CN111303884A - 在混合的水性酸溶液中使用臭氧生成锰(iii)离子的方法 - Google Patents
在混合的水性酸溶液中使用臭氧生成锰(iii)离子的方法 Download PDFInfo
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- CN111303884A CN111303884A CN201911239239.3A CN201911239239A CN111303884A CN 111303884 A CN111303884 A CN 111303884A CN 201911239239 A CN201911239239 A CN 201911239239A CN 111303884 A CN111303884 A CN 111303884A
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Abstract
在含有锰‑(II)物种的混合的水性酸溶液中通过将臭氧气体注入所述混合的水性酸溶液中使得臭氧将锰‑(II)物种的至少一些氧化为锰‑(III)物种来生成和再生锰‑(III)物种,具有至少60%Mn(III)生成效率。所述酸包含硫酸和烷烃磺酸。所述含有锰‑(III)和锰‑(II)物种的水性酸溶液用于蚀刻聚合物材料。所述蚀刻是不含铬的蚀刻方法。
Description
技术领域
本发明涉及在混合的水性酸溶液中使用臭氧生成锰-(III)离子的方法。更具体地,本发明涉及在硫酸和烷烃磺酸的混合的水性酸溶液中使用臭氧由锰-(II)离子生成锰-(III)离子的方法,其中用臭氧由锰-(II)离子生成锰-(III)离子的效率是至少60%。
背景技术
在金属化之前,典型地将含有有机聚合物的基材表面蚀刻以在基材表面与镀敷的金属之间实现良好的粘附。尽管多年来许多化学品供应商和镀敷行业已经作出巨大努力以替代当前使用的有毒的蚀刻溶液,但当前在市场上没有可用的不含六价铬或Cr(VI)的商业产品来提供金属化工业所希望的效率。
含有Cr(VI)的化合物被怀疑致癌。因此,处理这些化合物要遵守严格的环境法规。面对由释放Cr(VI)的化合物引发的潜在危险,不能排除禁止工业使用含有Cr(VI)的化合物。
多年来,本行业已经提出多种化学物种在湿蚀刻工艺中用作不含铬的氧化剂以改性有机聚合物表面。此类氧化剂包括Mn(VII)、Mn(VI)、Mn(IV)、Ce(IV)、过硫酸盐、H2O2、有机溶剂(如二噁烷)、Fe、Cu、Ti、Zn和Mg的金属卤化物以及硝酸盐。氧化剂被蚀刻过程或者由于氧化剂的不稳定性消耗。因此,需要频繁的补充或再生方法。对于工业环境尤其优选再生方法。Mn(VII)是最常用的氧化剂之一。在水溶液中,其典型地呈离子物种MnO4 -的形式。在碱性溶液中Mn(VII)的电化学再生已经用于不同的行业中,如用于电路板的制造。与在碱性介质中相比,在酸性介质中Mn(VII)的再生似乎更困难。使用催化剂如Ag(I)或Bi(III)用于电化学氧化的公开文献是稀少的。Fleischmann等人(J.Appl.Electrochem.[应用电化学杂志]第1卷,第1页,1971)的研究已经表明Ag(I)是用于电化学氧化有机和无机物种两者的良好的催化剂。Park等人(J.Electrochem.Soc.[电化学会志]第151卷,第E265页,2004)公开了硼掺杂金刚石(BDD)电极上的Bi(III)还可以充当电子转移介质以使Mn(II)氧化为Mn(VII)。Boardman(J.Electroanal.Chem.[电分析化学杂志]第149卷,第49页,1983)和Comninellis(Electrochimica Acta[电化学学报],第36卷,第8期,第1363页,1991)已经证明在硫酸介质中在Ag(I)存在下由Mn(II)电化学形成Mn(VII)的可能性和用来增加Mn(VII)形成的电流效率的实验条件。U.S.2011/0140035公开了在用于预处理塑料表面的高锰酸盐酸性酸洗溶液中使用的类似方法。
然而,在酸性或者碱性介质中,Mn(VII)是不稳定的并且倾向于还原至其较低的氧化态,尤其是还原至Mn(IV),从而形成大量不可溶的MnO2并且在经处理的聚合物表面上引起质量问题。因此,在工业规模操作中需要从高锰酸盐蚀刻溶液中频繁除去MnO2沉淀物。
Mn(VII)的替代性蚀刻物种是Mn(III)。基于Mn(III)的蚀刻溶液的一个优点是不存在MnO2沉淀物。用于酸洗用于金属镀敷的聚合物的基于Mn(III)的不含铬的蚀刻溶液需要持续再生在蚀刻聚合物表面中消耗的Mn(III)。常规地,通过电解完成从其还原态Mn(II)(重新)-氧化为Mn(III)。电解再生可以用玻璃碳、网状玻璃碳或织造碳纤维阳极在0.1-0.4A/dm2的低电流密度范围内或用铂、镀铂的钛或镀铂的铌阳极在最高达8A/dm2的高电流密度下完成。在低电流密度范围内操作具有以下缺点:这需要非常大的阳极表面并且那些电解槽设备所需的空间对于工业规模应用变得不方便。例如,能够在24小时内镀敷1000m2聚合物材料的镀敷线需要至少1.6m2的阳极表面在0.25A/dm2的电流密度下操作。
在铂阳极的情况下,在较高电流密度下的电流效率仅是30%-50%。此外,由于较低的电流效率,因此在阳极处释放氧气,这因为铂腐蚀降低了阳极寿命。例如,能够在24小时内镀敷1000m2塑料的镀敷线在5A/dm2阳极电流密度下需要仅0.23m2的镀铂的阳极表面。然而,由于在此电流密度下约200g/m2/年的铂腐蚀,铂厚度为10μm的阳极寿命被预期为大约一年(根据Génie Electroch.[电化学工程];编辑:H Went和G.Kreysa,Dunod-Paris[巴黎杜诺德出版社];第307页(2001))。
此外,在Mn(III)的电解再生中,氢气在阴极处以化学计算量产生并且需要用足够量的空气稀释以使得处于爆炸范围(在空气中低于4%H2)之外。由于以上原因,电解再生方法具有低效、昂贵以及潜在危险的缺点,其中电解槽占据相当大的工厂空间。
因此,需要使用Mn(III)离子作为蚀刻物种的不含铬的蚀刻方法,所述方法在连续操作期间对于生成蚀刻物种是有效的并且是不危险且环保的。
发明内容
本发明的方法包括提供包含一种或多种有机聚合物的基材;提供包含硫酸、一种或多种烷烃磺酸以及Mn(II)离子和抗衡阴离子的水性酸溶液;将臭氧气体注入所述水性酸溶液中以用臭氧使所述Mn(II)离子氧化以生成至少15mmol/L Mn(III)离子,其中用臭氧使Mn(II)离子氧化以生成所述至少15mmol/L Mn(III)离子的效率是至少60%;以及
使所述包含一种或多种有机聚合物的基材与含有所述至少15mmol/L Mn(III)离子的水性酸溶液接触以蚀刻所述基材的一种或多种聚合物。
本发明的使用臭氧作为氧化剂以使Mn(II)离子氧化为Mn(III)离子的方法使得能够实现用于生成和再生Mn(III)离子蚀刻物种的高效率方法。本发明的方法消除了对生成和再生Mn(III)离子物种的电极和电解以及低效率的电解方法的需要。本发明的使用臭氧生成Mn(III)的方法生成环境友好的废产物,如水和氧气。使用臭氧使Mn(II)快速氧化为Mn(III)还减少或消除了可能损害使Mn(II)氧化为Mn(III)的效率的任何不希望的副反应。
本发明的方法在金属化之前使用不含铬的水性酸溶液蚀刻基材的一种或多种聚合物,因此消除了危险且环境上不希望的化合物。这些方法使用溶解的Mn(III)离子作为蚀刻剂代替Cr(VI)以使一种或多种聚合物粗糙化。Mn(III)离子在水性酸溶液中比Mn(VII)离子物种更稳定,不像Mn(VII)那样容易形成不可溶的MnO2。在水性酸溶液中通过用臭氧使Mn(II)离子氧化生成和再生Mn(III)离子。本发明的方法可以是连续方法,其中用臭氧由Mn(II)离子生成Mn(III)离子并且通过臭氧将在蚀刻过程期间还原回Mn(II)离子的Mn(III)离子氧化或再生为Mn(III)离子。
硫酸和一种或多种有机酸的混合物增加了Mn(II)和Mn(III)离子的溶解度,使得Mn(II)和Mn(III)离子基本上完全溶解在水性酸溶液中以提供Mn(III)氧化剂在溶液中的至少15mmol/L的浓度并且使用标准溶液循环和过滤系统在生产条件下操作。此外,已知,由于硫酸的吸湿性,具有较高硫酸含量的溶液容易从大气中吸附水。通过用一种或多种有机酸替代部分硫酸,可以减少或防止水吸附,由此保持良好的蚀刻性能。
此外,镀敷在本发明的经蚀刻的聚合物上的金属具有良好的剥离强度。此类剥离强度为7N/cm以及更大,或如10N/cm以及更大。
附图说明
图1是用含有7.2mol/L硫酸和5.4mol/L甲烷磺酸的臭氧化的混合酸溶液(溶液A)、25mmol/L Mn(II)在7.2mol/L硫酸和5.4mol/L甲烷磺酸中的含有Mn(II)的混合酸溶液(溶液B)、以及在将10mL的溶液A添加到40mL的溶液B中之后的溶液的1cm比色皿测量的吸光度对比波长(nm)的UV光谱,以及0.100mmol/L Mn(III)的参比光谱。
图2是在臭氧注入含有Mn(III)的水性酸反应溶液中18分钟后相比于含有Mn(VII)离子的水性酸溶液的吸光度对比波长(nm)的UV/VIS光谱。
图3是含有用臭氧再生的Mn(III)的水性酸溶液的吸光度对比波长(nm)的UV/VIS光谱,以及通过将可商购的乙酸Mn(III)溶解在水性酸溶液中制备的Mn(III)的参比光谱。
图4是用臭氧再生的Mn(III)水性酸溶液蚀刻的ABS表面在25,000倍放大倍率下的SEM图像。
图5是用臭氧再生的Mn(III)水性酸溶液蚀刻的PC-ABS表面在10,000倍放大倍率下的SEM图像。
具体实施方式
如本说明书通篇所使用的,除非上下文另有明确说明,否则下面给出的缩写具有以下含义:℃=摄氏度;g=克;L=升;M=摩尔或摩尔/升;mM=毫摩尔或毫摩尔/升;mol=摩尔;mmol=毫摩尔;mL=毫升;g/L=克/升;m=米;UV=紫外线;VIS=可见;nm=纳米;μm=微米;cm=厘米;mm=毫米;min=分钟;wt%=重量百分比;N=牛顿;kg=千克;Mn=元素锰;Mn(II)=锰二价氧化态;Mn(III)=锰三价氧化态;Mn(VII)=锰七价氧化态;Mn(VI)=锰六价氧化态;Mn(IV)=锰四价氧化态;Cr(VI)=铬六价氧化态;O3=臭氧(48g/mol的分子量);Ag=银;Bi=铋;Ce=铈;Pb=铅;H2SO4=硫酸;MnO4 -=高锰酸根;KMnO4=高锰酸钾;MSA=甲烷磺酸;ABS=丙烯腈、丁二烯和苯乙烯的嵌段共聚物;PC-ABS=聚碳酸酯以及丙烯腈、丁二烯和苯乙烯的嵌段共聚物的共混物;PTFE=聚四氟乙烯;吸光度=-log10=(I/I0);I=W/m2=透射光谱辐射功率;I0=W/m2=入射光谱辐射功率;SEM=扫描电子显微镜;以及ASTM=美国标准测试方法。
术语“生成”意指使Mn(II)离子氧化为Mn(III)离子。术语“再生”意指使Mn(II)离子氧化回Mn(III),其中水性酸溶液中的Mn(III)离子已经被还原为Mn(II)离子。所有数值范围都是包含端值的,并且可以按任何顺序组合,除了此类数值范围被解释为加起来最高达100%是合乎逻辑的的情况之外。除非另外指出,否则所有量是重量百分比并且所有比率按重量计。术语“一个/种(a/an)”被理解为包括单数和复数二者。
蚀刻溶液包含以下项(优选地由其组成):Mn(II)离子、Mn(II)离子的抗衡阴离子、和至少15mmol/L Mn(III)离子、硫酸和一种或多种烷烃磺酸,其中通过臭氧使Mn(II)离子氧化为Mn(III)。优选地,Mn(III)离子的浓度范围为30-60mmol/L、更优选35-55mmol/L。
通过臭氧使Mn(II)离子氧化以生成或再生Mn(III)离子在与蚀刻隔室(第二隔室)分开的隔室(第一隔室)中发生,使得在蚀刻过程期间用于使Mn(II)离子氧化为Mn(III)离子的臭氧都不与有待蚀刻的基材相互作用。Mn(III)离子的生成或再生可以通过分批或连续模式进行,其中用于通过臭氧使Mn(II)氧化的隔室(第一隔室)与进行基材的蚀刻的隔室(第二隔室)处于流体连通。连续模式是优选的操作模式。可以使用常规设备用于分批和连续模式操作。
用于蚀刻一种或多种聚合物并使其粗糙化的活性蚀刻剂是溶解的Mn(III)离子。水性酸溶液不是悬浮液、分散液或胶体溶液。水性酸溶液的所有溶质基本上溶解在水性酸溶液中。水性酸溶液不含铬。添加足够的水以使溶液达到100wt%。所添加的水的量可以是溶液的15-40wt%、优选18-30wt%、最优选19-25wt%。如果水的浓度太高,则损害溶液的蚀刻性能和溶液中Mn(III)离子的稳定性。
通过将臭氧气体注入水性酸溶液中以使Mn(II)离子氧化而使Mn(III)离子的浓度保持在至少15mmol/L的量以蚀刻聚合物基材或使其粗糙化,使得通过臭氧的Mn(III)生成和再生效率是至少60%、优选至少70%、更优选80%至95%。Mn(III)生成和再生效率根据以下方程被定义为通过臭氧至Mn(III)的转化效率:
Mn(III)(重新)生成效率=((重新)生成的Mn(III)的量)/(使得与溶液接触的臭氧的量×2)×100%。(方程1)
作为气体的臭氧可以使用对于工业应用以最高达750g的臭氧/小时以及更多的大容量范围可用的常规臭氧发生器来产生。臭氧的产生可以由空气或纯氧完成,在后者的情况下,可以达到最高达16wt%的臭氧浓度。当将臭氧气体混合物注入蚀刻溶液中时,以下反应顺序发生并占主导:
(1)O3(气体)→O3(溶解的)
(2)O3(溶解的)+2Mn2++2H+→2Mn3++H2O+O2
整个反应的速率决定步骤是将臭氧从气体转移至液相(反应1)。使溶解在液相中的臭氧与Mn(II)离子反应以在5秒或更短时间内形成Mn(III)。因此,为了实现高的Mn(III)生成和再生效率,使气液界面最大化并且延长气泡在液相中的保留时间。通过使臭氧气体以非常小的气泡形式与液体接触使气液界面最大化,这可以通过经由微孔扩散器或经由文氏管注射器注入臭氧实现。此类装置在本领域是众所周知的并且可以从各种供应商,例如荷兰的Lenntech BV公司获得。
气泡的保留时间在以分批模式再生的情况下可以通过增加气泡行进的液柱的长度或通过减小气泡直径(这降低其上升速度)来增加。气泡的保留时间此外可以通过搅拌溶液增加。在以连续模式再生的情况下,保留时间可以通过设计反应器(即用于Mn(II)氧化的隔室)调整。例如,在具有液体和气泡的并流流动的活塞流反应器的情况下,气泡的保留时间是反应管的长度(cm)与气液混合物的线性流速(cm/min)之间的比率。线性流速是体积流速(mL/min)与反应管的截面面积(cm2)之间的比率。因此,保留时间可以通过降低体积流速或通过增加反应管的截面面积而降低线性流速来增加。实现高Mn(III)再生效率(即大于60%)所需的保留时间取决于气泡的尺寸。气泡越小,气液界面将越大,并且因此臭氧从气体转移到液体中将越快。例如,当经由具有3μm孔径的PTFE玻璃料(frit)注入臭氧时,气泡的直径可以是约0.5-1.0mm。在此类气泡直径的情况下,78%的Mn(III)再生效率可以在6秒的气泡保留时间内获得(例如,实例2)。
臭氧能够在最初不含Mn(III)离子的水性酸溶液中引发Mn(II)离子至Mn(III)离子的氧化,或臭氧可以在含有两种物种的水性酸溶液中由Mn(II)生成Mn(III)。此外,如果在水性酸蚀刻溶液中任何Mn(III)被还原回Mn(II),则臭氧可以再生Mn(III)离子物种。本发明的臭氧方法可以是在蚀刻过程期间生成和再生Mn(III)离子物种的连续方法。当在一个隔室中将基材的一种或多种聚合物在水性酸蚀刻溶液中蚀刻时,使臭氧气体在分开的隔室中与水性酸溶液连续接触以将一些Mn(II)离子氧化以生成Mn(III)离子,或其中任何Mn(III)离子物种被还原回Mn(II),再生Mn(III)离子。
发生的反应产生在溶液中的水和氧气的环境友好的废产物以及产生到环境中的氧气。反应(2)发生的快速率显著减少例如(1a)和(2a)的不希望的副反应:
(1a)2O3(溶解的)→3O2(自分解)
(2a)4O3(溶解的)+RSO3H→H2SO4+CO2+H2O+4O2其中R是未取代的、直链或支链的(C1-C5)烷基。此类不希望的副反应可能损害本发明的方法的效率。
将臭氧以至少0.05g/L/h、优选0.10g/L/h至10g/L/h、更优选0.20g/L/h至7g/L/h的速率注入水性酸溶液中。
溶液中Mn(III)离子的浓度可以通过UV/VIS光谱法在530nm至520nm的波长范围内容易地确定。溶液中的Mn(II)离子浓度然后通过在通过原子吸收光谱法(AAS)确定的溶液中的总Mn浓度与溶液中的Mn(III)离子浓度之间的差来确定。UV/VIS和AAS是本领域众所周知的以及通常使用的用于分析溶液中的金属浓度的分析方法。Mn(III)离子是在15mmol/L或更高、优选15-70mmol/L、更优选30-60mmol/L并且甚至更优选35-55mmol/L的浓度下。
Mn(II)离子的来源包括但不限于Mn(II)-硫酸盐、Mn(II)-磷酸盐、Mn(II)-磷酸氢盐、Mn(II)-连二磷酸盐、Mn(II)-碳酸盐、Mn(II)-氧化物、Mn(II)-氢氧化物、Mn(II)-卤化物、Mn(II)-硝酸盐、Mn(II)-乙酸盐、Mn(II)-乳酸盐、Mn(II)-草酸盐、Mn(II)-柠檬酸盐、Mn(II)-乙酰丙酮化物、Mn(II)-硫化物、Mn(II)-甲酸盐、Mn(II)-乙二胺四乙酸盐-络合物(EDTA)、Mn(II)-次氮基三乙酸(NTA)络合物、具有氮-螯合物的锰(II)物种,如卟吩(如5,10,15,20-四苯基-21H,23H-卟吩和2,3,7,8,12,13,17,18-八乙基-21H-23H-卟吩)和酞菁。此类锰化合物是本领域已知的并且在文献中是已知的并且一些是可商购的。它们以足以提供至少5mmol/L至水性酸溶液中的饱和浓度、优选10-100mmol/L、更优选15-65mmol/L的Mn(II)离子浓度的量包含在溶液中。
硫酸以1wt%至84wt%、优选15wt%至70wt%的量包含在水性酸溶液中。烷烃磺酸包括甲烷磺酸、乙烷磺酸和丙烷磺酸。优选地,有机酸是乙烷磺酸和甲烷磺酸。最优选地,烷烃磺酸是甲烷磺酸。烷烃磺酸以1wt%至84wt%、优选15wt%至70wt%的量包含在水性酸溶液中。优选地,有机酸与硫酸的浓度比(wt/wt)大于0.20、更优选大于0.40、最优选大于0.60,使蚀刻溶液的吸湿性最小化。
任选地,可以将一种或多种催化剂添加到蚀刻溶液中以加速再生过程并且增加Mn(III)离子的蚀刻活性。此类催化剂包括但不限于选自Ag(I)、Bi(III)、Bi(V)、Ce(IV)和Pb(II)离子的金属离子。此类金属离子可以以25-1000mg/L金属的量、优选以100-500mg/L金属的量包含在蚀刻溶液中。此类催化剂的来源在本领域和文献中是已知的并且许多是可商购的,如硝酸银(I)、硫酸银(I)、氧化银(I)、甲烷磺酸银(I)、碳酸银(I)、甲烷磺酸铋(III)、氧化铋(III)、硝酸铋(III)、碳酸铋(III)、氧化铋(V)、铋(V)酸钠、乙酸铅(II)或硝酸铈(IV)铵。
将具有一种或多种有机聚合物的基材浸入水性酸溶液中或将所述溶液喷涂在所述基材上。在10℃至135℃、优选20℃至100℃、更优选30℃至80℃的溶液温度下进行有机聚合物的蚀刻。
有机聚合物包括但不限于热固性树脂、热塑性树脂及其组合。热塑性树脂包括但不限于缩醛树脂,丙烯酸类如丙烯酸甲酯,纤维素树脂如乙基醋酸纤维素,丙酸纤维素,乙酸丁酸纤维素和硝酸纤维素,聚醚,尼龙,聚乙烯,聚丙烯,聚苯乙烯,苯乙烯共混物如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯-苯乙烯(ABS)共聚物,聚碳酸酯(PC),聚三氟氯乙烯,和乙烯基聚合物和共聚物如乙酸乙烯酯,乙烯醇,乙烯醇缩丁醛,氯乙烯,氯乙烯-乙酸酯共聚物,偏二氯乙烯和乙烯醇缩甲醛。
热固性树脂包括但不限于邻苯二甲酸烯丙酯、呋喃、三聚氰胺-甲醛、苯酚-甲醛和苯酚-糠醛共聚物、单独或混合有丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯(ABS)共聚物、聚丙烯酸酯、硅氧烷、脲甲醛、环氧树脂、烯丙基树脂、邻苯二甲酸甘油酯和聚酯。
其他种类的聚合物树脂包括但不限于环氧树脂(如双官能和多官能环氧树脂,双马来酰亚胺/三嗪和环氧树脂(BT环氧)、环氧/聚亚苯基氧化物树脂)、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯(PC)、聚亚苯基氧化物(PPO)、聚苯醚(PPE)、聚苯硫醚(PPS)、聚砜(PSU)、聚酰胺(PA)、聚酯如聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)、聚醚酮(PEEK)、液晶聚合物(LCP)、聚氨酯(PU)、聚醚酰亚胺(PEI)、环氧化物及其复合物。
任选地,在用本发明的水性酸溶液和方法蚀刻之前,可以使用常规方法步骤对基材的聚合物进行清洁和溶剂溶胀。可商购的清洁剂的实例是清洁剂PM-900并且对于溶剂溶胀剂是调节剂PM-920。用水性酸蚀刻溶液将具有有机聚合物的基材处理10秒至30分钟、优选2分钟至15分钟。在将基材的有机聚合物蚀刻之后,将基材用水冲洗并且然后使用常规方法进一步加工为金属化准备。为金属化准备的此类步骤可以包括用活化剂处理基材的聚合物用于无电镀金属化,如钯-锡胶体催化剂。可商购的钯-锡胶体催化剂的实例是CATAPOSITTM PM-957胶体钯-锡催化剂。任选地,可以用促进剂,如ACCELERATORTM PM-964溶液对基材的聚合物进行处理。然后使用常规金属镀敷方法和金属镀敷浴,如镍和铜使其金属化。可商购的镍浴的实例是NIPOSITTM PM-988无电镀镍溶液。可商购的镀铜浴的实例是ECOPOSITTM 950铜电镀浴。所有前述商业产品是从马萨诸塞州马尔堡的罗门哈斯电子材料有限公司(Rohm and Haas Electronic Materials LLC,Marlborough,MA)可获得的。
包括以下实例以进一步说明本发明,但是并不旨在限制其范围。
实例1
含有臭氧的混合酸溶液(溶液A)通过使臭氧通过400mL/L硫酸96wt%(7.2M硫酸)和550mL/L甲烷磺酸70wt%(5.4M甲烷磺酸)的溶液来制备。臭氧用OZONETECH ICT-10TM臭氧发生器(从臭氧技术系统OTS AB公司(Ozone Tech Systems OTS AB)可获得)以4.99g/h(5.87g/L/h)臭氧气体的臭氧生产速率由纯氧产生。将臭氧/氧气气体混合物(11.2wt%的臭氧)以0.5L/min的速率通过0.85L混合酸溶液的溶液持续10min(0.83g O3)。水性酸溶液的pH小于1。在1升玻璃瓶中经由具有4个0.5mm直径的孔的PTFE气体分配器使臭氧与水性酸溶液接触,使得臭氧气体通过溶液的行进长度是10cm。在臭氧通过此溶液之后,通过在259nm处的UV吸光度确定溶解在溶液中的臭氧浓度。臭氧化的混合酸溶液的臭氧浓度是0.296mmol/L(14.21mg/L)。
制备含有400mL/L硫酸96wt%(7.2M硫酸)、550mL/L甲烷磺酸70wt%(5.4M甲烷磺酸)、73mL/L水、4.22g/L一水合硫酸锰(II)(25.0mmol/L)的混合酸Mn(II)溶液(溶液B)。
在快速搅拌下将10mL的含有臭氧的混合酸溶液A添加到40mL的混合酸Mn(II)溶液B中。在将两种溶液混合之后立即(在少于5秒内)出现来自通过臭氧与Mn(II)反应产生的Mn(III)的浅紫色。反应之后的溶液的UV光谱与Mn(III)的参比光谱相匹配(图1)。在259nm处的臭氧的UV吸收峰在反应之后的溶液中完全不存在,表明所有臭氧已经反应并且不再存在水性臭氧。从在282nm处的吸光度确定了Mn(III)浓度为0.0999mmol/L。因此,通过将两种溶液混合使水性臭氧与Mn(II)反应的Mn(III)形成效率(相对于臭氧的量的产率)是:
效率=0.0999mmol/L×50mL/(0.296mmol/L×10mL×2)=84.4%。
此实例示出水性臭氧与Mn(II)在混合酸溶液中非常快地反应以形成Mn(III),其效率大于80%。因此,当使臭氧气体与含有Mn(II)的硫酸和甲烷磺酸的混合酸溶液接触时,臭氧与Mn(II)反应以在气/液界面处形成Mn(III)使得在大部分的溶液中不存在臭氧。
实例2
OZONETECH ICT-10TM臭氧发生器(从臭氧技术系统OTS AB公司可获得)用于由纯氧生成5.22g/h(4.35g/L/h)的臭氧气体。将臭氧/氧气气体混合物(11.7wt%臭氧)在60℃下以0.5L/min通过1.2L的400mL/L硫酸96wt%(7.2M硫酸)、550mL/L甲烷磺酸70wt%(5.4M甲烷磺酸)、73mL/L水、11g/L一水合硫酸锰(II)(65.1mmol/L)和470mg/L甲烷磺酸银(2.31mmol/L)的溶液持续18min(1.57g O3)。水性酸蚀刻溶液的pH小于1。在4.3cm内径的垂直管中经由具有3μm孔径的PTFE玻璃料使臭氧与水性酸蚀刻溶液接触使得臭氧气体通过溶液的行进长度是75cm。气泡行进75cm的溶液所需的时间是约6秒。
在臭氧注入水性酸蚀刻溶液期间,颜色从淡黄色变成紫色,这表明Mn(III)离子的形成,如通过溶液的UV/VIS光谱证实(用HITACHI U-2910分光光度计记录)在525nm处示出吸光度最大值。以下方程说明发生的反应:
1)将臭氧溶解:O3(气体)→O3(溶解在水性酸溶液中)。
2)使溶解的臭氧在水性酸溶液中与Mn(II)离子在5秒或更短时间内反应,如通过以下化学方程式示出。
O3(溶解在水性酸溶液中)+2Mn2++2H+→2Mn3++H2O+O2(气体)
Mn(III)的浓度从0至2.34g/L(42.6mmol/L),这对应于78.3%的Mn(III)生成效率(根据方程1计算)。当Mn(III)达到如通过在525nm处UV/VIS吸光度测量的42.6mmol/L的浓度时,停止臭氧注入。未反应的Mn(II)以一水合硫酸锰(II)计的浓度在停止臭氧注入时是1.23g/L。
生成的蚀刻物种的量=42.6mmol/L×1.2L=51.12mmol
与水性酸溶液接触的臭氧的量=5.22g/h×18min/48g/mol=32.63mmol(48g/mol=臭氧的摩尔质量)
臭氧转化效率=(51.12mmol)/32.63mmol×2)×100%=78.3%。
实例3(对比)
OZONETECH ICT-10TM臭氧发生器(从臭氧技术系统OTS AB公司可获得)用于由纯氧生成6.75g/h(4.21g/L/h)的臭氧气体。将臭氧/氧气气体混合物(12.7wt%臭氧)在60℃下以0.6L/min通过1.6L的400mL/L硫酸96wt%(7.2M硫酸)、550mL/L甲烷磺酸70wt%(5.4M甲烷磺酸)、73mL/L水、11g/L一水合硫酸锰(II)(65.1mmol/L)和470mg/L甲烷磺酸银(2.31mmol/L)的溶液持续15min(1.68g O3)。水性酸蚀刻溶液的pH小于1。在2L洗气瓶中经由具有3μm孔径的PTFE玻璃料使臭氧与水性酸蚀刻溶液接触使得臭氧气体通过溶液的行进长度是12cm。气泡行进12cm的溶液所需的时间是约1秒。在臭氧注入水性酸蚀刻溶液期间,颜色从淡黄色变成紫色,这表明Mn(III)离子的形成,如通过溶液的UV/VIS光谱证实(用HITACHI U-2910分光光度计记录)在525nm处示出吸光度最大值。
Mn(III)的浓度从0至0.747g/L(13.6mmol/L),这对应于30.9%的Mn(III)生成效率(根据方程1计算)。未反应的Mn(II)以一水合硫酸锰(II)计的浓度在停止臭氧注入时是2.82g/L。
生成的蚀刻物种的量=13.6mmol/L×1.6L=21.76mmol
与水性酸溶液接触的臭氧的量=6.75g/h×15min/48g/mol=35.16mmol(48g/mol=臭氧的摩尔质量)
Mn(III)生成效率=(21.76mmol)/(35.16mmol×2)×100%=30.9%。
实例4(对比)
在如在实例2中描述的臭氧注入期间,Mn(III)在水性酸溶液中是最高氧化物种,如通过UV/VIS光谱法证明的并在图2中示出。图2中的虚线示出使用2mm比色皿在臭氧注入18min之后400至700nm的水性酸溶液的UV/VIS光谱,同时实线UV/VIS光谱示出源自将10mmol/L高锰酸钾溶解在酸基质中的Mn(VII)物种具有如在实例2中公开的浓度。两种物种通过其在可见光区域的不同的吸光度最大值(525nm:Mn(III),480nm:Mn(VII))来区分。
图3示出稀释20倍(为了在UV区域也能得到更好的峰的分辨率)的实例2的水性酸溶液的UV/VIS光谱与通过将可商购的乙酸Mn(III)(从西格玛-奥德里奇公司(Sigma-Aldrich)获得的)溶解在酸基质中制备的Mn(III)的参比光谱的对比。将每种样品置于2mm比色皿中。实例2中的水性酸溶液的UV/VIS光谱由虚线示出。实线是溶解在实例2的酸基质中的可商购的乙酸Mn(III)的UV/VIS光谱。两个光谱在220nm至700nm的整个光谱范围内基本上匹配。光谱的匹配表明用臭氧氧化产生的水性酸蚀刻溶液中没有形成Mn(VII)。
实例5
将ABS测试基板使用常规的并且可商购的清洁剂PM-900(从罗门哈斯电子材料有限公司可获得)在45℃下清洁3min。随后,将ABS塑料零件在65℃下浸入水性酸蚀刻溶液中持续10min并且然后在室温下用去离子水冲洗。在干燥之后,样品在25,000倍下进行SEM观察,其在图4中示出。如在图4中所示,含有Mn(III)的水性酸蚀刻溶液使ABS表面显著粗糙化,如通过许多孔证明的。
将另一个ABS测试基板使用清洁剂PM-900在45℃下清洁3min。清洁剂处理从表面除去污垢和指纹,但使得表面是未改性的或未改变的并且疏水的。随后,将ABS基板在60℃下浸入上述的蚀刻溶液中持续7min并且然后在室温下用去离子水冲洗。ABS的表面看起来基本上如图4所示。
然后将ABS用CATAPOSITTM PM-957胶体钯-锡催化剂的活化剂溶液在30℃下处理3min(从罗门哈斯电子材料有限公司可获得)。然后将经催化的ABS在45℃下用ACCELERATORTM PM-964溶液(从罗门哈斯电子材料有限公司可获得)处理3min并且然后使用NIPOSITTM PM-988无电镀镍溶液(从罗门哈斯电子材料有限公司可获得)用无电镀镍镀敷。在33℃下进行无电镀镍以沉积0.3μm的镍层。随后,将镀镍的ABS使用基于焦磷酸铜的电镀浴用碱性铜预镀(strike)以1A/dm2在42℃下电镀6min以确保足以用于后续步骤的电导率。然后,使用ECOPOSITTM 950铜电镀浴(从罗门哈斯电子材料有限公司可获得)对零件进行酸性镀铜。在室温下以3A/dm2进行酸性镀铜直至沉积40μm铜层。然后将镀镍和镀铜的ABS在70℃下加热1小时。
使用具有先进测力计Mecmesin AFG-100N的Mecmesin Versa测试(类似于ASTMB533-85)测量剥离强度。用1cm剥离带以25mm/min剥离速度测量金属沉积物的剥离强度。确定剥离强度是10N/cm。
实例6
将PC-ABS测试基板使用清洁剂PM-900在45℃下清洁3min。然后,将PC-ABS基板在30℃下浸入溶剂溶胀溶液调节剂PM-920中持续2min。在冲洗之后,将PC-ABS基板在65℃下浸入实例2的水性酸蚀刻溶液中持续20min并且然后用去离子水冲洗。在干燥之后,PC-ABS在10,000倍下进行SEM观察,其在图5中示出。如在图5中所示,含有Mn(III)的水性酸蚀刻溶液使PC-ABS表面显著粗糙化,如通过许多孔证明的。
将第二PC-ABS测试基板使用清洁剂PM-900在45℃下清洁3min。清洁剂处理从表面除去污垢和指纹,但使得表面是未改性的并且疏水的。然后,将PC-ABS基板在30℃下浸入溶剂溶胀溶液调节剂PM-920中持续2min。在冲洗之后,将PC-ABS基板在65℃下浸入实例2的蚀刻溶液中持续20min并且然后在室温下用去离子水冲洗。然后将PC-ABS用CATAPOSITTM PM-957胶体锡/钯催化剂的活化剂溶液在30℃下处理3min。然后将经催化的PC-ABS在45℃下用ACCELERATORTM PM-964溶液处理3min并且然后使用NIPOSITTM PM-988无电镀镍溶液用无电镀镍镀敷。在33℃下进行无电镀镍以沉积0.3μm的镍层。随后,将镀镍的PC-ABS使用基于焦磷酸铜的电镀浴用碱性铜预镀以1A/dm2在42℃下电镀6min以确保足以用于后续步骤的电导率。然后,使用ECOPOSITTM 950铜电镀浴(从罗门哈斯电子材料有限公司可获得)对零件进行酸性镀铜。在室温下以3A/dm2进行酸性镀铜直至沉积40μm铜层。然后将镀镍和镀铜的PC-ABS在70℃下加热1小时。
使用具有先进测力计Mecmesin AFG-100N的Mecmesin Versa测试(类似于ASTMB533-85)测量剥离强度。用1cm剥离带以25mm/min剥离速度测量金属沉积物的剥离强度。确定剥离强度是7N/cm。
实例7(对比)
使用常规的用于制备常规的基于高锰酸盐的不含铬的蚀刻组合物的臭氧方法由Mn(II)离子生成高锰酸根离子(Mn(VII))的效率在下面描述。制备含有在表1中示出的量的组分的测试溶液。
表1
组分 | 量(mol/L) |
硫酸锰(II) | 0.07 |
甲烷磺酸 | 4 |
硫酸 | 8 |
使用可商购的臭氧发生装置,将臭氧气体吹入测试溶液(1L)中持续一小时,并且通过抗坏血酸滴定法获得在浴中生成的高锰酸根离子的浓度。臭氧气体的产量是200mg/h或1000mg/h,并且吹入量是2L/min。
通过使用以下方法中的任一种吹入臭氧气体:通过使用具有1.5mm的尖端直径的玻璃管吹入臭氧气体的方法(一般鼓泡)或通过提供具有直径约为30μm的浮石的玻璃管的末端吹入以微泡形式的臭氧气体的方法(微鼓泡)。结果在表2中公开。
表2
通过臭氧生成高锰酸根的效率使用以下方程确定:
效率=(产生的高锰酸根的量×5(转移的电子))/(通过溶液的臭氧的量×2(转移的电子)×100%。
效率数据在以下表3中公开。
表3
前述常规方法的臭氧处理仅具有7.57%高的效率。相比之下,如在以上实例2中公开的本发明的方法具有78.3%的效率。
Claims (10)
1.一种方法,其包括:
a)提供包含一种或多种有机聚合物的基材;
b)提供包含硫酸、一种或多种烷烃磺酸以及Mn(II)离子和抗衡阴离子的水性酸溶液;
c)将臭氧气体注入所述水性酸溶液中以用臭氧使所述Mn(II)离子氧化以生成至少15mmol/L Mn(III)离子,其中用臭氧使Mn(II)离子氧化以生成所述至少15mmol/L Mn(III)离子的效率是至少60%;以及
d)使所述包含一种或多种有机聚合物的基材与含有所述至少15mmol/L Mn(III)离子的水性酸溶液接触以蚀刻所述基材的一种或多种聚合物。
2.如权利要求1所述的方法,其中,所述效率是至少70%。
3.如权利要求2所述的方法,其中,所述效率是80%至95%。
4.如权利要求1所述的方法,其中,将臭氧气体以至少0.05g/L/h的速率注入所述水性酸溶液中。
5.如权利要求4所述的方法,其中,将所述臭氧气体以0.1g/L/h至10g/L/h的速率注入所述水性酸溶液中。
6.如权利要求5所述的方法,其中,将所述臭氧气体以0.2g/L/h至7g/L/h的速率注入所述水性酸溶液中。
7.如权利要求1所述的方法,其中,所述Mn(III)离子的浓度是15-70mmol/L。
8.如权利要求7所述的方法,其中,所述Mn(III)离子的浓度是30-60mmol/L。
9.如权利要求8所述的方法,其中,所述Mn(III)离子的浓度是35-55mmol/L。
10.如权利要求1所述的方法,其中,所述水性酸溶液进一步包含一种或多种金属离子的来源。
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JP2020094209A (ja) | 2020-06-18 |
US20200181787A1 (en) | 2020-06-11 |
TW202022090A (zh) | 2020-06-16 |
KR102361126B1 (ko) | 2022-02-09 |
TWI777109B (zh) | 2022-09-11 |
EP3666926B1 (en) | 2021-09-15 |
JP6928640B2 (ja) | 2021-09-01 |
US10889905B2 (en) | 2021-01-12 |
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