CN108570571A - 滑动材料及其制造方法、以及滑动构件和轴承装置 - Google Patents

滑动材料及其制造方法、以及滑动构件和轴承装置 Download PDF

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Publication number
CN108570571A
CN108570571A CN201810063902.8A CN201810063902A CN108570571A CN 108570571 A CN108570571 A CN 108570571A CN 201810063902 A CN201810063902 A CN 201810063902A CN 108570571 A CN108570571 A CN 108570571A
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Prior art keywords
sliding
copper alloy
base material
rake
sliding material
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CN201810063902.8A
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CN108570571B (zh
Inventor
户田和昭
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DAIDO METAL INDUSTRIES Ltd
Daido Metal Co Ltd
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DAIDO METAL INDUSTRIES Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02—Parts of sliding-contact bearings
    • F16C33/04—Brasses; Bushes; Linings
    • F16C33/06—Sliding surface mainly made of metal
    • F16C33/12—Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
    • F16C33/121—Use of special materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B22D13/02—Centrifugal casting; Casting by using centrifugal force of elongated solid or hollow bodies, e.g. pipes, in moulds rotating around their longitudinal axis
    • B22D13/023—Centrifugal casting; Casting by using centrifugal force of elongated solid or hollow bodies, e.g. pipes, in moulds rotating around their longitudinal axis the longitudinal axis being horizontal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/08—Casting in, on, or around objects which form part of the product for building-up linings or coverings, e.g. of anti-frictional metal
    • B22D19/085—Casting in, on, or around objects which form part of the product for building-up linings or coverings, e.g. of anti-frictional metal of anti-frictional metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/16—Casting in, on, or around objects which form part of the product for making compound objects cast of two or more different metals, e.g. for making rolls for rolling mills
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045—Directionally solidified castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
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    • 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
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    • 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
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • 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
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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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Abstract

本发明提供含有Sn的铜合金层和基材的接合强度提高了的滑动材料及其制造方法。本发明的滑动材料具有基材和铜合金层，铜合金层由含有2.0～15.0质量％的Sn的铜合金构成。铜合金层具有包含滑动面的滑动主体部、和包含与基材的接合面的倾斜部，倾斜部的锡浓度从滑动主体侧朝着与基材的接合面变小。滑动材料通过将铜合金的熔液浇铸在基材上并使其单向凝固来制造。

Description

滑动材料及其制造方法、以及滑动构件和轴承装置
技术领域
本发明涉及滑动材料，具体而言，涉及在基材上设有含锡的铜合金层的滑动材料。此外，本发明还涉及该滑动材料的制造方法、以及使用该滑动材料的滑动构件和轴承装置。
背景技术
作为内燃机等的滑动轴承、或轴瓦、推力垫圈等各种滑动构件，提出了在钢材等里衬金属上覆盖不含铅的、含锡铜基滑动合金而得的滑动构件(例如专利文献1)。铜合金中的锡因为能提高铜合金的强度、改善耐磨耗性，还能提高耐腐蚀性和滑动特性，所以该含锡的铜合金的滑动性、耐烧结性和耐磨耗性优良。作为将这样的铜合金层覆盖在里衬金属上的手段，利用在里衬金属上对铜合金粉末进行烧结的方法(例如专利文献2)。
另一方面，专利文献3中，作为浇铸熔敷法(日文：鋳込溶着法)或固体接合法，记载了使高强度黄铜合金以固体、液体或半熔融状态直接接触在铁系材料上的复合材料的制造方法。在该方法中，记载了因为在高强度黄铜合金和铁系材料之间不产生脆弱的金属间化合物，所以可得到足够的接合强度。
现有技术文献
专利文献
专利文献1：日本专利特开2010-150649号公报
专利文献2：日本专利特开平8-209264号公报
专利文献3：日本专利特开平11-58034号公报
发明内容
发明所要解决的技术问题
近年来，伴随由发动机的高输出化、发动机的小型化引起的因轴承面积减少等造成的对轴承的负荷的增加，要求滑动材料的强度的提高。通常，若提高合金的强度，则合金的韧性减小。在里衬金属上覆盖有高强度的(韧性小的)铜合金滑动层的滑动材料中，在滑动中产生的剪切应力倾向于集中在铜合金和里衬金属的接合界面，剥离的危险性变大。因此，为了提高滑动材料的强度，不仅要提高铜合金的强度，还需要提高接合强度。
在将铜合金粉末烧结在里衬金属上的现有方法中，因为滑动合金自身的成分设计容易，所以即使能提高强度，也不能同时提高接合强度。
此外，如专利文献3那样，在从钢材侧背面喷射冷却剂而使其单向凝固的方法中，通过急速的冷却能提高合金强度，但铜合金的凝固收缩的速度变大，使铜合金和钢材剥离的力变大，所以妨碍接合并导致接合力的降低。
因此，本发明的目的是提供在基材上形成由含锡的铜合金构成的层时，使铜合金层和基材的接合强度提高的方法。此外，本发明的目的是提供含锡的铜合金层和基材的接合强度提高了的滑动材料、以及由该滑动材料制作的滑动构件。
解决技术问题所采用的技术方案
如上所述，使含锡的铜合金层和基材的接合强度降低的主要因素是与基于锡的固溶的强度提高相伴的韧性的减少、及根据情况的锡系金属间化合物的析出。于是，本发明中，通过减少与接合界面接触的锡固溶量或锡系金属间化合物的析出，提高基材和铜合金层的接合强度。
本发明提供具有基材和铜合金层的滑动材料，上述铜合金层是与基材接合的滑动层。铜合金层由含有2.0～15.0质量％的Sn的铜合金构成，铜合金层具有包含滑动面的滑动主体部、和包含与基材的接合面的倾斜部(日文：傾斜部)，倾斜部内的锡浓度从滑动主体部侧朝着接合面变小。
根据一个具体例，倾斜部内的锡浓度的比率优选为0.1～0.8，更优选0.1～0.6。“倾斜部内的锡浓度的比率”是指与基材的接合面附近的锡浓度相对于在与滑动主体部接触的位置处的锡浓度的比率(参照下述)。
根据一个具体例，铜合金包含2.0～15.0质量％的Sn、0～30.0质量％的Bi、以总量计为5.0质量％以下的选自Al、Zn、Mn、Si、Ni、Fe、P、Zr、Ti、Mg的1种或2种以上，余部是铜和不可避免的杂质。
铜合金可进一步以总量10.0体积％以下包含MoS2、石墨中的任一方或双方。
根据一个具体例，滑动材料可进一步在铜合金层上具有覆层。
根据一个具体例，优选基材的厚度为1.0～25.0mm，铜合金层的厚度为0.1～3.0mm。
根据一个具体例，优选倾斜部的厚度为5～50μm。倾斜部厚度的下限更优选为10μm，进一步优选15μm，倾斜部厚度的上限更优选为40μm，进一步优选30μm。
基材优选为亚共析钢、共析钢、过共析钢、铸铁、高速度钢、工具钢、奥氏体系不锈钢、铁氧体系不锈钢等铁基材料、或纯铜、磷青铜、黄铜、铬铜、铍铜、科森合金等铜基材料。
本发明还提供制造上述滑动材料的方法。该方法包括：准备基材的步骤；将铜合金熔融的步骤；将熔融后的铜合金浇铸在基材的待接合的表面上的步骤；从与基材的待接合的表面相反的一侧面用冷却剂将基材冷却，使铜合金单向凝固的步骤。
根据一个具体例，该方法还包括在自浇铸起经过规定时间后，减少冷却剂的供给量的步骤。
根据一个具体例，冷却剂可使用水或油。
根据一个具体例，准备基材的步骤包括将由一个或多个基材构成的圆筒形状体成形的步骤，浇铸步骤包括一边使圆筒形状体沿着圆筒形状的中心轴线的圆周旋转一边浇铸的步骤。
另外，本发明可提供由上述滑动材料制造的滑动构件。该滑动构件可以是例如对开轴承等滑动轴承，但也可以是其他轴瓦、推力垫圈等滑动轴承。
本发明还提供具有上述滑动构件和轴的轴承装置。该轴承装置只要构成轴和轴承的单元即可，更具体而言，优选用于各种发动机。
以下，参照附带的示意图对本发明及其更多的优点进行详细说明。附图仅以例示的目的来表示非限定性的实施例。
附图说明
图1是本发明的滑动材料的一例的剖面示意图。
图2是图1的滑动材料的与基材的边界附近的铜合金层的截面组织的示意图。
图3是表示本发明的滑动材料的制造方法中的冷却工序的一例的图。
图4是表示离心铸造法的示意图。
图5是剪切试验的示意图。
图6是表示倾斜部的锡浓度比与剪切强度/拉伸强度的关系的图。
符号说明
1滑动构件
2基材
3铜合金层
5倾斜部
6滑动主体部
7接合面
8滑动面
11密封构件
12旋转装置
13浇口
具体实施方式
图1示意地表示本发明的滑动材料1的一例的剖面。滑动材料1在基材2上设有成为滑动层的铜合金层3。在图1中，铜合金层3直接设置在基材2上。
基材2支承铜合金层3，并确保滑动材料1的强度。其原材料可以是例如亚共析钢、共析钢、过共析钢、铸铁、高速度钢、工具钢、奥氏体系不锈钢、铁氧体系不锈钢等通常市售的铁基材料、或纯铜、磷青铜、黄铜、铬铜、铍铜、科森合金等铜基材料，也可以是其他材料。
铜合金层3作为具有滑动面8的滑动层起作用，由相对于铜合金整体的质量含有2.0～15.0质量％的Sn的铜合金构成。铜合金中，除Sn以外，还含有0～30.0质量％的Bi、以总量5.0质量％以下含有选自Al、Zn、Mn、Si、Ni、Fe、P、Zr、Ti、Mg的1种或2种以上。铜合金可进一步以总量10.0体积％以下包含MoS2、石墨中的任一方或双方。此外，还可分散有金属的硼化物、硅化物、氧化物、氮化物、碳化物、金属间化合物等硬质粒子。
滑动材料中，优选基材的厚度为1.0～25.0mm，铜合金层的厚度为0.1～3.0mm。
本发明的滑动材料1可以在铜合金层3上进一步实施覆层。覆层可使用例如Sn、Bi等软质金属层、或者分散有固体润滑剂的树脂层等公知的材料。另外，即使在实施了覆层的情况下，也将实施了铜合金层3的覆层的滑动侧表面简便地称为滑动面。
图2表示滑动材料1的与基材2的边界附近的铜合金层3的截面的示意图。
铜合金层3包含滑动主体部6和倾斜部5。滑动主体部6是作为铜合金层3的滑动层起作用的主要部分，其表面形成有由该滑动材料1构成的滑动构件的滑动面8。因此，滑动主体部6的组成、尤其是锡浓度与形成铜合金层3的铜合金的组成大致相同。倾斜部5位于滑动主体部6和基材2之间，其中一方的表面形成铜合金层3和基材的接合面7。在倾斜部5内，锡浓度朝向界面7逐渐减小。铜合金层3内的锡浓度在滑动主体部6内大致固定，其值与铜合金的组成大致相同，但在倾斜部5内从与滑动主体部6的界面朝向接合面7减小。但是，倾斜部5内的锡浓度的减少可以不一定是单调减少，也可以是阶梯状，也可以在途中增大。即，只要锡浓度整体在倾斜部5内朝向接合面7减少即可。但是，优选在倾斜部5中锡浓度值从滑动主体部6侧朝向接合面7侧单调减少的形态。
通常，在含有锡的铜合金中，通过固溶锡或锡类金属间化合物的析出使强度向上、具有高的滑动性，并且耐烧结性、耐磨耗性优良，但韧性小。另一方面，若锡浓度变小，则强度变小，但具有韧性、延展性。
在倾斜部5内，从滑动主体部6朝向界面7，随着锡浓度的减少，强度变小，但韧性、延展性变大。因此，倾斜部5起到“应力缓和层”的作用以减轻凝固收缩对接合面7的负荷或滑动中的剪切应力在接合面发生应力集中，且提高相对于剪切应力的接合强度。藉此，可得到维持由含锡的铜合金产生的滑动性、耐烧结性、耐磨耗性，并且与基材2的接合强度也优良的滑动材料1。
此外，该滑动材料1中，将铜合金层3和基材2直接接合，不需要使用带有昂贵的铜镀层的钢材，因此能降低滑动材料1的成本。
为了使倾斜部5作为应力缓和层起作用，倾斜部5优选具有5μm以上的厚度。厚度在5μm以上时，负荷或剪切应力在该区域内有效地分散，可实现接合力的提高。倾斜部5的厚度更优选为10μm以上，进一步优选15μm以上。另一方面，若倾斜部5的厚度过于大，则铜合金层3整体的强度下降，所以上限优选为50μm。倾斜部5的厚度更优选为40μm以下，进一步优选30μm以下。
此外，倾斜部5特别作为应力缓和层起作用的是从接合面7起到50μm以内的区域，因此，该区域的锡浓度的减少率很重要。因此，从接合面7起到50μm以内的区域的锡浓度的减少以质量％计，最小锡浓度与最大锡浓度的比率优选为0.1～0.8，更优选0.2～0.6。
通常，在倾斜部5内，达到最大锡浓度的是与滑动主体部6接触的位置，锡浓度在与基材的界面7附近为最小值。因此，倾斜部5在接合面7附近的锡浓度相对于倾斜部5在与滑动主体部6接触的位置处的锡浓度的比率优选为0.1～0.8，更优选0.2～0.6。在本说明书中，将倾斜部5的锡浓度的该比率称为“锡浓度的比率”或“锡浓度比”。
接着，对铜合金的成分组成进行说明。
Sn：2.0～15.0质量％
Sn具有将铜合金的Cu基质固溶强化的作用、或形成金属间化合物而提高铜合金的强度的作用，能提高耐磨耗性。不仅如此，Sn还能提高耐腐蚀性和滑动特性。该效果在Sn小于2.0质量％时是不足够的。Sn若超过15.0质量％，则铜合金变得过于硬，滑动特性变差，并且合金变脆，损害韧性。因此，Sn成分为2.0～15.0质量％。
Bi：0～30.0质量％
Bi形成分散在铜合金基质中的软质的Bi相，有利于提高耐磨耗性、非烧结性。但是，因为Bi自身的强度小，所以若Bi超过30.0质量％，则铜合金的强度倾向于降低。此外，更优选Bi成分为8.0～25.0质量％。
以总量5.0质量％以下包含选自Al、Zn、Mn、Si、Ni、Fe、P、Zr、Ti、Mg的1种或2种以上。
这些元素具有将铜合金的Cu基质固溶强化的作用、或形成金属间化合物而提高铜合金的强度的作用。因此，如果以5.0质量％以下含有这些元素，则有利于提高滑动材料的强度。但是，如果这些元素的含量较多，则金属间化合物量增多，铜合金的韧性有降低的倾向，所以优选最大为5.0质量％。更优选0.1质量％以上1.1质量％以下。
铜合金可包含固体润滑剂，且可进一步以总量10.0体积％以下包含MoS2、石墨中的任一方或双方的固体润滑剂。通过含有这些固体润滑剂，能提高铜合金层的耐磨耗性、非烧结性。如果固体润滑剂的含量增多，则强度降低，所以理想的是含量最大为10.0体积％。优选最大为5.0体积％，更优选0.5体积％以上2.5体积％以下。
铜合金可进一步含有10.0体积％以下的硬质粒子。优选的含量为0.5体积％以上且2.5体积％以下。硬质粒子优选具有1～45μm的尺寸，可采用金属的硼化物、硅化物、氧化物、氮化物、碳化物、金属间化合物。硬质粒子能提高耐磨耗性，通过混合在铜合金层中的例如Bi相，能提高滑动材料的耐磨耗性和非烧结性。
接着，对本发明的滑动材料1的制造方法进行说明。在本发明中，通过将上述组成的铜合金以熔融状态浇铸在基材2上，使铜合金熔液与基材2直接接触，并使其凝固。这样，本发明中，利用铸造法，通过使铜合金层3与基材2接合，可制造滑动材料1。
首先，准备基材2。基材2可以制成上述说明的材质的平板或圆筒体，或者也可以是其他形状。
将上述说明的组成的铜合金熔融，将熔融的铜合金浇铸在基材2的接合表面上。此时，为了防止氧化，优选采用惰性气体或还原性的气氛，或者使用熔剂。
对于基材，利用冷却剂从待接合铜合金层3的基材表面(接合表面)的相反的一侧表面冷却基材2。冷却剂可采用例如水或油，通过将水或油喷射到基材2的与接合表面相反的一侧表面而进行冷却。
由此，通过进行铜合金的浇铸、冷却，铜合金从与基材2的接合表面接触的铜合金起优先地单向凝固。在本实施方式中，从铜合金的自由表面侧(相当于与铜合金层的接合表面相反的一侧)不进行冷却。
本发明中，利用因为青铜合金的凝固温度范围宽而引起的锡的微偏析。在本发明的方法中，因为从与被冷却的基材2的接合表面接触的铜合金起开始凝固，所以在基材2的接合表面附近析出初晶的Cu(α相)，作为副成分的Sn残留在液相中并从接合面侧向液相侧移动。其结果是，如果适当地设定冷却条件，当铜合金层3形成时，形成与铜合金层3和基材2的接合面7接触的Sn成分相对变少的倾斜部。
由此，本发明中，通过控制冷却速度及时间，使铜合金从基材2的接合表面单向凝固，接合界面附近急速凝固，铜合金层3的与接合面相反的一侧的滑动面8的附近逐渐冷却。由此，可形成与接合界面接触的锡的浓度的倾斜(日文：傾斜)。
此外，铸造法中，因为可使整体熔融以形成基质，所以通过利用铸造法将铜合金形成为内衬，相较于利用烧结法的粉末合金彼此的接合，更能确保作为铜合金层而具备的足够的合金强度。
本发明中，在凝固工序中，通过控制向基材2的与接合表面相反的一侧表面供给的冷却剂的供给量，能进行组织控制。例如，图3中示出冷却条件的一例。横轴表示从浇铸开始的时间，纵轴表示铜合金层的接合面(A)和作为自由表面的滑动面(B)的温度。冷却初期(第一阶段)增大冷却剂的供给量并缩短冷却时间(例如，将向每1cm2的基材喷射的冷却水流量设为0.250L/分钟以上，冷却时间设为对于基材的每1mm厚度冷却2.0～10.0秒)，在其以后的第二阶段减少冷却剂的供给量并延长冷却时间(例如，将向每1cm2的基材喷射的冷却水流量设为0.100L/分钟以下)，在第二阶段之后进行放冷。在第一阶段的最后时期，铜合金层的接合面的温度比铜合金的凝固开始温度Ts低，且开始凝固，但滑动面的温度仍比Ts高，因此是熔融的状态。在第二阶段，滑动表面也慢慢地凝固。通过该控制，使该接合界面附近的αCu相优先析出，能以到规定区域为止锡浓度发生倾斜的方式控制组织。通过调整冷却剂的供给量，能控制倾斜部的厚度和锡浓度的倾斜。
作为实施本发明的方法的一个具体例，可以是在平板基材的表面上设置堰，将铜合金的熔液浇铸在由堰包围的基材表面上的方法。此时，为了防止基材和铜合金的氧化，优选采用惰性气体或还原性的气氛，或者使用熔剂。在浇铸后，从基材里侧开始进行使用上述冷却剂的冷却。
作为其他的具体例，也可采用离心铸造。当然，本发明并不局限于这些铸造方法。
图4中示出离心铸造法的示意图。将成为基材的板材2成形为圆筒形状，将两端部用密封构件11密封。利用例如旋转滚转机等旋转装置12使上述成形为圆筒形状的基材2以高速水平旋转。圆筒形状内，优选设为真空或还原或惰性气体气氛。从设置在基材的圆筒形状的端部的浇口(日文：ゲート)13注入熔融后的铜合金。通过从外表面供给冷却剂来冷却基材2。熔融铜合金通过离心力而紧贴在基材2的内表面，以内径正圆的状态凝固，形成铜合金层。离心铸造方法可适用于例如圆筒形状的滑动轴承等。
对铜合金层的与基材的接合面处的倾斜部的测定方法进行说明。利用电子显微镜(例如1000倍的倍率)观察滑动材料的截面组织，沿着与接合面垂直的方向、即厚度方向，通过EDS对基材和铜合金层的接合面的附近的铜合金进行线分析或面分析，测定锡浓度分布。如上所述，滑动主体部的锡组成与形成铜合金层3的铜合金整体的组成大致相同且大致固定，所以将锡浓度从固定处朝向接合面逐渐减少的区域作为倾斜部。
实施例
制造以下的实施例1～21和比较例1～5的各试样，进行了倾斜部和接合强度的评价。
基材的准备
作为基材，使用SPCC制的钢板，为了防止熔液泄漏，使周边部残留，将上面中央部切削，加工成在周边部形成有堰的箱形状。浇铸厚度设定为5mm。成为滑动材料的基材的部分的壁厚为6mm。作为抗氧化剂，利用熔融硼砂覆盖基材表面，在含H2气体的还原性气氛中以1000℃～1200℃进行了基材的预热。
铜合金的铸造
作为铜合金，以成为表1和表2示出的实施例1～21和比较例1～5的各组成的条件，将纯铜、纯锡及其他成分的材料掺合，在大气中进行了熔化。铜合金的熔液在大气中保持在1000℃～1200℃，浇铸在预热后的基材上。
冷却工序
浇铸后，从设置于基材下部的洒水喷嘴朝向基材底面喷射冷却水。比较例中，以少量的一定流量连续地喷射冷却水(以冷却水流量40L/分钟冷却180秒)。另一方面，实施例1～7和13～21如图3所示，在冷却初期(第一阶段)，与比较例相比使冷却水量较多、使冷却时间较短(以冷却水流量85L/分钟冷却30秒)，在冷却初期之后(第二阶段)，使冷却水量比第一阶段少、使冷却时间较长(以冷却水流量20L/分钟冷却60秒)，有意地采用不连续的两阶段的冷却条件。在两阶段的冷却工序结束后，在大气中放冷，缓慢冷却至室温。实施例8～12中，与实施例1～7和13～21相比，使第一阶段的冷却水量增大(以冷却水流量130L/分钟冷却20秒)，以增大冷却效果。第二阶段以后，与实施例1～7和13～21的条件相同。
锡浓度比评价方法
利用EPMA装置(型号:日本电子株式会社(JEOL)制JXA-8530F场发射电子探针微量分析仪(FIELD EMISSION ELECTRON PROBE MICROANALYZER))，对各试样的截面观察长85μm、宽116μm的视野，以使接合面为横向的方式进行拍摄。利用EPMA装置的EDS进行线分析，测定了接合面附近的锡浓度。接着，将通过线分析得到的锡元素的强度比作为锡浓度比进行了评价。对于每个试样的10处以上拍摄截面组织照片。
接合强度测定
根据铜合金层和基材的剪切强度与铜合金的拉伸强度的比率(剪切强度/拉伸强度)来评价铜合金层和基材的接合强度。剪切强度受到拉伸强度的影响，所以为了能比较成分不同的材料，用剪切强度/拉伸强度的比作为接合强度的指标。
剪切强度是如图5所示加工成铜合金层和基材以规定的接合面积接合的试验片，在对两端施加拉伸负荷(拉伸力)时，以接合部发生破坏的最高拉伸应力表示的数值(参照日本专利特开2002-224852号公报)。
表1中，将是否观察到倾斜部、有倾斜部时其厚度(μm)、倾斜部内的锡浓度比、接合强度(剪切强度/拉伸强度)的测定结果分别示于“有无倾斜部”、“倾斜部的厚度(μm)”、“锡浓度比”和“剪切强度/拉伸强度”的栏中。此外，不存在倾斜部时的“锡浓度比”由接合面附近处的锡浓度与铜合金层中的自接合面起50μm的位置处的锡浓度的比率表示。
比较例1～5、实施例1～7、实施例8～12如上所述，各自的冷却条件不同。根据表1的结果，在没有采用两阶段冷却的比较例中，没有观察到倾斜部，但在实施例的任一试样中都观察到了倾斜部。可知在相同的锡成分中，根据冷却条件，锡浓度比有较大不同，冷却程度较大的实施例8～12中锡浓度比最小。由此，通过控制冷却条件，与Sn成分无关，能使锡浓度比在0.8以下，进一步在0.6以下。在比较例1～5的冷却条件下，不仅没有观察到倾斜部，有时也没有观察到接合面附近的锡浓度的减少。
在实施例1～7的冷却条件下，与Sn含量无关，Sn浓度比大致固定，但在实施例8～12的冷却条件下，可观察到若Sn含量增加，则锡浓度比减少的倾向。
关于锡浓度比为0.8以下的实施例1～12的剪断强度，剪切强度/拉伸强度为0.76以上，大大超过比较例1～5的值。图6中示出剪切强度/拉伸强度与锡浓度比的关系。可知锡浓度比的值与剪切强度/拉伸强度的值在很大程度上相关。特别是当锡浓度比为0.6以下时(实施例8～12)，可得到剪切强度/拉伸强度为约0.88以上的优良的接合强度。
[表1]
实施例13～21是在实施例5的合金组成(Cu-约8％Sn)中添加其他合金元素(Bi、Zn、Al、Fe、Ni、Mn、Si、P、Zr、Ti、Mg)或硬质粒子Mo2C、固体润滑剂粒子石墨(Gr)的实施例。实施例13～21的冷却条件与实施例5的条件相同。
表3中示出试验结果。根据表3可知，即使添加上述添加成分，锡浓度比也在0.64％～0.79％的范围内，是与实施例5的锡浓度比0.72同等的值。因此，接合强度(剪切强度/拉伸强度)为0.76～0.87，与实施例5的0.86为同等程度。由该结果可知，添加成分对锡浓度比和接合强度的影响较小。
[表2]
*合金成分中没有记载“体积%”的数值为“质量％”。

Claims (14)

1.一种滑动材料，其为具有基材和与该基材接合的铜合金层的滑动材料，其特征在于，所述铜合金层由含有2.0～15.0质量％的Sn的铜合金构成，所述铜合金层具有包含滑动面的滑动主体部、和包含与基材的接合面的倾斜部，所述倾斜部的锡浓度从所述滑动主体部侧朝着所述与基材的接合面变小。
2.如权利要求1所述的滑动材料，其特征在于，所述倾斜部内的锡浓度的比率为0.1～0.8。
3.如权利要求2所述的滑动材料，其特征在于，所述比率为0.2～0.6。
4.如权利要求1～3中任一项所述的滑动材料，其特征在于，所述铜合金包含2.0～15.0质量％的Sn、0～30.0质量％的Bi、以总量计为5.0质量％以下的选自Al、Zn、Mn、Si、Ni、Fe、P、Zr、Ti、Mg的1种或2种以上，余部是铜和不可避免的杂质。
5.如权利要求1～4中任一项所述的滑动材料，其特征在于，所述铜合金进一步以总量10.0体积％以下包含MoS2、石墨中的任一方或双方。
6.如权利要求1～5中任一项所述的滑动材料，其特征在于，在所述铜合金层上进一步具有覆层。
7.如权利要求1～6中任一项所述的滑动材料，其特征在于，所述基材的厚度为1.0～25.0mm，所述铜合金层的厚度为0.1～3.0mm。
8.如权利要求1～7中任一项所述的滑动材料，其特征在于，所述倾斜部的厚度为10～50μm。
9.一种滑动材料的制造方法，其为制造权利要求1～8中任一项所述的滑动材料的方法，其特征在于，包括：
准备所述基材的步骤；
将所述铜合金熔融的步骤；
将熔融后的所述铜合金浇铸在所述基材的待接合的表面上的步骤；以及
利用冷却剂从与所述基材的待接合的表面相反的一侧面将所述基材冷却，使所述铜合金单向凝固的步骤。
10.如权利要求9所述的滑动材料的制造方法，其特征在于，进一步包括在自浇铸起经过规定时间后，减少所述冷却剂的供给量的步骤。
11.如权利要求9或10所述的滑动材料的制造方法，其特征在于，所述冷却剂是水或油。
12.如权利要求9～11中任一项所述的滑动材料的制造方法，其特征在于，所述准备基材的步骤包括由一个或多个基材成形为圆筒形状体的步骤；所述浇铸步骤包括一边使所述圆筒形状体沿着圆筒形状的中心轴线的圆周旋转一边浇铸的步骤。
13.一种滑动构件，其特征在于，包括权利要求1～8中任一项所述的滑动材料。
14.一种轴承装置，其特征在于，具有权利要求13所述的滑动构件和轴。
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