CN1639085A - 金属化钛酸盐基陶瓷的方法 - Google Patents

金属化钛酸盐基陶瓷的方法 Download PDF

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CN1639085A
CN1639085A CNA038046199A CN03804619A CN1639085A CN 1639085 A CN1639085 A CN 1639085A CN A038046199 A CNA038046199 A CN A038046199A CN 03804619 A CN03804619 A CN 03804619A CN 1639085 A CN1639085 A CN 1639085A
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伊里·劳巴尔
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Abstract

一种湿法化学金属化钛酸盐基陶瓷的方法,包括如下步骤:蚀刻陶瓷,活化在(a)步骤中蚀刻的陶瓷,将(b)步骤中得到的陶瓷进行化学金属化,其特征在于步骤(a)中,在温度为130-170℃下,用于蚀刻的硫酸溶液浓度范围按重量计为65-90%。

Description

金属化钛酸盐基陶瓷的方法
本发明涉及一种金属化钛酸盐基陶瓷的方法,其中将所述的陶瓷在硫酸中蚀刻。
下面描述的处理顺序通常用于湿法化学金属化陶瓷零件:
1,蚀刻
2,活化
3,化学金属沉积,产生导电表面
4,任选进一步的金属沉积,根据需要可以是电或无电镀的。
为了获得金属层与基质的牢固结合,金属层必须被结合在基底材料表面上。若表面具有微尺寸范围特定的粗糙度和类穴结构,就能够实现这一点。
在一些情况下,在制备陶瓷基质后已存在这种结构,但在其它情况下,基质的表面是光滑的,因此就需要施加“蚀刻”处理步骤,以使粘附层能够被沉积。蚀刻剂必须非均匀地侵蚀陶瓷,从而能得到具有大量微空穴的所期望的结构。能够均匀侵蚀基底材料的蚀刻剂不适合用作预处理,因为这类蚀刻剂的作用不能得到上述的结构。
钛酸盐基陶瓷,例如钛酸钡或含有稀土元素的钛酸盐用来生产零件,并且在特定的情况下,必须被金属化以用在电子工业中。陶瓷零件表面的光滑度取决于其组成和制备方法。具有光滑表面的陶瓷零件在金属化前必须进行蚀刻。
在DE-OS 3 345 353中描述的方法中,其中基于氧化铝、钛酸钡和氧化铍的陶瓷在含有氢氟酸的介质中被蚀刻。在其说明书的实施例2中描述了钛酸钡电容器陶瓷的金属化。随后在浓氢氟酸中蚀刻,可达到5N/mm的粘附力。但是,由于环保原因氟化物的使用通常是不期望的。另外,在处理氢氟酸和含有氟化物的溶液时,必须遵守严格的安全规则。
在DE-OS 3 523 957中描述的方法中,其中陶瓷在碱金属氢氧化物熔体或在酸熔体中进行预处理,并向蚀刻介质中加入粘附促进剂和/或感光剂和/或活化剂和/或催化剂。在其说明书的实施例5中描述了钛酸钡陶瓷的金属化。用硫酸氢铵熔体使其粗糙化,并向其中加入醋酸锡(II)。在200℃下将陶瓷零件处理10分钟。但该方法的缺点在于,就设备而言,使用熔体需要较高额的费用。该相对高的工作温度另外与增加能量消耗相关联,并且陶瓷有被热负荷破坏的危险。
DE-OS 3 737 757中描述了一种金属化氧化铝陶瓷的方法,其中用浓磷酸在250-360℃下蚀刻。但该方法的缺点在于也使用了高温,其一方面导致能量的高效耗,另一方面也导致陶瓷被破环。
DE-OS 3 833 441中描述了一种金属化氧化铝陶瓷的方法,其中用磷酸/硫酸混合物在220℃下作为蚀刻剂。但在如此高的温度下,存在形成酸蒸气的危险,所述的酸蒸气有非常强的腐蚀性,因此应可能避免。由于高温,就设备而言进一步需要相对高的费用。
在EP 0 254 201 A1中建议使用基于无机酸的蚀刻剂,如氢氟酸、氢氯酸、磷酸、硝酸和其它无机酸。175℃下在浓磷酸中处理陶瓷,在实施例中描述了随后在氟化氢铵溶液中处理。但这种两步法的缺点在于步骤上的不经济。另外由于环保的原因氟化物化合物也是不期望的。
因此形成本发明基础的目的在于提供一种金属化陶瓷的方法,该方法没有如上所述的缺点。
通过本发明权利要求1的方法实现上述目的。
在进一步的权利要求中描述了本方法实施方式的优点。
图1和图2表示根据本发明实施例1蚀刻之前(图1)之后(图2)得到的由稀土钛酸盐组成的陶瓷表面的扫描电镜照片。
图3和图4表示根据本发明实施例14蚀刻后得到的钛酸钡基陶瓷表面的不同放大倍数的扫描电镜照片。与此相比,图5是蚀刻前相同材料表面的电镜照片。
图6是根据本发明实施15蚀刻后的钛酸钡-钛酸钐基陶瓷的扫描电镜照片。
若根据本发明的方法,相对于目前的方法,可实现以下优点:
●与已有技术相比,蚀刻中使用了较低的温度,
●不再需要使用氢氟酸或氟化物,
●不再需要对氢氧化物或盐熔体进行复杂的处理。
本方法涉及一种钛酸金属盐基陶瓷,为了使陶瓷零件获得期望的性能,碱土金属如钙和钡,稀土元素如镧和钐,及其它元素也可作为金属以小的比例使用。
已发现硫酸溶液非常适合蚀刻钛酸盐基陶瓷。由此在陶瓷表面上产生这样的结构,其能够使随后沉积的金属层具有优异的粘附力。
硫酸的浓度按重量计为65-90%,优选按重量计为70-80%。
在按重量计浓度低于65%时,陶瓷仅能轻微被侵蚀,并且由此产生的粘附力也不令人满意。为了获得有利的粘附力,所用硫酸的浓度为65-90wt%,优选为70-80wt%。在这些条件下,陶瓷被非均匀侵蚀,形成微尺寸范围的类穴结构,该结构能使随后沉积的金属层牢固地粘附。浓度高于90wt%时,由于在温度约为130℃时有相当多的酸雾形成,这一点应当尽量避免,因此不是有利的。另外,用浓硫酸并不能形成类穴的微结构,从而随后施加的金属涂层仅有很低的粘附力。
溶液在蚀刻时的工作温度为130-170℃,优选为140-160℃。温度范围在145-155℃时被证明是特别有利的。温度和浓度优选这样设定以使处理时间为5-20分钟。
在温度低于130℃时,陶瓷表面的侵蚀过慢,或者陶瓷不能被充分侵蚀。侵蚀的强度随着所用温度的增加而增加。超过170℃时,此时由于酸雾形成的量相当大,因此该温度不优选。
所用温度的上限进一步受到硫酸溶液与浓度相关的沸点的限制,由于在沸点以上不应进行任何工作。
出于环境工程的考虑,硫酸的挥发应尽保持尽可能的低。随着硫酸的浓度和温度增加,气相中硫酸的比例增加。硫酸的挥发与形成白色的酸性烟雾有关。因此,对浓度和温度进行选择以使形成的酸蒸气最少是有益的。从这一点考虑,较高浓度时应该选择较低的温度。
蚀刻后,陶瓷零件用水彻底冲洗。为了从表面上除去松散的陶瓷颗粒,用超声波辅助清洗是有益的。为了达到甚至更彻底的清洗,在蚀刻后可使用酸、碱或中性溶液来清洗陶瓷表面,这些清洗液中可能含有表面活性剂。优选的清洗方式是在超声波处理辅助下进行。
经过冲洗,和任选的另外清洗步骤后,对陶瓷表面进行活化。可使用已知的工业上可获得的方法,如基于钯的化合物,用于这一目的。
活化后,用无电镀法将金属层沉积到陶瓷的表面。无电镀槽,如无电镀镍槽或铜槽,来实现这一目的。
这些镀槽中含有金属盐、络合剂、稳定剂、还原剂和其它添加剂。用次磷酸盐或硼化合物,如二甲氨基硼烷,可在市场上购买到用作镀镍槽的还原剂。市场上可购买到的无电镀铜槽通常含有甲醛作为还原剂。
一旦陶瓷表面在无电镀槽中被涂布后,根据需要可用无电镀或电法沉积另外的层。如下组合物可用作实施例:铜、锡或锡-铅;铜、镍、金;铜、镍。金属层可用已知的方法进行构造,从而在陶瓷表面上形成金属图样。
通过以下实施例对本发明作更详细的描述:
实施例
例1
将由稀土钛酸盐组成的陶瓷零件在150℃的硫酸中(按重量计为74%)处理10分钟,随后用水冲洗,干燥。
从扫描电镜图(图1和图2)可以清楚地看出蚀刻溶液的效果。图1表示蚀刻前的陶瓷,其表面相对光滑,且晶界能够清楚地分辨。图2表示蚀刻后的表面。与图1相比,可观察到陶瓷被非均匀地侵蚀,并且主要在晶界处被侵蚀。形成的凹陷和空穴能粘附随后沉积的金属沉积层。
蚀刻后,用工业上购买的钯胶体基活化剂活化陶瓷,并且在化学镀镍槽中用镍进行无电镀涂布,其中所用的二甲氨基硼烷作为还原剂。从酸性铜槽中铜被电沉积到该导电层上。该层的厚度为20μm。
当剥离该金属层(DIN 53494)时,可观察到具有良好的粘附力(6N/cm)。
实施例2-13
将与实施例1中描述的相同类型的陶瓷零件在各种硫酸溶液中被蚀刻,硫酸的浓度、温度和接触时间依照表1中给出的详细条件进行变化。粘附力随后根据DIN 53494进行计算。
结果列于如下的表1中。
表1:
实施例编号      酸浓度[wt.%]    温度(℃)      处理时间    粘附力
                                                [分钟]     [N/cm]
    1                74            150            10        6.0
    2                69            150            20        10.0
    3                74            130            60        8.0
    4                74            130            180       11.5
    5                74            140            20        5.9
    6                74            140            30        12.8
    7                74            150            20        13.5
    8                74            160            5         4.0
    9                74            160            10        15.5
    10               80            140            20        5.5
    12               87            150            20        5.2
    13               87            150            60        6.3
实施例14
将用钛酸钡基陶瓷制备的小片在74%的硫酸中150℃下处理30分钟。图3和图4表示蚀刻后的陶瓷表面不同放大倍数的扫描电镜照片。图5所示的蚀刻前的照片作为对比。从扫描电镜照片中可清楚地看出,在蚀刻后的表面上形成了类空穴的凹陷。
将相同类型的陶瓷零件蚀刻后在水中冲洗,可通过超声波强化冲洗。随后进行活化,如实施例1描述的化学镍镀涂布和电镀铜涂布,得到的粘附力可通过剥离试验(DIN 53494)来定量确定。测量值为6-7N/cm。将蚀刻槽中接触时间延长至90分钟得到的粘附力值为14-16N/cm。
实施例15
将钛酸钡-钛酸钐基陶瓷零件在74%的硫酸中蚀刻,在150℃下处理30分钟。随后按照实施例14的方法进行清洗和活化,将陶瓷零件在化学镀铜槽中进行金属化,其中甲醛作为还原剂。然后在酸性铜槽中通过电镀以强化沉积。剥离法(DIN 53494)测得粘附力为10N/cm。
该良好的粘附力值与蚀刻得到的表面结构相一致。蚀刻后陶瓷表面的扫描电镜照片如图6所示。
对比例
将与实施例1相同的陶瓷零件在浓硫酸(按重量计为96%)中处理,在150℃下处理不同的时间。然后进行活化,按照实施例1相同的方法,进行化学镀镍涂布和电镀铜涂布,用DIN 53494测量粘附力。
    处理时间[min]     粘附力[N/cm]
    20     0
    60     <2
    90     2
从对比例中可以清楚地看出,用浓硫酸蚀刻后的陶瓷表面仅具有较低的粘附力。

Claims (9)

1.一种湿法化学金属化钛酸盐基陶瓷的方法,包括如下步骤:
(a)蚀刻陶瓷,
(b)活化在(a)步骤中蚀刻的陶瓷,
(c)将(b)步骤中得到的陶瓷进行化学金属化,
其特征在于步骤(a)中,在温度为130-170℃下,用于蚀刻的硫酸溶液浓度范围按重量计为65-90%。
2.如权利要求1的方法,其特征是在温度为140-160℃下,所用的硫酸浓度按重量计为70-80%。
3.如权利要求1或2的方法,其特征是所述的陶瓷随后在步骤(d)中进行电或化学金属化。
4.如权利要求1-3任一项的方法,其特征是所述的陶瓷含有钛酸钡。
5.如权利要求1-4任一项的方法,其特征是所述的陶瓷含有稀土元素。
6.如权利要求1-5任一项的方法,其特征是所述的陶瓷在步骤(c)中用化学法涂布铜。
7.如权利要求1-6任一项的方法,其特征是所述的陶瓷在步骤(c)中用化学法涂布镍。
8.如权利要求1-7中任一项的方法,其特征在于随后的蚀刻步骤,以及在步骤(b)之前,陶瓷用中性溶液和/或碱性溶液和/或酸性溶液进行清洗。
9.如权利要求8的方法,其特征是清洗在超声波辅助下进行。
CNB038046199A 2002-02-26 2003-02-19 金属化钛酸盐基陶瓷的方法 Expired - Fee Related CN1301937C (zh)

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CN109574714A (zh) * 2019-01-21 2019-04-05 深圳市纳明特科技发展有限公司 陶瓷基体表面t处理方法
CN112500193A (zh) * 2020-11-09 2021-03-16 麦德美科技(苏州)有限公司 一种钛酸钙镁陶瓷的化学粗化及金属化工艺
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CN102842433B (zh) * 2012-08-28 2016-08-03 四川大学 超级电容器电极材料及制备方法和由其制作的超级电容器
CN109574714A (zh) * 2019-01-21 2019-04-05 深圳市纳明特科技发展有限公司 陶瓷基体表面t处理方法
CN112500193A (zh) * 2020-11-09 2021-03-16 麦德美科技(苏州)有限公司 一种钛酸钙镁陶瓷的化学粗化及金属化工艺
CN116462531A (zh) * 2023-03-21 2023-07-21 沈阳富创精密设备股份有限公司 一种陶瓷表面处理方法

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