CN107190249B - 一种多孔金属泡沫铜的制备方法 - Google Patents

一种多孔金属泡沫铜的制备方法 Download PDF

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CN107190249B
CN107190249B CN201710443844.7A CN201710443844A CN107190249B CN 107190249 B CN107190249 B CN 107190249B CN 201710443844 A CN201710443844 A CN 201710443844A CN 107190249 B CN107190249 B CN 107190249B
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万晔
张海啸
张雨乐
刘晶
彭磊
徐拥军
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Shenyang Jianzhu University
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Abstract

本发明涉及一种多孔金属泡沫铜的制备方法，包括如下步骤：(1)除油；(2)一次粗化；(3)二次粗化；(4)一次还原；(5)敏化；(6)活化；(7)二次还原；(8)化学镀铜；(9)电镀铜；(10)热处理。该方法解决了现有制备技术存在的孔结构分布不均匀、孔隙率低、镀层质量差、比表面积小等问题。提供了一种简单易操作，过程可控性高，原料来源广，价格低廉，所制备的泡沫铜具有良好的孔结构，镀层质量好，比表面积大，具有较好的强度。

Description

一种多孔金属泡沫铜的制备方法
技术领域
本发明涉及多孔泡沫金属材料制备技术领域，尤其涉及一种多孔金属泡沫铜的制备。
背景技术
泡沫铜是一种新型功能材料，具有轻质、高强、比表面积大、孔隙率高等优点，可以应用在过滤、催化、导热、消音屏蔽、缓冲、电极材料等领域。由于泡沫铜的导电性能比泡沫镍更好，生产成本更低，现在作为泡沫镍的替代材料被用于电极材料的制备中，作为镍锌电池、双电层电容器等新型电池的电极骨架材料。由于泡沫铜比表面积较大，泡沫金属具有优良的导热性能，综合效益最佳，作为电子元件、电器的散热材料，先进消防器材的阻燃材料。
目前泡沫铜的制备工艺较多，但大部分存在成本较高、工艺复杂、质量难以控制的问题，且随制备工艺的不同，泡沫铜的性能也各有差异，而电沉积方法制备的泡沫材料往往具有较高的孔隙率，且较渗流法、定向凝固法等开孔率较高，均匀度也较好，应用最为广泛。
发明内容
本发明为了解决现有泡沫铜制备工艺中得到的金属泡沫铜孔结构不均匀，比表面积小等问题，提供了一种操作简单，过程易控制，成本低廉的金属泡沫铜制备方法。
为实现上述目的，得到具有良好孔结构和高比表面积的金属泡沫铜，本发明的技术方案如下：
一种多孔金属泡沫铜的制备方法，按照以下步骤进行：
(1)除油：将孔隙率≧90％的聚氨酯泡沫塑料样品浸入除油液中，于50-60℃水浴中超声清洗5-10min，取出泡沫，用50-60℃温水浸泡3min，再用流动的蒸馏水冲洗5min；
(2)一次粗化：将步骤(1)处理后的聚氨酯泡沫塑料基体放入一次粗化液中，在水浴加热条件下进行粗化处理15-25min,水浴温度为40-60℃，粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，烘干；
(3)二次粗化：将步骤(2)一次粗化处理后的聚氨酯泡沫塑料放入二次粗化液中，在水浴加热条件下进行粗化处理30-40min，水浴温度为60-70℃，粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，烘干；
(4)一次还原：将步骤(3)二次粗化处理后的聚氨酯泡沫塑料放入一次还原溶液中，在20-30℃水浴条件下处理5-10min，然后将样品在流动蒸馏水中冲洗5min，烘干；
(5)敏化：将步骤(4)所得聚氨酯泡沫塑料样品放入敏化液中，敏化液配方为：30g/L二氯化锡、50ml/L浓盐酸，溶液中加入锡粒，水浴30-35℃，处理时间10-15min，然后将样品在流动蒸馏水中冲洗10min，烘干；
(6)活化：将步骤(5)所得聚氨酯泡沫塑料样品放入活化液中，室温活化5min，活化后用蒸馏水冲洗10min，烘干；
(7)二次还原：将步骤(6)所得聚氨酯泡沫塑料样品放入二次还原溶液中浸泡30s，用流动蒸馏水反复冲洗10min后，烘干；
(8)化学镀铜：将步骤(7)所得聚氨酯泡沫塑料样品放入化学镀液中，在50-60℃水浴条件下处理10-15min,然后将样品在流动蒸馏水中冲洗5min，烘干；
(9)电镀铜：将步骤(8)所得聚氨酯泡沫塑料样品放入电镀液中，水浴温度为40-50℃，先以2.5A/dm2的电流密度下电镀2-3min，然后在1.2-1.4A/dm2电流密度下继续电镀30-40min,然后将样品在流动蒸馏水中冲洗5min，烘干；
(10)热处理：将步骤(9)所得聚氨酯泡沫塑料样品放入电热炉中，由室温加热至600℃，升温速率5℃/min，在600℃下保温1.5-2.5h，然后缓慢冷却至室温，得到金属泡沫铜。
其中，步骤(1)所述除油过程，除油液配方为：45g/L碳酸钠、35g/L磷酸三钠、60g/L氢氧化钠、0.5ml/L表面活性剂OP-10，期间体系需进行超声处理，频率为35-40KHz，处理时要注意使聚氨酯泡沫塑料基体充分浸润在除油液中，并不断用玻璃棒挤压，除去基体中的气泡。
其中，步骤(2)所述一次粗化过程，一次粗化液配方为：5-10vol.％硝酸，9mol/L双氧水，5-7g/L高锰酸钾，调节溶液pH2-3，粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。
其中，步骤(3)所述二次粗化过程，二次粗化液配方为：10g/L三氧化铬、浓硫酸、磷酸按质量比为4:2:1的比例配制，粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。
其中，步骤(4)所述一次还原过程，一次还原溶液配方为：15g/L草酸溶液。
其中，步骤(5)所述敏化过程，敏化液配方为：30g/L二氯化锡、50ml/L浓盐酸，溶液中加入锡粒，敏化过程中需不断用玻璃棒搅拌翻动泡沫，挤出其中气泡。
其中，步骤(6)所述活化过程，活化液配方为：7-9g/LAgNO3、12ml/L的25％氨水。
其中，步骤(7)所述二次还原过程，二次还原溶液配方为：10ml/L的37％甲醛溶液。
其中，步骤(8)所述化学镀铜过程，化学镀液配方为：15–20g/L硫酸铜、1.1-1.3g/L硫酸镍、30-40g/L次磷酸钠、6-8g/L葡萄糖、50mg/L聚乙二醇、20-25g/L柠檬酸钠、6g/L氢氧化钠。
其中，步骤(9)所述电镀过程，电镀液配方为：160–180g/L硫酸铜、15-20ml/L硫酸、40-50mg/L聚乙二醇、50mg/L氯化钠。
本发明的有益效果为：操作过程简单，可控性好，所用试剂可二次利用，试剂价格低廉，成本低。所制备的金属泡沫铜具有良好的孔结构，孔隙率高，镀层质量好，比表面积大，具有一定的强度。
附图说明
图1为本发明实施例3金属泡沫铜样品超景深显微观形貌图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
(1)除油：将孔隙率≧90％的聚氨酯泡沫塑料样品浸入除油液中，于50℃水浴加热，处理5min，期间对体系进行超声处理，频率为35KHz。然后取出泡沫，用50℃温水浸泡3min，再用流动的蒸馏水冲洗5min。处理时要注意使聚氨酯泡沫塑料基体充分浸润在除油液中，并不断用玻璃棒挤压，除去基体中的气泡。
(2)一次粗化：将步骤(1)处理后的聚氨酯泡沫塑料基体放入一次粗化液中,在水浴加热条件下进行粗化处理。一次粗化液配方为：硝酸(5vol.％)，双氧水(9mol/L)，高锰酸钾(5g/L)，调节溶液pH＝2。处理时间15min,水浴温度为40℃。粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，除去水分备用。
(3)二次粗化：将步骤(2)一次粗化处理后的聚氨酯泡沫塑料放入二次粗化液中，在水浴加热条件下进行粗化处理。二次粗化液配方为：三氧化铬(10g/L)、浓硫酸、磷酸按质量比为4:2:1的比例配制，处理时间30min，水浴温度为60℃。粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，除去水分备用。
(4)一次还原：将步骤(3)二次粗化处理后的聚氨酯泡沫塑料放入草酸溶液(15g/L)中，在20℃水浴条件下处理5min。然后将样品在流动蒸馏水中冲洗5min，除去水分备用。
(5)敏化：将步骤(4)所得聚氨酯泡沫塑料样品放入敏化液中，敏化液配方为：二氯化锡(30g/L)、浓盐酸(50ml/L)，溶液中加入锡粒。水浴30℃，处理时间10min，敏化过程中不断用玻璃棒搅拌翻动泡沫，然后将样品在流动蒸馏水中冲洗10min，除去水分备用。
(6)活化：将步骤(5)所得聚氨酯泡沫塑料样品放入活化液中，活化液配方为：AgNO3(7g/L)、25％氨水(12ml/L)，室温活化5分钟。活化后用蒸馏水冲洗10min，除去水分备用。
(7)二次还原：将步骤(6)所得聚氨酯泡沫塑料样品放入37％甲醛溶液(10ml/L)中浸泡30s,然后用流动蒸馏水反复冲洗10min，烘干备用。
(8)化学镀铜：将步骤(7)所得聚氨酯泡沫塑料样品放入化学镀液中，配方为：硫酸铜(15g/L)、硫酸镍(1.1g/L)、次磷酸钠(30g/L)、葡萄糖(6g/L)、聚乙二醇(50mg/L)、柠檬酸钠(20g/L)、氢氧化钠(6g/L)。在50℃水浴条件下处理10min,然后将样品在流动蒸馏水中冲洗5min，除去水分备用。
(9)电镀铜：将步骤(8)所得聚氨酯泡沫塑料样品放入电镀液中，配方为：硫酸铜(160g/L)、硫酸(15ml/L)、聚乙二醇(40mg/L)、氯化钠(50mg/L)。水浴温度为40℃，先以2.5A/dm2的电流密度下电镀2min，然后在1.2A/dm2电流密度下继续电镀30min,然后将样品在流动蒸馏水中冲洗5min，烘干备用。
(10)热处理：将步骤(9)所得聚氨酯泡沫塑料样品放入电热炉中，气氛为氢气与氮气按体积比2:1混合气体，由室温加热至600℃，升温速率5℃/min，在600℃下保温1.5h，然后缓慢冷却至室温，得到金属泡沫铜。
实施例2
(1)除油：将孔隙率≧90％的聚氨酯泡沫塑料样品浸入除油液中，于60℃水浴加热，处理10min，期间对体系进行超声处理，频率为40KHz。然后取出泡沫，用60℃温水浸泡3min，再用流动的蒸馏水冲洗5min。处理时要注意使聚氨酯泡沫塑料基体充分浸润在除油液中，并不断用玻璃棒挤压，除去基体中的气泡。
(2)一次粗化：将步骤(1)处理后的聚氨酯泡沫塑料基体放入一次粗化液中,在水浴加热条件下进行粗化处理。一次粗化液配方为：硝酸(10vol.％)、双氧水(9mol/L)、高锰酸钾(7g/L)，调节溶液pH＝3。处理时间25min,水浴温度为60℃。粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，除去水分备用。
(3)二次粗化：将步骤(2)一次粗化处理后的聚氨酯泡沫塑料放入二次粗化液中，在水浴加热条件下进行粗化处理。二次粗化液配方为：三氧化铬(10g/L)、浓硫酸、磷酸按质量比为4:2:1的比例配制，处理时间40min，水浴温度为70℃。粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀。粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，除去水分备用。
(4)一次还原：将步骤(3)二次粗化处理后的聚氨酯泡沫塑料放入草酸溶液(15g/L)中，在30℃水浴条件下处理10min。然后将样品在流动蒸馏水中冲洗5min，除去水分备用。
(5)敏化：将步骤(4)所得聚氨酯泡沫塑料样品放入敏化液中，敏化液配方为：二氯化锡(30g/L)、浓盐酸(50ml/L)，溶液中加入锡粒。水浴35℃，处理时间15min，敏化过程中不断用玻璃棒搅拌翻动泡沫，然后将样品在流动蒸馏水中冲洗10min，除去水分备用。
(6)活化：将步骤(5)所得聚氨酯泡沫塑料样品放入活化液中，活化液配方为：AgNO3(9g/L)、25％氨水(12ml/L)，室温活化5分钟。活化后用蒸馏水冲洗10min，除去水分备用。
(7)二次还原：将步骤(6)所得聚氨酯泡沫塑料样品放入37％甲醛溶液(10ml/L)中浸泡30s,然后用流动蒸馏水反复冲洗10min，烘干备用。
(8)化学镀铜：将步骤(7)所得聚氨酯泡沫塑料样品放入化学镀液中，配方为：硫酸铜(20g/L)、硫酸镍(1.3g/L)、次磷酸钠(40g/L)、葡萄糖(8g/L)、聚乙二醇(50mg/L)、柠檬酸钠(25g/L)、氢氧化钠(6g/L)。在60℃水浴条件下处理15min,然后将样品在流动蒸馏水中冲洗5min，除去水分备用。
(9)电镀铜：将步骤(8)所得聚氨酯泡沫塑料样品放入电镀液中，配方为：硫酸铜(180g/L)、硫酸(20ml/L)、聚乙二醇(50mg/L)、氯化钠(50mg/L)。水浴温度为50℃，先以2.5A/dm2的电流密度下电镀3min，然后在1.4A/dm2电流密度下继续电镀40min,然后将样品在流动蒸馏水中冲洗5min，烘干备用。
(10)热处理：将步骤(9)所得聚氨酯泡沫塑料样品放入电热炉中，气氛为氢气与氮气按体积比2:1混合气体，由室温加热至600℃，升温速率5℃/min，在600℃下保温2.5h，然后缓慢冷却至室温，得到金属泡沫铜。
本实施所制备的金属泡沫铜超景深微观形貌图见图1。

Claims (1)

1.一种多孔金属泡沫铜的制备方法，其特征在于，按照以下步骤进行：
(1)除油：将孔隙率≧90％的聚氨酯泡沫塑料样品浸入除油液中，于60℃水浴中，采用频率为40KHz的超声清洗10min，取出泡沫，用60℃温水浸泡3min，再用流动的蒸馏水冲洗5min；处理时要注意使聚氨酯泡沫塑料基体充分浸润在除油液中，并不断用玻璃棒挤压，除去基体中的气泡；除油液配方为：45g/L碳酸钠、35g/L磷酸三钠、60g/L氢氧化钠、0.5ml/L表面活性剂OP-10；
(2)一次粗化：将步骤(1)处理后的聚氨酯泡沫塑料基体放入一次粗化液中，在水浴加热条件下进行粗化处理25min,水浴温度为60℃，粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，烘干；其中，一次粗化液配方为：10vol.％硝酸，9mol/L双氧水，7g/L高锰酸钾，调节溶液pH=3；粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀；
(3)二次粗化：将步骤(2)一次粗化处理后的聚氨酯泡沫塑料放入二次粗化液中，在水浴加热条件下进行粗化处理40min，水浴温度为70℃，粗化处理后，用流动蒸馏水冲洗聚氨酯泡沫塑料5min，烘干；其中，二次粗化液配方为：10g/L三氧化铬、浓硫酸、磷酸按质量比为4:2:1的比例配制，粗化过程中不断用玻璃棒搅拌翻动泡沫，除去其中气泡，保证粗化均匀；
(4)一次还原：将步骤(3)二次粗化处理后的聚氨酯泡沫塑料放入15g/L的草酸溶液中，在30℃水浴条件下处理10min，然后将样品在流动蒸馏水中冲洗5min，烘干；
(5)敏化：将步骤(4)所得聚氨酯泡沫塑料样品放入敏化液中，敏化液配方为：30g/L二氯化锡、50ml/L浓盐酸，溶液中加入锡粒，水浴35℃，处理时间15min，然后将样品在流动蒸馏水中冲洗10min，烘干；
(6)活化：将步骤(5)所得聚氨酯泡沫塑料样品放入活化液中，活化液配方为：7-9g/LAgNO3、12ml/L的25％氨水，室温活化5min，活化后用蒸馏水冲洗10min，烘干；
(7)二次还原：将步骤(6)所得聚氨酯泡沫塑料样品放入10ml/L的37％甲醛溶液二次还原溶液中浸泡30s，用流动蒸馏水反复冲洗10min后，烘干；
(8)化学镀铜：将步骤(7)所得聚氨酯泡沫塑料样品放入化学镀液中，在60℃水浴条件下处理15min,然后将样品在流动蒸馏水中冲洗5min，烘干；其中，化学镀液配方为：20g/L硫酸铜、1.3g/L硫酸镍、40g/L次磷酸钠、8g/L葡萄糖、50mg/L聚乙二醇、25g/L柠檬酸钠、6g/L氢氧化钠；
(9)电镀铜：将步骤(8)所得聚氨酯泡沫塑料样品放入电镀液中，水浴温度为50℃，先以2.5A/dm2的电流密度下电镀3min，然后在1.4A/dm2电流密度下继续电镀40min,然后将样品在流动蒸馏水中冲洗5min，烘干；所述的电镀液配方为：160–180g/L硫酸铜、15-20ml/L硫酸、40-50mg/L聚乙二醇、50mg/L氯化钠；
(10)热处理：将步骤(9)所得聚氨酯泡沫塑料样品放入电热炉中，由室温加热至600℃，升温速率5℃/min，在600℃下保温2.5h，然后缓慢冷却至室温，得到具有良好的孔结构，孔隙率高，镀层质量好，比表面积大，具有一定强度的金属泡沫铜。
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