CN102031523A - 一种降低铅的量的方法 - Google Patents

一种降低铅的量的方法 Download PDF

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CN102031523A
CN102031523A CN2010102788567A CN201010278856A CN102031523A CN 102031523 A CN102031523 A CN 102031523A CN 2010102788567 A CN2010102788567 A CN 2010102788567A CN 201010278856 A CN201010278856 A CN 201010278856A CN 102031523 A CN102031523 A CN 102031523A
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克劳迪奥·沃隆特
斯泰方诺·卡雷拉
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Abstract

一种降低铅的量的方法,所述铅通过当由含铅的金属合金制成的水系统组件与意欲用于制作为人所用饮料的液体接触时,由所述水系统组件释放,所述方法至少包括依次的下列步骤:初步降低包含在构成所述组件的材料中的铅的量,至少在与所述液体接触的表面上,通过沉积锡层来涂布如此处理的所述组件,至少在通过沉积锡层而处理的表面上,通过电解沉积覆盖的金属合金来涂布所述水系统组件。

Description

一种降低铅的量的方法
技术领域
本发明涉及一种降低有害于人类健康的元素(特别是铅)的量的方法,所述元素在当由金属合金如青铜和黄铜制成的水系统组件接触意欲用于制备人类消费用饮料的液体时,通过所述组件而释放。
背景技术
水系统组件意指管、管接头、龙头(tap)、阀和煮器,它们通常用于管道系统中,和用于制作为人所用饮料的设备例如咖啡制作和分配机的构造中,所述咖啡制作和分配机还包括热冷牛奶的分配和浸液例如茶和甘菊茶的制作。
在这些设备中加工并且意欲为人所用的液体必须满足严格的标准,所述标准对有害于人类健康的材料(所述材料中有铅和镍)的允许量施加了一定限制。
已知上述水系统组件通常由分别为铜锡合金和铜锌合金的青铜或黄铜制成。
还已知在这些合金中存在某一百分比的铅,这是因为将铅加入铜合金,从而使材料变得更容易加工。
将铅加入铜锌合金和铜锡合金导致以下风险:在使用由它们形成的部件的水系统时,由这些合金制成的组件可将铅(尽管以最小且非常易变的量)释放到液体中,然后铅可通过消费用该液体制成的饮料而被摄取。
因为认为上述元素随时间推移而非常有害于人类健康,所以考虑到大幅限制其在饮料中的存在,已设定更严格和更严厉的标准。
在欧洲,参照的标准是CE No.1935/2004。
另一方面,在美国,其为标准NSF(NATIONAL SANITATION FOUNDATION)4,所述标准对铅浓度施加了非常低的限制(不大于15μg/l),除了通过用于清洗水系统组件的程序之外,难以实现所述限制;这些程序具有经济处罚性,特别是当考虑到关于水系统组件的性质和它们的用途时。
根据已知技术,为了限制由铅从水系统组件迁移到通过所述组件的液体而产生的问题,已经提出降低在制造组件的铜合金中存在的游离铅的量。
该技术(可定义为脱铅)的实例描述于EP-A 1,134,306和US-A-5,958,257中。根据此现有技术,将水系统组件在含有羧酸的浴中进行清洗。
然而,实际上已经发现,虽然简单地清洗组件相当大地降低了转移到在由铜基合金制成的水系统组件内的流体中的铅量,但是不足以防止残余的游离铅的迁移。
例如,因为已知物理和化学现象受温度影响,所以如果将如在US-A-5,958,257中或例如在EP 1,134,306中所述的已进行脱铅处理的水系统组件在用于市政水管的常温下使用,那么它可给予在最大允许极限之下的转移,然而,如果将相同组件在其特征为明显更高的操作温度例如在煮咖啡机中存在的温度的设备中使用,那么会超过该极限。
已经发现,通过在含有羧酸的浴中清洗的脱铅操作导致组件表面中的微孔结构,这又有利于将进一步残余的游离铅从材料的最内层向通过所述组件的液体显著迁移。
通过由电解法或化学法对镍层的沉积,可实现铅迁移方面的显著降低。
锡涂层也可产生对铅迁移的有效防止。然而,由于锡的性质,此类涂层的特征在于不令人满意的耐久性。
至于镍涂层,虽然一方面其以令人满意的方式降低了铅迁移,但是,另一方面,其引入超出对于镍迁移的允许极限的问题。
为防止此迁移过度,已经开发出特定合金,所述合金除其他物质外还包含镍和锡,并且所述合金具有仍接近于镍表面强度的表面强度,但同时由于锡的存在而限制了镍迁移。
然而,该合金具有局限性,这是因为它可以单独地进行电化学沉积,从而具有不良的进入某些组件内孔的渗入。因此,尽管已经对它们进行脱铅操作,但是不能将其单独有效地用于构成组件的涂层。
另一已知技术是,用含有硝酸铋的组合物涂布青铜或黄铜水系统组件,所述组合物通过将其浸渍在含有所述组合物的浴中来施涂,期望所述涂层能防止铅原子迁移通过所述组件与液体接触的涂布面。
该技术的实例描述于US-A-5,544,859。
然而,实际上,该技术不能保证铅(或可能镍)迁移随时间推移的非渗透性,这是因为远在所述组件平均有效寿命结束之前,所述涂层将在一定时间后磨损。
发明内容
本发明的目的是解决铅从水系统组件如由铜基合金制成的管、龙头、管接头和煮器等迁移到通过所述组件的液体中的问题,从而以耐久性和经济性有利的方式有效满足欧洲健康标准(Regulation CE No.1935/2004)及美国健康标准(NSF 4)的要求。
该目的通过一种降低铅的量的方法来实现,所述铅通过当由含铅的金属合金制成的水系统组件与意欲用于制作为人所用饮料的液体接触时,由水系统组件释放,所述方法至少包括依次的下列步骤:
-初步降低包含在构成组件的材料中的铅的量,
-至少在与液体接触的表面上,通过沉积锡层来涂布如此处理的组件,
-至少在通过沉积锡层而处理的表面上,通过电解沉积覆盖的金属合金来涂布水系统组件。
根据本发明,将由黄铜或青铜制成并且意欲用于为人所用饮料的液体流动的水系统组件进行初步处理,以减少其中含有的游离铅量。
该处理可由在含有羧酸(特别是丙烯酸)的浴中清洗的步骤构成。
在该步骤后,对所述组件进行优选化学沉积而不使用电力的锡层涂布,从而达到2-4μm的厚度。
已经发现所述锡层导致实质上将材料的固有多孔结构和作为所述方法第一步骤中进行的初步脱铅处理的结果而产生的多孔结构密封,因此尽管存在上述问题,但也证明是有用的。
化学沉积锡的步骤之后,接着是借助通过锡与镍的金属合金的电解沉积而覆盖所述锡层的方式的表面涂布步骤。
已经发现,与补充和加强对抗铅迁移的保护一样,沉积优选厚度为2-4μm的覆盖层可赋予锡底层充分的抵抗性(resistance),改进长期有效性。
根据本发明,用于覆盖锡层的金属合金包含镍与锡,并优选比例为约35%镍与65%锡。
由以下给出的实施例所见,对通过根据本发明的方法处理的水系统组件样品与通过现有技术的方法处理的相应组件样品进行的试验显示,根据本发明的方法,将铅元素从水系统组件向通过所述组件的液体的迁移相当大地降低至迁移性大体上为0的程度,完全满足了现行健康标准。
具体实施方式
实施例1
将容量约2.9升,由焊接黄铜组件的组件制成的,可用于专用煮咖啡机的此类煮器,进行常规的浸酸和冲洗步骤。
然后向其填充1.7升的水,所述水中已添加少量盐酸,从而通过将pH降低到5的值来增强其侵蚀性(aggressiveness)。
将如此填充的煮器在对应于温度122.6℃的相对饱和蒸汽压1.2bar下保持24小时,从而反映对于作为咖啡机中经受最大热应力的组件的此类组件所期望的工作条件。
在达到上述时间后,利用石墨炉通过APAT CNR IRSA原子吸收光谱测试法分析容纳于煮器中的水。
得到铅含量为10.72μg/l。
实施例2
将如实施例1所述的具有焊接黄铜组件的铜组件的煮器进行常规的浸酸和冲洗步骤,接着是通过浸渍于含有丙烯酸的浴而进行的脱铅步骤。干燥后,如实施例1所述,填充煮器并进行相同的热处理。
在达到处理时间后,通过与实施例1相同的设备进行水的分析,检测到铅含量为2.154μg/l。
实施例3
将如实施例1和2所述的具有焊接黄铜组件的铜组件的煮器,在浸酸、冲洗和脱铅之后,用包含镍与锡的合金进行电解涂布。
在如实施例1和2所述的热处理后,通过与实施例1和2相同的设备进行水的分析,所得结果是存在1.423μg/l的铅。
实施例4
将如前述实施例所述的具有焊接黄铜组件的铜组件,其类型为特别用于浓咖啡的咖啡机的煮器,在脱铅步骤之后,进行用于化学沉积锡的处理,从而获得其厚度在2-4μm之间变化的层。在锡层上进行包含镍与锡的合金的电化学沉积,形成厚度在2-4μm之间变化的层。
各沉积步骤之后,接着是在水中清洗并干燥的步骤。
在如前述实施例所述的那样填充补充有盐酸的水并热处理后,通过与前述实施例相同的设备进行水的分析,检测到铅量不大于0.075μg/l,该值为所用分析设备检测能力的极限。
实施例5
将完全由黄铜制成且具有与前述实施例所用煮器相同容量的煮器,进行脱铅、化学沉积锡层以及通过电解沉积含有镍与锡的合金层而将其涂布的相同处理,从而给出如实施例4所示的层厚度。
各沉积步骤之后,接着是在水中清洗并干燥的步骤。
在如前述实施例所述的那样填充补充有盐酸从而调节pH值至5的水并热处理后,用与前述实施例所用的相同的设备进行水的分析,检测到铅量不大于0.075μg/l,这是所用分析设备检测能力的极限。
将试验结果总结于下表中。
  组件   铅(μg/l)
  实施例1的煮器   10.72
  实施例2的煮器   2.154
  实施例3的煮器   1.423
  实施例4和5的煮器   不大于0.075*
由这些结果所见,当对水系统组件例如由焊接黄铜组件的铜组件制成的用于咖啡机的煮器以及完全由黄铜制成的煮器按照根据本发明的方法进行处理时,导致铅迁移到水中的量为小于0.075μg/l,充分满足了现行的将此量限定到不大于15μg/l值的健康标准。

Claims (13)

1.一种降低铅的量的方法,所述铅通过当由含铅的金属合金制成的水系统组件与意欲用于制作为人所用饮料的液体接触时,由所述水系统组件释放,所述方法至少包括依次的下列步骤:
-初步降低包含在构成所述组件的材料中的铅的量,
-至少在与所述液体接触的表面上,通过沉积锡层来涂布如此处理的所述组件,
-至少在通过沉积锡层而处理的表面上,通过电解沉积覆盖的金属合金来涂布所述水系统组件。
2.根据权利要求1所述的方法,其中,所述初步降低包含在构成所述组件的材料中的铅的量的步骤包括将所述组件浸渍在至少含有羧酸的浴中。
3.根据权利要求1所述的方法,其中,所述沉积锡层通过化学方法进行。
4.根据权利要求3所述的方法,其中,所述锡层具有厚度为2-4μm。
5.根据权利要求1-4任一项所述的方法,其中,要电解沉积在所述锡层上的所述覆盖的金属合金为包含镍和锡的金属合金。
6.根据权利要求5所述的方法,其中,所述覆盖的金属合金包含35%的镍和65%的锡。
7.根据权利要求1-6任一项所述的方法,其中,所述覆盖的金属合金具有厚度为2-4μm。
8.根据权利要求1-7任一项所述的方法,其特征在于,所述方法包括在各沉积步骤完成时,在水中清洗所述水系统组件的步骤。
9.根据权利要求1-8任一项所述的方法,其中,构成所述水系统组件的所述材料为青铜。
10.根据权利要求1-8任一项所述的方法,其中,构成所述水系统组件的所述材料为黄铜。
11.根据权利要求1-8任一项所述的方法,其中,构成所述组件的所述材料为焊接至黄铜的铜。
12.一种水系统组件,其按照根据权利要求1-8中一项或多项所述的方法处理。
13.一种用于浓咖啡的咖啡机的煮器,其由焊接至黄铜组件的铜组件制成,并通过根据权利要求1-8中一项或多项所述的方法处理。
CN2010102788567A 2009-09-25 2010-09-08 一种降低铅的量的方法 Pending CN102031523A (zh)

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US10760693B2 (en) 2016-01-18 2020-09-01 Nibco Inc. Weldable, low lead and lead-free plumbing fittings and methods of making the same
US10234043B2 (en) 2016-01-18 2019-03-19 Nibco Inc. Weldable, low lead and lead-free plumbing fittings and methods of making the same

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EP1038990A1 (en) * 1997-12-03 2000-09-27 Toto Ltd. Method of reducing elution of lead in lead-containing copper alloy, and city water service fittings made of lead-containing copper alloy
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