CN1039138C - 增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品 - Google Patents

增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品 Download PDF

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CN1039138C
CN1039138C CN92110351A CN92110351A CN1039138C CN 1039138 C CN1039138 C CN 1039138C CN 92110351 A CN92110351 A CN 92110351A CN 92110351 A CN92110351 A CN 92110351A CN 1039138 C CN1039138 C CN 1039138C
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zinc
alloy
coating
cobalt
wire
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CN1070436A (zh
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W·J·冯奥纪
J·吉瑞哈
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Pirelli Coordinamento Pneumatici SA
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Abstract

本发明涉及用来增强弹性材料制品尤其是增强车用轮胎的金属丝。所述的金属丝具有由锌-镍或锌-钴合金的两个同心层构成的镀层，其中径向内镀层的锌含量为95%至98%，径向外镀层的镍或钴含量为50%至90%。

Description

增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品
本发明涉及带有双镀层的金属丝，具体地说，涉及用来增强弹性材料制品的钢丝，以及用这种金属丝增强的弹性材料制品，尤其是车用轮胎。
已知的保护掺入弹性材料中的金属丝免遭腐蚀并且使金属丝和弹性材料粘合良好，是用金属合金将金属丝包覆起来。
一种已长期用来镀敷增强弹性材料制品用的金属丝的合金是铜和锌的合金，更具体地说，是一种含有约60％-70％铜和约40％-30％锌的合金。
正如已经知道的，镀有上面提到的一层合金的金属丝，在一段时间后对弹性材料的粘结变差，而且不能满意地防止腐蚀。为克服这两种缺点，曾提出使用其它类型的合金来镀敷金属丝。
特别是，曾经提出用黄铜(Cu-Zn)与加入的镍或钴或其它金属作为合金第三元素的三元合金来构成金属丝的镀层。用这类合金，在减少对弹性材料的粘结随时间变差和防止金属丝腐蚀方面有所改进，但是这些改进不足以使按此方式增强的弹性体制品(尤其是轮胎)的质量水平有重大改进。
在本申请人持有的欧洲专利283,738中叙述了在这两方面都令人满意的一种不同的解决方法。该方法包括用两个同心的叠合镀层镀覆金属丝，二层由选自锌-镍合金和锌-钴合金的合金制成，其中径向更靠内的一层含锌是在60％和90％之间(包括首尾数值)，径向更靠外的一层的含镍或钴量在60％和80％之间(包括首尾数值)。
根据上述欧洲专利的金属丝虽然解决了防止腐蚀和对弹性材料的粘结随时间变差合乎要求这两个问题，但是对大规模工业生产来说仍然存在一些问题。
工业生产中不能令人满意之处发生在镀层形成后金属丝的拉伸阶段，包括金属丝在拉丝期间过分频繁地断裂，而且在拉板上磨损过多。
根据本发明，已经发现有可能制得用来增强弹性材料制品的金属丝和用这种金属丝增强的弹性材料制品，它们保持着根据欧洲专利283,738已经令人满意地达到的那些良好性能，即，在一段时间内对弹性材料的粘结和金属丝的耐腐蚀性合乎要求，而且这些金属丝还没有该专利存在的拉丝方面的缺点，令人惊奇的是，这是通过调节径向内层中的镍量或钴量做到的。
本发明的第一方面涉及用来增强弹性材料制品的金属丝，该金属丝带有两个同心镀层，径向上彼此叠合，两层均由选自锌-钴合金和锌-镍合金的合金构成，其特点在于，构成径向内层的合金的锌含量大于90％，而构成径向外层的合金的镍或钴含量大于50％。
本发明的另一方面涉及复以网状物的弹性材料混合物制品，特别是车用轮胎，在弹性材料中掺有增强用的金属丝，金属丝上带有在径向上彼此叠合的两个同心层构成的镀层，两层均由选自锌-钴合金和锌-镍合金的合金构成，该制品的特点在于，构成径向内镀层的合金含锌量大于90％，构成径向外镀层的合金的含镍或含钴量大于50％。
根据以下以实施例形式给出的对本发明某些实施方式的说明，特会更好地理解本发明。
本发明中使用的金属裸丝是通常的金属丝，尤其是在橡胶工艺、特别是轮胎工艺中众所周知的钢丝。在这种裸丝的表面上，用选自锌-钴合金和锌-镍合金的合金形成第一镀层。
适合用来形成本发明金属丝第一镀层的特殊的锌-钴和锌-镍金属合金，其特点是锌含量大于90％。
如果在用来形成第一镀层的金属合金中存在钴，则钴对锌的相对百分含量的降低会提高金属丝的“拉伸性”。
根据以上所述，钴含量以少于5％为宜，最好是不超过2％。
金属丝的第一镀层可以用任何已知方法形成，尤其是欧洲专利申请283,738中所说的两种方法之一。
例如，采用用电镀槽同时沉积锌和镍两种金属的方法，其中用来在根据本发明的金属丝上形成第一镀层的两种金属的数量如前所述，电镀槽液组成和沉积的操作方法如下：槽温在10和30℃之间(包括首尾数值)电镀槽液pH在4和8之间(包括首尾值)电流强度(安/平方分米)在5和30之间(包括首尾值)硫酸镍六水合物，170克/升硫酸锌10克/升硼砂10克/升氯化铵14克/升十二烷基硫酸钠1克/升
作为实例，如果本发明金属丝的第一镀层是上述特定百分含量的锌-钴合金，则电镀槽和操作方法如下：槽温55℃槽液pH2±0.1电流强度(安/平方分米)在60和80之间(包括首尾值)硫酸钴七水合物120克/升硫酸锌七水合物620克/升硫酸钠75克/升
在形成镀层本身期间和带镀层的金属丝受拉伸之前，第一镀层的优选厚度调节在0.25至2微米之间(首尾值包括在内)。
这一厚度的检验是用常用一类的定量分析方法进行的。
本文中提到的各个厚度值应用这种方法检验。
在第一层之上，本发明的金属丝具有由选自镍-锌和钴-锌合金的一种合金构成的第二镀层，其特点在于，它的镍含量或钴含量大于50％；镍含量最好是在70％和100％之间(首尾值包括在内)，或者是，钴含量应在70％和90％之间。
第二镀层也按照欧洲专利283,738所述的方法，利用在电镀槽中同时沉积各金属组分的方法形成。
例如，对于用来形成本发明金属丝第二镀层的电镀槽，当第二层是具有上述优选百分含量的锌和镍的合金时，电镀槽的操作条件如下：槽温60℃pH2.5±0.1电流强度(安/平方分米)在25和35之间硫酸镍六水合物550克/升硫酸锌20克/升硼酸35克/升硫酸钠35克/升
再次作为实例，如果第二镀层由上述优选百分含量的锌和钴的合金构成，所用的电镀槽的操作条件应如下所示：浴温55℃pH2±0.1电流强度(安/平方分米)在60和80之间(首尾值包括在内)硫酸锌620克/升硫酸钴125克/升硫酸钠75克/升
在形成镀层期间和将带镀层的金属丝拉伸之前，第二层的优选厚度在0.25与2微米之间(首尾值包括在内)。
因此，在离开镀槽时金属丝的整个镀层厚度是在0.5和4微米之间(首尾值包括在内)。
将完成了具有上述特征的两个同心叠合镀层的本发明金属丝通过常用的拉板进行通常的拉丝操作，以便将其总外径减小到通用的数值，使之适合于弹性材料制品的增强用。
特别是在用于车辆轮胎的场合，拉丝操作以接连通过的方式进行，直到金属丝的初始直径(可以在0.70和3.70毫米之间变化)减小到0.12毫米和0.30毫米之间(首尾值在内)，使得第一镀层的值在0.15和0.40微米之间(首尾值在内)，第二镀层在0.05和0.20微米之间(首尾值在内)，镀层的总厚度最终在0.20和0.60微米之间(首尾值在内)。
测定拉伸金属丝上两镀层的存在可以用x-射线衍射技术和/或俄歇电子能谱(AES)方法。
正如下面报导的实验结果所证实的，根据本发明的金属丝解决了先前所述的问题。
对于这些试验，使用三种根据本发明的特定的金属丝，文中标作金属丝A、B和C，还使用一种根据欧洲专利283,738的已知的特定金属丝，文中标作金属丝N1。
上述这些特定的金属丝全由C70钢(一种普通钢，用来制造轮胎中指定使用的金属丝，其碳含量最高达0.70％)制成，具有相同的尺寸和结构；更准确地说，在拉伸之前，这些金属丝的总外径均为1.40毫米，带有由两个同心叠合层构成的镀层，各层的厚度不大于2微米。
上述金属丝的特征列在表1：
                 表1金属丝名称    A       B         C        N1第一层       95％Zn   98％Zn    98％Zn   70％Zn
         5％Co    2％Co     2％Co    30％Co第二层       80％Ni   80％Ni    90％Ni   80％Ni
         20％Zn   20％Zn    10％Zn   20％Zn
所有上述的特定的金属丝都进行拉丝处理，将它们的最终直径减小到0.25毫米，镀层平均厚度内层为0.35微米，外层0.15微米。
为此，使用19个基本上已知的V32型碳化钨制成的拉板，在普通的润滑剂浴中(Zeller Grnelin公司的VSV351/IL油)拉丝，所得结果列在表2中。
表2具体列出了由于拉丝造成的镀层重量损失的平均百分数，在必须更换拉板时已拉伸的金属丝重量的平均百分数，以及对于每次断丝而言，已拉丝重量的平均百分数，N1金属丝的值假定为100。
                  表2金属丝名称              A，B，C    N1镀层重量损失            20-30％    最少40％每个拉板制造的金属丝量    300      100每次断丝制造的金属丝量    400      100
列在表2的实验结果清楚地表明，使用本发明的金属丝，减少在金属丝完成镀覆后进行的拉丝期间在拉板上的磨损和降低在拉丝期间金属丝的破裂频率这两个问题都得到了解决。
对于用根据欧洲专利283,738的已知金属丝和用本发明的金属丝制成的小帘布作了进一步的试验，以确定对弹性材料的粘结值和小帘布与弹性材料之间的粘结随时间的恶化情况。
对于这些进一步的试验，使用根据表3配方配制的混合物。
            表3混合物的组分             重量用量天然橡胶                   100氧化锌                     86PPD抗臭氧剂               2TMQ抗氧化剂                1络合钴盐(Manobond 680C)    0.5HAF灯黑                    50加速剂-Santocure MCR       1硫                         6
对于后面这些试验，试样按ASTM D2229-80准备，它规定将弹性材料的棱形小块在151℃硫化30分钟，弹性材料中掺杂着小帘布(由5根直径0.25毫米的金属丝组合而成)，彼此间隔约12毫米，包埋在弹性材料内12.5毫米深处。
测定橡胶与金属的粘结的试验包括测定从含有帘布的棱形小块中拉出各个帘布所需的力，以及测定从小块中用力拉出的帘布被弹性材料覆盖的程度。
为了测定粘结随时间恶化的情况，试验仍如先前所述，但是在试样经老化处理之后进行对帘布的抽拉试验，老化处理是将试样在温度为65℃、相对湿度90％的环境内放置预定的4天。
使用上述的混合物和小帘布制备试样，其数目与用带有上述不同类型镀层的金属丝构成的小帘布的数目相同。
试验结果列在表4。
             表    4由含小帘布的混合物制成的试样          A，B，C    N1从未经老化的试样中拉出小帘布所需    537牛顿    414牛顿之力的平均值从老化后的试样中拉出小帘布所需之力的  450牛顿    350牛顿平均值从未经老化的试样中拉出的小帘布的覆盖    4          4指数从老化后的试样中拉出的小帘布的覆盖指数  3          2
本文中覆盖指数的数值有以下含义：覆盖指数4表示小帘布完全被弹性材料覆盖；覆盖指数3表示小帘布的2/3被弹性材料覆盖；覆盖指数2表示小帘布的1/3被弹性材料覆盖；覆盖指数1表示小帘布完全没有弹性材料覆盖。
还用由本发明金属丝制成的小帘布和由镀黄铜(67.5％铜和32.5％锌)N2金属丝制成的小帘布掺加到硫化的弹性材料中作了进一步的试验，以便确定这些帘布与弹性材料的粘结特点的差别以及对构成帘布的金属丝的腐蚀情况。
上述小帘布仍是5×0.25形式的小帘布(即，由5根直径0.25毫米的金属丝构成)，彼此的不同只是制成它们的金属丝不同；因此这些帘布在本文中用标记制成它们的金属丝的同样标记表示。
使用上述混合物形成缓冲层，以及根据本发明的小帘布A、B、C和上面提到的镀黄铜的帘布N2，制成尺寸165R13型具有P4胎面的轮胎。
从轮胎上割下20厘米宽的断片，在盐水雾室中进行老化处理。
试样经受的处理条件如下：暴露时间        20到40天盐水浓度        5％氯化钠水溶液雾密度          在80平方厘米面积上
            1.5毫升/时室内温度                45℃
按此方式老化后，除去断片中形成胎面的弹性材料以便回收含有小帘布(研究对象)的缓冲结构层，注意小帘布与它们掺入的弹性材料的粘结特点和构成小帘布的金属丝中腐蚀的存在。
对于未在盐水雾室中老化的断片记录类似的数据，即，由硫化轮胎本身记录数据。
测定粘结值时，从缓冲层织物小条中撕下3个小帘布，每个帘布由一个小帘布与相邻的小条隔开，保持撕裂角恒定为90度。
记录的数据列在表5。
              表5
                        粘结力 覆盖度 腐蚀迹象
带有帘布A，B，C的缓冲
层的轮胎，未在盐水雾    11牛顿   4       无
水中处理
带有帘布A，B，C的缓冲
层的轮胎，在盐水雾室    9牛顿    4       无
中处理20天
带有帘布A，B，C缓冲层
的轮胎，在盐水雾室中    6牛顿    3       无
处理40天带有N2帘布缓冲层的轮胎，未经盐水雾室处      8牛顿    4    无带有N2帘布缓冲层的轮胎，在盐水雾室中处理    6牛顿    3    无20天带有N2帘布缓冲层的轮胎，在盐水雾室中处理    3牛顿    1    痕量40天
前面列出的从小块中抽拉试验(ASTM D2229-80)得到的粘结力值和刚刚列出的对护胎层织物小条撕裂试验的数值之间的差别是由于所进行的试验类型不同。
总之，根据所有这些试验结果，由根据本发明的金属丝制成的小帘布在掺入弹性材料中之后，显示出比用镀黄铜金属丝制成的小帘布更好的粘结性和耐腐蚀性。

Claims (14)

1.一种用来增强弹性材料制品的金属丝，带有由两个径向上叠合排列的同心层构成的镀层，两层均由选自锌-钴合金和锌-镍合金的合金制成，其特点在于，构成径向内镀层的合金的锌含量为95％-98％，构成径向外镀层的合金含镍量为50％至90％。
2.根据权利要求1的金属丝，其特点在于，径向内镀层由锌钴的合金构成。
3.根据权利要求1的金属丝，其中径向内镀层由锌-钴合金构成，径向外镀层由镍含量在70％至90％之间的锌-镍合金构成。
4.根据权利要求1的金属丝，其中径向内镀层由锌-钴合金构成，径向外镀层由钴含量在70％至90％之间的锌-钴合金构成。
5.根据权利要求3和4的金属丝，其特点在于，径向内镀层中的钴含量最好低于5％。
6.根据权利要求3和4的金属丝，其特点在于，径向更靠内镀层的钴含量最好不超过2％。
7.网状弹性材料混合物形式的制品，其中掺夹带有镀层的增强金属丝，镀层由彼此径向叠合的两个同心层构成，两层均由选自锌-钴合金和锌-镍合金的合金制成，该制品的特点在于，构成径向内镀层的合金的锌含量为95％-98％，构成径向外镀层的合金含镍量为50％至90％。
8.根据权利要求7的制品，其特点在于，增强金属丝的径向内镀层由锌-钴合金构成。
9.根据权利要求7的制品，其特点在于，增强金属丝的径向内镀层由锌含量高于90％的锌-钴合金构成，金属丝的径向外镀层由镍含量在70％和100％(首尾值包括在内)之间的锌-镍合金构成。
10.根据权利要求7的制品，其特点在于，增强金属丝的径向内镀层由锌含量高于90％的锌-钴合金构成，金属丝的径向外镀层由钴含量在70％和90％之间(首尾值包括的内)的锌-钴合金构成。
11.掺加带镀层的增强金属丝的汽车轮胎，该镀层由径向上彼此叠合排列的两个同心层构成，两层均由选自锌-钴合金和锌-镍合金的合金构成，所述轮胎的特点在于，构成径向更靠内镀层的合金的锌含量高于90％，构成径向更靠外镀层的合金的含镍或含钴量高于50％。
12.根据权利要求11的轮胎，其特点在于，增强金属丝的径向内镀层由锌-钴合金构成。
13.根据权利要求11的轮胎，其特点在于，增强金属丝的径向内镀层由锌含量高于90％的锌-钴合金构成，金属丝的径向外镀层由镍含量在70％和100％之间(首尾值包括在内)的锌-镍合金构成。
14.根据权利要求11的轮胎，其特点在于，增强金属丝的径向内镀层由锌含量高于90％的锌-钴合金构成，金属丝的径向外镀层由钴含量在70％和90％之间(首尾值包括在内)的锌-钴合金构成。
CN92110351A 1991-09-09 1992-09-08 增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品 Expired - Fee Related CN1039138C (zh)

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3635121B4 (de) * 1985-10-15 2004-03-04 Bridgestone Corp. Verfahren zur Herstellung eines gummiartigen Verbundmaterials
IT1273334B (it) * 1994-02-24 1997-07-08 Pirelli Filo metallico trattato superficialmente per renderlo adatto all'impiego in elementi compositi in materiale elastomerico e procedimento per la sua realizzazione
FR2725730A1 (fr) * 1994-10-12 1996-04-19 Michelin & Cie Fil en acier inoxydable pour renforcer le sommet des enveloppes de pneumatiques
IT1277689B1 (it) * 1995-12-21 1997-11-11 Pirelli Cordicella metallica di rinforzo da impiegarsi particolarmente in manufatti compositi a matrice elastomerica procedimento ed apparato
DE19615134C2 (de) * 1996-04-17 2003-04-17 Continental Ag Haftvermittlersubstanz zwischen vulkanisierbarem Polymer und metallischem Festigkeitsträger, Verfahren zu deren Aufbringung sowie deren Verwendung
EP0949356B1 (en) * 1998-03-27 2002-10-23 PIRELLI PNEUMATICI Società per Azioni Surface-treated metal component for reinforcing structures for manufactured products made of vulcanized elastomeric material and article of manufacture comprising the same
US6475640B1 (en) * 1998-10-28 2002-11-05 Pirelli Pneumatici S.P.A. Coated metal wire wire-reinforced elastomeric article containing the same and method of manufacture
FR2864556B1 (fr) 2003-12-24 2006-02-24 Michelin Soc Tech Cable a couches pour armature de carcasse de pneumatique
US20060121302A1 (en) * 2004-12-07 2006-06-08 Erickson Gary C Wire-arc spraying of a zinc-nickel coating
EP2233611A1 (de) * 2009-03-24 2010-09-29 MTV Metallveredlung GmbH & Co. KG Schichtsystem mti verbesserter Korrosionsbeständigkeit
DE102014004657A1 (de) * 2014-03-29 2015-10-01 Daimler Ag Bauteil, insbesondere Strukturbauteil, für einen Kraftwagen, sowie Verfahren zum Herstellen eines Bauteils
CN110722963A (zh) * 2019-10-28 2020-01-24 厦门银丰科技有限公司 一种汽车天窗用遮阳帘卷簧及其制备方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296838A (en) * 1937-11-01 1942-09-29 Nat Standard Co Rubber adherent metal
NL7702643A (nl) * 1977-03-11 1978-09-13 Akzo Nv Voorwerp bekleed met een metaallegering, waaraan elastomeer materiaal is gehecht, alsmede werkwijze voor het vervaardigen van dat voorwerp.
GB1598388A (en) * 1978-05-26 1981-09-16 Bekaert Sa Nv Steel wire reinforcing elements
US4226918A (en) * 1978-08-03 1980-10-07 National-Standard Company Rubber adherent ternary Cu-Zn-Ni Alloy coated steel wires
FR2445764A1 (fr) * 1979-01-05 1980-08-01 Bekaert Sa Nv Nouveaux elements a base de fils d'acier pour le renforcement de compositions de caoutchouc
JPS59162292A (ja) * 1983-03-05 1984-09-13 Sumitomo Metal Ind Ltd 塗装後耐食性にすぐれた複層メツキ鋼板
JPS6050195A (ja) * 1983-08-30 1985-03-19 Nippon Steel Corp めっき層濃度傾斜型Ζｎ合金めつき鋼板
US4446198A (en) * 1983-09-08 1984-05-01 The Goodyear Tire & Rubber Company Copper-zinc-iron ternary alloy coated steel wire reinforcers in tires
US4659631A (en) * 1984-05-17 1987-04-21 Sumitomo Metal Industries, Ltd. Corrosion resistant duplex plated sheet steel
CA1258999A (en) * 1984-09-13 1989-09-05 Thomas W. Starinshak Quaternary brass alloy coated steel element and rubber reinforced therewith
GB8426746D0 (en) * 1984-10-23 1984-11-28 Bekaert Sa Nv Ferrous substrate
GB8500323D0 (en) * 1985-01-07 1985-02-13 Bekaert Sa Nv Steel reinforcing elements
DE3635121B4 (de) * 1985-10-15 2004-03-04 Bridgestone Corp. Verfahren zur Herstellung eines gummiartigen Verbundmaterials
US4828000A (en) * 1986-10-31 1989-05-09 N. V. Bekaert S.A. Steel substrate with brass covering layer for adhesion to rubber
IT1225871B (it) * 1987-03-02 1990-12-07 Pirelli Miglioramenti ai fili metallici per rinforzo di materiali elastomerici
DE3850246T2 (de) * 1987-10-26 1995-01-26 Sumitomo Electric Industries Metall und komposit des metalls mit kautschuk.
US4746408A (en) * 1987-11-05 1988-05-24 Whyco Chromium Company, Inc. Multi layer corrosion resistant coating
JP2989889B2 (ja) * 1989-07-21 1999-12-13 エヌ・ブイ・ベカルト・エス・エイ エラストマー補強用スチール基材

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