墨内含物的最大许可数目。内含物的最大许可数目是指在该数目之上，由于内含物所占据的表面积的增长比例，被涂覆部分的性能恶化得不能接受。关键的性能因素可包括工作流体的非泄漏性、滑动摩擦系数、抗划和抗磨损性以及磨损寿命。我们已经发现，大体上高于500/mm2的石墨内含物表面密度是可容忍的，并且如上文所描述的那样是有利的。
在加强层23的沉积末期的短时期期间，非晶金刚石层30到氮化物形式的加强层23的粘附度可在一些情况下通过引入包含碳的气体(例如甲烷)来提高。这可在加强层23和非晶金刚石层30之间引起碳氮化物和/或碳化物材料的薄过渡区。在其它情况下，粘合度可通过在加强层23的沉积末期的短时期期间关闭所有反应气体来提高。这可在加强层23和非晶金刚石层30之间造成薄金属层。也已经注意到，在非晶金刚石层30的过滤电弧沉积期间甲烷的引入增加了覆层沉积速度，并且也可提高覆层硬度和抗划性。在其它情况下，例如，在非晶金刚石层30将沉积在热氧化金属表面的情况下，需要将分开的粘附增强层21沉积在加强层23和非晶金刚石层30之间。例如，用于粘附层21的合适材料可包括耐熔碳化物形成金属(例如Ti和W)，以及不同的过渡金属(例如Cr)，并且也包括那些金属的碳化物。
根据示例性实施例，非晶金刚石层对水中颗粒的滑动磨损和磨蚀作用提供有利的物理耐受性。此外，非晶金刚石材料本身对市政给水中以一定浓度呈现的普通供水组分(例如，比如是氯化物和氟化物的离子，类似次氯酸盐的氧化剂等)是化学惰性的。
衬底也可由对于这些给水组分抗腐蚀的材料形成。根据示例性实施例，例如是陶瓷(比如氧化铝)、金属(例如Zr和Ti)和合金(例如不锈钢)的材料可用作衬底。根据特定示例性实施例，衬底可由基于氧化铝和不同数量的氧化锆和硅石的陶瓷材料形成，以为衬底提供减少的氟化物敏感性(sensitivity)。
为了进一步耐受普通供水组分的腐蚀，加强层可由形成硬碳材料(例如碳化物材料)的材料形成。例如，加强层可以是碳或根据不同示例性实施例的下列任何材料的碳化物：Cr、Hf、La、Mn、Mo、Nb、Ti、Sc、Si、Ta、W、Zr。例如，碳或Hf、La、Nb、Ti、Sc、Si、Ta、W和Zr的碳化物可提供对于诸如次氯酸盐的氧化剂增强的抗腐蚀性。碳或Cr、Mn、Mo、Nb、Ta和W的碳化物可提供对于氟化物增强的抗腐蚀性。碳或Nb、Ta、和W的碳化物可提供对于诸如次氯酸盐的氧化剂和诸如氯化物和氟化物的一般腐蚀剂的总的抗腐蚀性。根据特定示例性实施例，加强层可使用碳和/或Nb的碳化物。
为了更容易地理解本发明，提供了下列示例。示例是示意性的，并不将本发明限定到所描述的详细特征。
示例1
纯不锈钢阀盘放置在结合有电弧蒸镀阴极和溅射阴极的真空沉积室中。电弧光源装配有过滤设备以减少引入覆层的大粒子，与例如在美国专利5480527和5840163(它们通过引用结合于本文中)中所描述的那样。氩和氮源通过带有可调阀的歧管连接到室，以控制各气体进入室的流速。溅射阴极连接到DC电源的负极输出。电源的阳极侧连接到室壁。阴极材料是铬。阀盘置于阴极前，并在沉积期间可旋转或可移动以确保均匀的覆层厚度。盘与室电隔离，并通过它们的安装支架连接到电源的负极输出，以便偏压可在涂覆期间应用到衬底。
在沉积之前，真空室被抽空至2x10e-5托或更少的压力。然后氩气以一定速率引入，足能保持约25毫托的压力。然后阀盘经受辉光放电等离子体净化，其中大约500伏特的负偏压应用到机架(rack)和阀盘。净化持续的时间大约为5分钟。
具有约为20纳米厚的铬层通过溅射沉积在阀盘上。在铬粘附层沉积后，具有约为3微米厚的氮化铬加强层通过反应溅射法沉积。
在氮化铬层沉积后，阀盘面向电弧光源放置，并且具有约为300纳米厚的顶部非晶金刚石层通过触发(strike)碳电极上的电弧和将衬底暴露于离开源极出口的碳等离子体来沉积。约500伏特的负DC偏压最初应用到衬底，以便为表面净化和键合改良提供高能离子轰击。在高偏压约5分钟后，偏压减少至约50伏特，以用于余下的沉积过程。在沉积期间，约0.5毫托的氩气压力保持在室内。脉冲或AC偏压可交替使用，也可维持更高或更低压力的氩，以便稳定电弧运行和优化覆层属性。
通过实验已经发现，由不锈钢制成的并且根据上述示例涂覆的阀盘在载有20微米硅砂的循环水中能经受住超过15000个测试循环，而标准的无覆盖层的氧化铝阀盘在相同的条件下在小于2500个循环内就会失效。
示例2
纯化(clean)锆阀盘置于热空气箱中，加热到560℃的温度，保持在这个温度大约6小时，然后冷却。因而，氧化锆的加强层形成在衬底表面上，其具有5至10微米的厚度。然后，将盘置于结合有过滤电弧蒸镀阴极和溅射阴极的真空沉积室中。具有约20纳米厚的铬粘附层通过如示例1所描述的溅射法沉积在阀盘上。在铬粘附层沉积后，非晶金刚石层如示例1所描述的那样沉积。
由锆制成并且如描述那样进行处理以在其表面形成多层结构的阀盘被用来测试抗划性，其使用具有变动载荷的刮痕试验机。在3牛顿负载作用下，具有100微米半径的针尖在处理过的Zr盘上产生的刮痕深度大约为4.7微米，而在未处理的Zr盘上产生的刮痕大约是9.5微米厚或超过深度的两倍。刮痕测试性能被认为是在行业应用中抗划性和抗磨损性的相关预测器。
示例3
纯化模制玻璃阀盘放置在结合有激光烧蚀源、PECVD源和溅射阴极的真空沉积室中。该阀盘通过已知的设备经受RF(射频)放电等离子体净化。然后，具有约20纳米厚的钛粘附层通过溅射沉积在阀盘上。然后，具有约3微米厚的DLC加强层通过使用已知沉积参数的PECVD沉积在粘附层的顶部。然后，具有约300纳米厚的非晶金刚石层通过使用典型沉积参数的激光烧蚀而沉积在DLC层的顶部。
示例4
纯化不锈钢阀盘放置在包含过滤电弧蒸镀源和溅射阴极的真空室内。室被抽空，氮气被引入，在盘和室壁之间建立等离子体放电，并且盘表面根据已知参数被等离子体氮化。氮扩散进入不锈钢衬底中以形成比大块(bulk)衬底更硬的表面层，并且过程持续一段时间，足能使层深度达到约2微米。由氮化碳和氮化锆的多个交替层组成的超晶格然后分别通过过滤电弧蒸镀和溅射沉积在氮化的不锈钢表面上。交替的单层约为10纳米厚，并且大约100层的各材料被沉积以达到总厚度约为2微米厚的超晶格厚度。在氮化碳层中氮与碳的比率优选地约为1.3，因为具有该N∶C比率的氮化碳+氮化锆超晶格已经示出具有主要的sp3键合碳(sp3-bonded carbon)并具有50吉帕斯卡范围内的硬度。本文所使用的氮化碳指具有N∶C的比率在约0.1到1.5之间的材料。
大量的薄层可通过将衬底安装在旋转的圆柱上而方便地沉积，使得衬底首先通过一个沉积源面前，然后通过另一个，以便一对层在圆柱每旋转一圈期间沉积。整个加强层厚度约为4微米，其包括等离子体氮化不锈钢层。具有约为200纳米厚的非晶金刚石层通过如示例1所描述的过滤电弧蒸镀沉积在超晶格层的顶部。
审阅本公开内容的那些人将了解到，在本发明的范围内多种组合是可能的。例如，根据示例性实施例，由氧化铝或另一种适宜材料组成的阀板可以涂覆上第一铬层和第二氮化铬层，在这之后，非晶金刚石层可应用在其上。根据另一个示例性实施例，由氧化铝或另一种适宜材料组成的阀板可具有设置在其上的第一钽层，在这之后，在应用非晶金刚石层之前，可提供碳化钽层或碳氮化钽层。根据又一个示例性实施例，由氧化铝或另一种适宜材料组成的阀板具有设置在其上的第一铌层，在这之后，在应用非晶金刚石层之前设置一层氮化铌、碳化铌或碳氮化铌。
在首选和其它示例性实施例中所示出的元件构造和布置仅仅是描述性的。虽然仅很少一部分实施例在本公开中得到详细描述，阅读本公开内容的本领域技术人员将容易了解到，在本质上不脱离本文所述主题的新颖性教导和优点下，作出许多修改是可能的(例如，大小、尺寸、结构，不同元件的形状和比例，参数值，材料的使用等变化)。例如，水龙头可包括在组件所包含的一个盘或两个盘上的非晶金刚石覆层。任何工艺或方法步骤的顺序或次序可根据备选实施例改变或重新定序。在不脱离本发明范围的情况下，在首选和其它示例性实施例的设计、运行条件和布置中可作其它的替换、修改、变化和删除。

Claims (15)

1.一种用于水龙头的阀板，包括：
包括基材的衬底(18)；
设置在衬底上的加强层(23)，该加强层(23)包括含铌的材料；以及
设置在加强层(23)之上的非晶金刚石材料层(30)，该非晶金刚石材料具有低于类钻碳的摩擦系数，并具有高于类钻碳的硬度。
2.如权利要求1所述的阀板，其特征在于，所述加强层(23)中的含铌的材料包括氮化铌。
3.如权利要求1所述的阀板，其特征在于，所述加强层(23)包括碳化钽和碳氮化钽中的至少一种。
4.如权利要求1所述的阀板，其特征在于，所述加强层(23)中的含铌的材料包括碳化铌和碳氮化铌中的至少一种。
5.如权利要求1所述的阀板，其特征在于，所述加强层(23)的硬度大于基材硬度。
6.如权利要求1所述的阀板，其特征在于，所述非晶金刚石材料层具有至少40％的sp3键、至少45GPa的硬度以及大于400GPa的弹性模数。
7.如权利要求1所述的阀板，其特征在于，所述基材包括选自下列成分组成的组中的材料：不锈钢、铝、铜、钛、锆、玻璃、金属陶瓷、含玻璃材料、聚合材料以及复合材料。
8.如权利要求1所述的阀板，其特征在于，所述非晶金刚石材料由碳组成。
9.如权利要求1所述的阀板，其特征在于，所述非晶金刚石材料具有小于10微米的厚度。
10.如权利要求1所述的阀板，其特征在于，进一步包括设置在加强层(23)和非晶金刚石材料层(30)之间的粘附增强材料层(21)，该粘附增强材料层(21)包括至少一种选自下列成分组成的组中的材料：铬、钛、钨和硅。
11.如权利要求1所述的阀板，其特征在于，所述阀板以盘的形式设置。
12.一种包括第一阀板的水龙头，其特征在于，所述第一阀板包括如权利要求1-11中任一项所述的结构。
13.如权利要求12所述的水龙头，其特征在于，所述水龙头还包括与第一阀板接触的第二阀板，其中，第二阀板具有如权利要求1-11中任一项所述的结构。
14.一种生产如权利要求1-11中任一项所述的阀板的方法，该方法包括：
使用汽相淀积工艺将包括有含铌的材料的加强层(23)沉积在衬底(18)之上；以及
使用过滤阴极电弧蒸镀或激光烧蚀方法将非晶金刚石材料层(30)沉积在加强层(23)之上。
15.如权利要求14所述的方法，其特征在于，所述非晶金刚石材料层(30)使用过滤阴极电弧蒸镀法而被沉积。
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