CN104066882A - 包含三元或四元黄铜合金涂层的狭长钢元件及相应的方法 - Google Patents
包含三元或四元黄铜合金涂层的狭长钢元件及相应的方法 Download PDFInfo
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Abstract
采用Cu-M-Zn的三元或四元合金涂层覆盖用于橡胶产品增强的狭长钢元件,M是选自钴、镍、锡、铟、锰、铁、铋和钼中的一种或两种金属。涂层中的铜含量为58重量%-75重量%,涂层中的所述一种或两种金属的含量为0.5重量%-10重量%,余量是锌和不可避免的杂质。所述一种或两种金属存在于整个涂层中。磷以每平方米涂层0.3毫克-每平方米涂层1毫克的量存在于所述涂层之上和/或之中。涂层还缺少三唑残留物。已获得了欠固化黏附的良好结果。此外,公开了用于制造这样的狭长钢元件的相应方法。
Description
技术领域
本发明涉及适用于橡胶产品增强的狭长钢元件。本发明还涉及用于制造这样的狭长钢元件的方法。
背景技术
广泛使用狭长钢元件例如涂覆有黄铜的钢线材和钢丝帘线来增强橡胶产品例如轮胎。为了具有良好的黏附构造和降低黏附的劣化速率,特别地由于在热湿环境下老化,向橡胶化合物添加钴络合物。然而,认为钴对橡胶是一种有害物质,因为类似大多数过渡金属,钴是一种氧化催化剂。结果,由于钴的存在,将加速二烯基橡胶分子的氧化,这导致更早的橡胶老化。
此外,钴还加速橡胶的裂纹生长速率。
除了上述缺点以外,还存在下列问题:钴是一种战略材料且其相当昂贵。通过向全部橡胶化合物添加钴,添加了太多的钴,因为钴仅在黄铜表面具有积极作用。通常,认为仅有效使用了添加到橡胶中的钴的20%。
现有技术已经认识到这些问题中的一个或多个。已经进行许多尝试来将钴浓缩至其所属区域,即在钢线材或钢丝帘线的涂层之中或之上。
另外,在1936年曾尝试通过用于增强橡胶的在制品上的纯钴涂层来完全替代黄铜涂层(US2,240,805)。
US4,255,496(Bekaert)公开了使用三元合金铜-钴-锌涂层替代二元合金铜-锌(=黄铜)涂层。采用此三元合金,能显著降低由于在热湿环境下老化导致的黏合劣化速率。
US4,265,678(Tokyo Rope)教导了一种具有优异的可拉拔性和黏附性能的三元合金铜-锌-钴涂层的使用。
GB-A-2 076 320(Sod é tal)教导了在黄铜涂层顶部的薄钴层,随后进行拔丝,使得在黄铜涂层顶部存在高的钴梯度。
EP-A1-0 175 632(Goodyear)教导了一种在钢元件上的四元合金涂层铜-锌-镍-钴。
最后,WO-A1-2011/076746公开了一种具有三元或四元合金涂层且具有锌梯度的钢丝帘线。尽管给予了关于黏附的改进,但是所述锌梯度涉及线材或帘线的后处理,其意指该方法中有额外的操作步骤。
发明内容
本发明的一个目的是避免现有技术的缺点。
本发明的另一个目的是激发涂覆有三元合金和四元合金的狭长钢元件的黏附性能。
本发明的又一个目的是避免在制造方法中使用额外的操作步骤。
根据本发明的第一方面,提供适用于橡胶产品增强的狭长钢元件。采用Cu-M-Zn的三元合金或四元合金涂层覆盖此狭长钢元件。
M是选自钴、镍、锡、铟、锰、铁、铋和钼中的一种或两种金属。
此涂层中的铜含量为58重量%-75重量%,例如61wt%-70wt%。
该涂层中的一种或两种金属含量为0.5重量%-10重量%,例如2wt%-8wt%。所述一种或两种金属存在于整个涂层中,且不仅存在于直接表面。
余量是锌和不可避免的杂质,例如低于0.1wt%的数量的杂质。
涂层厚度为0.05μm-0.50μm,例如0.12μm-0.4μm。
可通过分析溶解技术且采用x射线荧光(XRFS)、电感耦合等离子体(ICP)、电感耦合等离子体-光学发射光谱(ICP-OES)或者原子吸收光谱学(AAS)测量铜、所述一种或两种金属以及余量锌的重量百分比。这些测量也适合于获得涂层重量和涂层厚度。
磷以每平方米涂层0.3毫克到每平方米涂层1毫克,例如小于0.99mg/m2,例如小于0.95mg/m2的量存在于涂层之上或之中。下限的实例是0.4mg/m2和0.5mg/m2。此磷量可以以磷酸盐(或酯)的形式存在。可利用电感耦合等离子体技术或通过紫外-可见光谱学测量磷量。
涂层或涂层表面还缺少在涂层中与铜络合以形成不溶性膜的化合物残留物。这些化合物包括三唑、咪唑和苯并吡唑。这样的化合物包括具有以下结构式的那些:
其中连接相邻的碳原子以形成苯或亚萘基环,所述环是取代的或未取代的,并且其中A和B选自-N-或者-CH-,A和B绝不同时等于-CH-。这样的化合物的实例是苯并三唑、甲苯基三唑、苯并咪唑、苯并吡唑、萘并三唑(naphthatriazole)。
这些残留物的不存在可通过飞行时间-二次离子质谱(ToF-SIMS)技术来测量。该技术提供最上面的1-3个单层的原子和分子组成的信息,其具有ppm级的灵敏度和可达100nm的横向分辨率。
ToF-SIMS不是本质上定量的技术,因为探测到的强度取决于周围材料的化学组成(“基质效应”)。如果待比较的样品的化学环境相似,则可获得半定量的信息。
在光谱测量模式中获得所关注的表面区域的总质谱。通常使用高质量分辨率和少量所用的初级离子来记录这些光谱。高质量分辨率对于二次离子信号和相应总式的可靠识别是必需的。有限数量的初级离子保证了探测到的信号对于样品表面原始化学组成是具有代表性的(静态SIMS极限)。
对于本发明的ToF-SIMS测量,使用ION-TOF“TOF-SIMS IV”SIMS仪器。以聚束模式使用在25keV下的铋离子进行表面的离子轰击。分析电流是0.2pA且分析面积是100×100μm2。
狭长钢元件可为钢线材或钢丝帘线。在钢丝帘线的情况下,本发明不限于特定类型的构造。
术语“适用于橡胶产品增强”是指具有合适线材或丝材直径、合适的钢组成和合适的拉伸强度的钢线材和钢丝帘线。
合适的钢组成是:例如最小碳含量为0.65%,锰含量为0.1%-0.70%,硅含量为0.05%-0.50%,最大硫含量为0.03%,最大磷含量为0.03%和甚至为0.02%,所有百分比均是重量百分比。仅有痕量的铜、镍和/或铬。余量通常是铁。
微合金化钢组成,例如进一步包含一种或多种以下元素的组成也可为合适的:
-铬(%Cr):0.10%-1.0%,例如0.10-0.50%的量;
-镍(%Ni):0.05%-2.0%,例如0.10-0.60%的量;
-钴(%Co):0.05%-3.0%,例如0.10%-0.60%的量;
-钒(%V):0.05%-1.0%,例如0.05%-0.30%的量;
-钼(%Mo):0.05%-0.60%,例如0.10%-0.30%的量;
-铜(%Cu):0.10%-0.40%,例如0.15%-0.30%的量;
-硼(%B):0.001%-0.010%,例如0.002%-0.006%的量;
-铌(%Nb):0.001%-0.50%,例如0.02%-0.05%的量;
-钛(%Ti):0.001%-0.50%,例如0.001%-0.010%的量;
-锑(%Sb):0.0005%-0.08%,例如0.0005%-0.05%的量;
-钙(%Ca):0.001%-0.05%,例如0.0001%到0.01%的量;
-钨(%W):例如约0.20%的量;
-锆(%Zr):例如0.01%-0.10%的量;
-铝(%Al):优选低于0.035%,例如低于0.015%,例如低于0.005%的量;
-氮(%N):小于0.005%的量;
-稀土金属(%REM):0.010%-0.050%的量。
在本发明的上下文中,不排除例如在EP-A-2268839中公开的低碳钢组成。这样的钢组成具有小于0.20%的碳含量。一个实例是0.04%-0.08%的碳含量,0.166%的硅含量,0.042%的铬含量,0.173%的铜含量,0.382%的锰含量,0.013%的钼含量,0.006%的氮含量,0.077%的镍含量,0.007%的磷含量,0.013%的硫含量,所有百分比均为重量百分比。
适用于橡胶产品增强的狭长钢元件的单根钢线材或钢丝材的直径通常为0.03mm-1.20mm,例如0.10mm-0.80mm,例如0.15mm-0.60mm。
在单根钢线材上测量的粗糙度Ra的水平在0.10μm-2.0μm,例如0.10μm-1.0μm,例如0.10μm-0.30μm之间变化。
适用于橡胶产品增强的狭长钢元件的拉伸强度很大程度上取决于直径并且通常为1500MPa-4500MPa,例如2000MPa-4000MPa。
如将在下文中说明的,涂层上的少量的磷连同三唑残留物的缺乏一起导致在欠固化下改善的黏附结果,欠固化即当将橡胶硫化约正常的固化时间的一半。低于0.3mg/m2,将注意到很少的影响或没有影响。如结果将显示的,注意到在磷含量高于1mg/m2的情况下在欠固化中更低的黏附性能。
EP-A1-0 257 667公开了用于橡胶增强的钢元件的黄铜合金涂层,其中黄铜合金涂层含有少量磷。将磷描述为改善橡胶和黄铜之间的黏附。然而,磷的量高于本发明。
根据本发明的第二方面,提供了用于制造狭长钢元件的方法。此方法包含以下步骤:
a)采用三元合金或四元合金的Cu-M-Zn涂层涂覆狭长钢元件,M是选自钴、镍、锡、铟、锰、铁、铋和钼中的一种或两种金属,涂层中的铜含量为58重量%-75重量%,涂层中的所述一种或两种金属的含量为0.5重量%-10重量%,余量是锌和不可避免的杂质,所述一种或两种金属存在于整个所述涂层中;
b)在含有磷化合物的水性润滑剂中拉拔如此涂覆的狭长钢元件,磷化合物的量为使得磷以每平方米所述涂层0.3毫克到每平方米所述涂层1毫克的量存在于涂层上。利用电感耦合等离子体技术测量磷量。润滑剂还缺少在涂层中与铜络合以形成不溶性膜的化合物。
该方法也缺少采用这样的化合物处理狭长钢元件的其它步骤。
润滑剂可以是乳液或分散液。
可利用双捻机或利用管式加捻机捻合如此拉拔的狭长钢元件。
如所述的,相对少量的磷导致欠固化下改善的黏附行为。因为利用湿的拔丝润滑剂将磷添加至三元合金或四元合金涂层,所以不需要额外的方法步骤以获得此改善的黏附。
本发明还涉及采用具有上文公开的特征的狭长钢元件增强的橡胶产品。
具体实施方式
具有1.98mm的直径两根样品钢线材提供有如下三元合金涂层:
i)在H2SO4溶液中酸洗以清洁钢线材表面;
ii)采用来自Cu2P2O7溶液的铜进行电镀;溶液含25g/l的铜和180g/l的焦磷酸盐;电流密度是8.6A/dm2或对于更高铜含量为更高;
iii)由CoSO4溶液电镀钴;溶液含40g/l的钴且电流密度是22A/dm2;
iv)采用来自ZnSO4溶液的锌进行电镀;溶液含50g/l的锌且电流密度是8.8A/dm2或对于更低锌含量为更低;
v)施加热扩散方法来产生三元合金Cu-Co-Zn;
vi)通过在酸中浸渍来移除在扩散过程期间形成的过量ZnO;
vii)冲洗和干燥。
钢线材1具有以下涂层组成:63.5wt%Cu,4.0wt%Co,余量是Zn。
钢线材2具有以下涂层组成:67.0wt%Cu,4.0wt%Co,余量是Zn。
在湿的拔丝操作中使钢线材经受直径的最终减小。
使用了三种不同的润滑剂:I-X-Y。
润滑剂I是在本发明的上下文中使用的润滑剂。润滑剂I是水性乳液,其包含大于90%的水、油、表面活性剂、皂、磷化合物和pH缓冲系统。该pH还通过胺的作用而得到部分缓冲。
更特别地,润滑剂I包含磷酸盐(或酯)、硫酸盐(或酯)、硝酸盐(或酯)、含氧烃和脂肪酸残留物、含氮烃。磷酸盐(或酯)可以以PO2-或PO3-离子存在。
参比润滑剂X是水性乳液,其包含大于90%的水、矿物油、表面活性剂、皂、磷化合物、极压添加剂、三唑类缓蚀剂(例如苯并三唑)和pH缓冲系统。该pH还通过胺的作用而得到部分缓冲。
更特别地,润滑剂X包含磷酸盐(或酯)、CN/CNO、苯并三唑、烃、脂肪酸和辛基磷酸。
参比润滑剂Y是水性乳液、其包含大于90%的水、植物油、表面活性剂、皂、磷化合物、极压添加剂、三唑类缓蚀剂(例如苯并三唑)和pH缓冲系统。该pH还通过胺的作用而得到部分缓冲。
更特别地,润滑剂Y包含磷酸盐(或酯)、CN/CNO、苯并三唑、烃、脂肪酸和辛基磷酸。
最终的钢线材直径是0.30mm。在湿的拔丝之后,将钢线材捻合成2×0.30钢丝帘线构造。
将两种钢线材1和2与三种润滑剂I、X、Y组合,给出六种不同的钢丝帘线样品1-I、1-X、1-Y、2-I、2-X和2-Y。使这六种不同的钢样品在橡胶化合物中硫化。已在这些样品上测量拉出力(POF)和显露率(APR)或橡胶覆盖率。
表1列出了三元合金涂层表面上的磷量及其它。
表1
inv=本发明,ref=参比,Ps=磷量
表2提及在欠固化下拉出测试和显露率测试的结果。
表2
样品 | 拉出力(N) | 显露率(%) |
1-I inv | 334 | 60 |
1-X ref | 263 | 48 |
1-Y ref | 223 | 33 |
2-I inv | 338 | 68 |
2-X ref | 279 | 60 |
3-Y ref | 255 | 50 |
本发明样品1-I inv和2-I inv在拉出测试和显露率测试中都明显地表现更好。
本发明样品1-I-inv和2-I-inv的黏附行为在正常固化(RC)下和在蒸汽时效(SA)后处于可接受的高水平,参见下文表3。
RC是TC90时间加上5分钟,而TC90是当橡胶达到在硫化温度下获取的流变仪曲线上其最大转矩的90%时的时间。
SA是在120℃下蒸汽蒸煮持续1或2天的RC样品。
表3
样品 | POF(RC) | POF(SA) | APR(RC) | APR(SA) |
1-I-inv | 421 | 359 | 85 | 83 |
2-I-inv | 379 | 256 | 80 | 58 |
3-I-ref | 377 | 142 | 80 | 28 |
3-X-ref | 387 | 197 | 78 | 43 |
3-Y-ref | 403 | 227 | 83 | 45 |
3意指具有更普通的黄铜涂层Cu-Zn的狭长钢元件。
在润滑剂I中拉拔3-I-ref并且在它的涂层中具有63.95wt%Cu且在它的涂层之上或之中具有0.81mg/m2的磷。
在润滑剂X中拉拔3-X-ref并且在它的涂层中具有64.30wt%Cu且在它的涂层之上或之中具有1.09mg/m2的磷。
在润滑剂Y中拉拔3-Y-ref并且在它的涂层中具有64.20wt%Cu且在它的涂层之上或之中具有1.28mg/m2的磷。
在下文表4总结了在本发明钢丝帘线样品1-I-inv上进行的ToF-SIMS分析的结果。
表4
根据本发明,狭长钢元件在涂层上缺乏三唑,所以它们也缺乏苯并三唑。然而,表4提及三唑的一些数值。然而,认为这些数值是“噪音水平”。认为数值高于5,例如高于10是高于噪音水平。
对咪唑和苯并吡唑同样是有效的:利用ToF-SIMS技术清楚的测量这些化合物将给出噪音数值。
在下文表5提及了两种可能的轮胎橡胶化合物配方连同其性质,其中注意到UC黏附的有效改善。
表5
组分 | 化合物1 | 化合物2 |
天然橡胶TSR10 | 100份 | 100份 |
ZnO-氧化锌 | 9phr | 9phr |
硬脂酸 | -- | 0.7phr |
炭黑HAFLS N326 | 65phr | 65phr |
抗降解化合物6PPD(*) | 1.8phr | 1.8phr |
硫来源Crystex HSOT20 | 6.4phr | 6.4phr |
促进剂DCBS | 0.8phr | -- |
钴盐酰化硼钴680C | 0.27phr | -- |
促进剂TBBS | -- | 0.7phr |
阻滞剂PVI | -- | 0.25phr |
性质 | ||
在150℃下的流变仪曲线 | ||
Tc2(分钟) | 1.8 | 3.5 |
Tc90(分钟) | 12.0 | 13.0 |
MH(dNm) | 31.5 | 30.6 |
在100℃下的门尼 | ||
黏度(MU) | 66 | 70 |
肖氏A硬度 | 70 | 66 |
断裂载荷(N) | 336 | 337 |
拉伸强度(MPa) | 22.5 | 23.0 |
模量100%(N/cm2) | 4.7 | 4.7 |
模量200%(N/cm2) | 10.3 | 11.1 |
模量300%(N/cm2) | 16.3 | 17.9 |
断裂延伸率(%) | 421 | 396 |
在60℃下10Hz动态应变的DMTA | ||
E’(MPa) | 12.61 | 8.58 |
E”(MPa) | 1.98 | 0.94 |
Tanδ(-) | 0.157 | 0.109 |
DMTA=动态力学热分析
在60℃下的Tanδ是滚动阻力(rolling resistance)的一个指标,该数值越高,滚动阻力越高。
与表1中提到的三元合金成分接近,还测试了以下组成:
%Cu | %Co |
67 | 4 |
67 | 2 |
63 | 4 |
70 | 2 |
70 | 4 |
67 | 6 |
63.5 | 8 |
63.5 | 1 |
由于改善的黏附性能和更好的橡胶化合物,可注意到提高的轮胎耐久性。
此外,在橡胶化合物中不存在钴降低了橡胶热老化。
最后,可注意到约2.5%-4.0%或甚至更高的滚动阻力降低。
Claims (7)
1.适用于橡胶产品增强的狭长钢元件,采用Cu-M-Zn的三元或四元合金涂层来覆盖所述狭长钢元件,
其中M是选自钴、镍、锡、铟、锰、铁、铋和钼中的一种或两种金属。
在所述涂层中的铜含量为58重量%-75重量%,
在所述涂层中的所述一种或两种金属含量为0.5重量%-10重量%,
余量是锌和不可避免的杂质,
所述一种或两种金属存在于整个所述涂层中,
磷,以每平方米所述涂层0.3毫克-每平方米所述涂层1毫克的量存在于所述涂层之上和/或之中,利用电感耦合等离子体技术测量所述磷量,
所述涂层还缺乏在涂层中与铜络合以形成不溶性膜的化合物残留物,其通过ToF-SIMS技术测量。
2.根据权利要求1所述的狭长钢元件,铜含量为61重量%-70重量%。
3.根据权利要求2所述的狭长钢元件,所述的一种或两种金属的含量为2重量%-8重量%。
4.根据上述权利要求中任一项所述的狭长钢元件,所述狭长钢元件是钢线材或钢丝帘线。
5.用于制造适用于橡胶产品增强的狭长钢元件的方法,所述方法包括下列步骤:
a.采用Cu-M-Zn三元合金或四元合金涂覆狭长钢元件,M是选自钴、镍、锡、铟、锰、铁、铋和钼中的一种或两种金属,所述涂层中的铜含量为58重量%-75重量%,所述涂层中的所述一种或两种金属的含量为0.5重量%-10重量%,余量是锌和不可避免的杂质,所述一种或两种金属存在于整个所述涂层中;
b.在含有磷化合物的水性润滑剂中拉拔所述涂覆的狭长钢元件,磷化合物的量是使得磷以每平方米所述涂层0.3毫克到每平方米所述涂层1毫克的量存在于所述涂层之上和/或之中,利用电感耦合等离子体技术测量所述磷量,
所述润滑剂还缺乏在涂层中与铜络合以形成不溶性膜的化合物,使得所述涂层缺乏通过ToF-SIMS技术测量的所述化合物的残留物。
6.根据权利要求5所述的方法,所述方法还包括捻合两个或更多个所述狭长钢元件的步骤。
7.增强的橡胶制品,包含橡胶化合物和狭长钢元件,其中所述狭长钢元件是根据权利要求1-4中任一项所述的狭长钢元件。
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- 2012-07-24 CN CN201280067804.2A patent/CN104066882B/zh active Active
- 2012-07-24 KR KR1020147021689A patent/KR101928130B1/ko active IP Right Grant
- 2012-07-24 RS RS20171203A patent/RS56637B1/sr unknown
- 2012-07-24 BR BR112014017588-8A patent/BR112014017588B1/pt active IP Right Grant
- 2012-07-24 ES ES12737831.3T patent/ES2642918T3/es active Active
- 2012-07-24 PL PL12737831T patent/PL2812480T3/pl unknown
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Also Published As
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BR112014017588B1 (pt) | 2020-12-15 |
HUE037204T2 (hu) | 2018-08-28 |
US20140378597A1 (en) | 2014-12-25 |
EP2812480B1 (en) | 2017-08-30 |
US20180230625A1 (en) | 2018-08-16 |
EP2812480A1 (en) | 2014-12-17 |
WO2013117248A1 (en) | 2013-08-15 |
US10619271B2 (en) | 2020-04-14 |
BR112014017588A2 (zh) | 2017-06-20 |
BR112014017588A8 (pt) | 2017-07-11 |
JP6069364B2 (ja) | 2017-02-01 |
KR101928130B1 (ko) | 2018-12-11 |
RS56637B1 (sr) | 2018-03-30 |
CN104066882B (zh) | 2017-03-08 |
PT2812480T (pt) | 2017-10-18 |
JP2015511998A (ja) | 2015-04-23 |
KR20140124758A (ko) | 2014-10-27 |
ES2642918T3 (es) | 2017-11-20 |
PL2812480T3 (pl) | 2018-02-28 |
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