CN113277875A - 双色陶瓷电子外观结构件、制备方法及其应用 - Google Patents

双色陶瓷电子外观结构件、制备方法及其应用 Download PDF

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CN113277875A
CN113277875A CN202110606298.0A CN202110606298A CN113277875A CN 113277875 A CN113277875 A CN 113277875A CN 202110606298 A CN202110606298 A CN 202110606298A CN 113277875 A CN113277875 A CN 113277875A
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周涛
雒文博
温兵
赵立宏
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Shenzhen Jingermei Precision Ceramic Technology Co ltd
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Abstract

本发明公开了一种双色陶瓷电子外观结构件及其制备方法和应用。该双色陶瓷电子外观结构件包括由陶瓷材料构成的多于一个孔的多孔陶瓷材料骨架，和填充在孔内的金属材料，其中陶瓷材料与金属材料在可见光范围内颜色不同。通过在多孔陶瓷内部浸渍颜色与陶瓷颜色不同的金属材料，从而实现了陶瓷色与金属色交替出现的斑点双色效果。通过调节孔径大小以及孔深，不仅能制备不同斑点小及密集度的双色效果，而且通过孔径、孔间距以及孔深的调节，能够保证金属与陶瓷的结合力，保证双色陶瓷电子外观结构件强度满足手机、手表等性能要求。

Description

双色陶瓷电子外观结构件、制备方法及其应用
技术领域
本发明涉及先进结构陶瓷电路领域，具体涉及一种双色陶瓷电子外观结构件、制备方法及其应用。
背景技术
随着手机通讯、智能手表等消费电子的迅猛发展，消费电子的外壳(背板)等结构件取得了长足的进步，也遇到新的问题。特别是5G对消费电子外壳(背板)的材质提出了更苛刻的要求。传统金属由于其屏蔽效果，对天线设计带来巨大的挑战，其不能用于5G外壳(背板)的制造，而塑料其先天的低强度、不耐磨限制了其在大尺寸屏幕、超薄领域的应用，另外随着消费审美的提高，传统单一的金属外壳和塑料材质的外壳(背板)也将难以打动消费者。
陶瓷具有高的强韧性、良好的硬度、高抗磨性，被广泛的应用于结构陶瓷和功能陶瓷领域，部分稳定氧化锆(TZP)已经通过粉末冶金方法制备了耐磨的手机外壳、手表表壳、表件和其它仪器零件，其也越来越被市场所接受，但陶瓷材料存在颜色单一，调色困难，通过现有喷涂着色工艺存在色彩层与陶瓷层结合力不足，容易脱落的问题，特别是现有的陶瓷制备技术难以制备对色、撞色、双色等时尚外观效果，来满足消费类电子对绚丽多彩外观的需求。
发明内容
有鉴于此，本发明针对现有陶瓷双色制备技术存在之缺失，目的之一是提供了一种双色陶瓷电子外观结构件，该外观件包括由陶瓷材料构成的多于一个孔的多孔陶瓷材料骨架，和填充在孔内的金属材料，其中陶瓷材料与金属材料在可见光范围内颜色不同。
优选的，陶瓷材料骨架的孔径在0.05mm～0.5mm之间，进一步优选的，陶瓷材料骨架的孔采用造孔剂制备得到。
优选的，陶瓷材料骨架的孔径在0.5mm～20mm之间，进一步优选的孔深小于孔深度方向的陶瓷材料骨架厚度的2/3。
优选的，陶瓷材料为氧化铝、氧化锆、碳化硅、氮化硅中一种或一种以上组合。
优选的，金属材料为熔点小于1100℃的合金材料。进一步优选的金属材料为铝合金。
本发明的目的之二是提供了一种双色陶瓷电子外观结构件制备方法，该制备方法包括以下步骤：
a)制备多于一个孔的多孔陶瓷材料骨架；
b)在多孔陶瓷材料骨架内浸渍金属材料；
c)去除表面金属层。
优选的，步骤b)中的浸渍为加压浸渍。
本发明的目的之三是提供了一种双色手机外壳、手表外壳，该双色手机外壳、手表外壳使用上述的双色陶瓷电子外观结构件制备得到。
本发明的有益效果：本发明公开了一种双色陶瓷电子外观结构件及其制备方法和应用。该双色陶瓷电子外观结构件包括由陶瓷材料构成的多于一个孔的多孔陶瓷材料骨架，和填充在孔内的金属材料，其中陶瓷材料与金属材料在可见光范围内颜色不同。通过在多孔陶瓷内部浸渍颜色与陶瓷颜色不同的金属材料，从而实现了陶瓷色与金属色交替出现的斑点双色效果。通过调节孔径大小以及孔深，不仅能制备不同斑点大小及密集度的双色效果，而且通过孔径、孔间距以及孔深的调节，能够保证金属与陶瓷的结合力，保证双色陶瓷电子外观结构件强度满足手机、手表等性能要求。
附图说明
图1为实施例1的双色陶瓷手机外壳产品局部外观图。
图2为实施例4的双色陶瓷产品结构示意图。
具体实施方式
下面对本发明作进一步详细描述，其中所用到原料和设备均为市售，没有特别要求。可以理解的是，此处所描述的具体实施例仅用于解释相关发明，而非对该发明的限定。
本发明提供了一种双色陶瓷电子外观结构件，该外观件包括由陶瓷材料构成的多于一个孔的多孔陶瓷材料骨架，和填充在孔内的金属材料，其中陶瓷材料与金属材料在可见光范围内颜色不同。通过在多孔陶瓷内部浸渍颜色与陶瓷颜色不同的金属材料，从而实现了陶瓷色与金属色交替出现的斑点双色效果。
作为本发明的一个实施例，陶瓷材料骨架的孔采用造孔剂制备得到，优选的陶瓷材料骨架的孔径在0.05mm～0.5mm之间，当孔洞在此范围内，可以实现不规则的细小斑点的金属异色点，特别是在旋转过程中，由于金属与陶瓷的折射率、反射率不同，会出现炫光的双色技术效果。
其中造孔剂为现有技术的造孔剂，根据需要的孔的大小和陶瓷的制备工艺选择，在本实施例中，优选的孔径小于0.1mm时，采用直径小于0.12mm的石墨造孔剂造孔，当所需陶瓷孔径在0.1mm～0.5mm之间时，采用直径在0.12mm～0.6mm的有机物塑料粒子造孔剂造孔，进一步的为了实现单分散均匀的孔洞，造孔剂使用前在石蜡煤油溶液中浸渍后烘干，然后使用，从而提升造孔剂在陶瓷粉体中的流动性，避免造孔剂聚集，造成孔不均匀，优选的石蜡煤油溶液中的石蜡含量为30％重量比。
作为本发明的一个实施例，陶瓷材料骨架的孔径在0.5mm～20mm之间。在本实施例中，由于孔径比较大，导致单个金属占比增大，对称结构更能产生美的效果，优选的孔为规则排列的三角形、正方形、正五边形、正六边形、圆形等具有规则结构，更优选的孔与孔的边距离在0.5mm～30mm之间，更优选的孔径越大，孔边距也更大，保证陶瓷骨架兼顾更好的强度和美观效果。进一步优选的孔深小于孔深度方向的陶瓷材料骨架厚度的2/3的盲孔，既能保证金属与陶瓷足够的接触深度，保证两者连接结合力，也通过盲孔设计，保证陶瓷骨架的足够强度，保证双色陶瓷电子外观结构件强度满足手机、手表等性能要求。
在本实施例中，陶瓷材料为氧化铝、氧化锆、碳化硅、氮化硅中一种或一种以上组合。
在本实施例中，金属材料为熔点小于1100℃的合金材料，例如锡合金、铝合金等，优选的金属材料为铝合金。
本发明提供了一种双色陶瓷电子外观结构件的制备方法，该制备方法包括以下步骤：
a)制备多于一个孔的多孔陶瓷材料骨架；其中陶瓷材料为铝、氧化锆、碳化硅、氮化硅中一种或一种以上组合。
作为本发明的一个实施例，当孔洞孔径为在0.05mm～0.5mm之间时，陶瓷材料骨架的孔采用造孔剂制备得到，本本实例中，造孔剂的含量为粉体重量比5％～15％，其中造孔剂为现有技术的造孔剂，根据需要的孔的大小和陶瓷的制备工艺选择，在本实施例中，优选的孔径小于0.1mm时，采用直径小于0.12mm的石墨造孔剂造孔，当所需陶瓷孔径在0.1mm～0.5mm之间时，采用直径在0.12mm～0.6mm的有机物塑料粒子造孔剂造孔，进一步的为了实现单分散均匀的孔洞，造孔剂使用前在石蜡煤油溶液中浸渍后烘干，从而提升造孔剂在陶瓷粉体中的流动性，避免造孔剂聚集，造成孔不均匀，且提升造孔剂与陶瓷粉体的粘结性，提升陶瓷坯体强度，在本实施例中优选的石蜡煤油溶液中的石蜡含量为30％重量比。
当造孔剂为石墨时，采用现有技术中的模压或者注塑工艺成型，而造孔剂为有机塑料粒子时，采用模压工艺成型得到多孔陶瓷材料骨架毛坯。
将成型得到的多孔陶瓷材料骨架毛坯烧结得到该多孔陶瓷材料骨架材料，优选的，为了实现均匀的开放多孔，利于后续浸渍，烧结致密度大于50％完成烧结，烧结温度比非多孔陶瓷的烧结温度低20～30℃，烧结时间小于2h，使得陶瓷颗粒与颗粒之间实现粘连，但孔洞不闭合。
在本制备方法中，当陶瓷材料骨架的孔径在0.5mm～20mm之间时，作为本发明的一个实施例，模具凹面加工0.6mm～24mm直径的规则排列的模针，模针高度小于模具深度的2/3，模针间隔0.6mm～36mm，模针的拔模斜度小于5°。其中模针的形状为三角形、正方形、正五边形、正六边形、圆形中的一种，优选的为圆形。通过现有技术中的模压成型脱模后经过脱脂、烧结得到该陶瓷材料骨架。
当陶瓷材料骨架的孔径在0.5mm～20mm之间时，作为本发明的一个实施例，采用现有技术中的闭孔陶瓷制备方法制备得到陶瓷坯体(致密度大于95％)。然后在陶瓷坯体表面采用CNC雕刻或者激光烧蚀得到孔洞，优选的孔深小于陶瓷材料骨架厚度的2/3，陶瓷孔为规则排列的三角形、正方形、正五边形、正六边形、圆形等具有规则结构的孔洞，孔与孔的边距离在0.5mm～30mm之间，经过CNC雕刻或者激光烧蚀得到孔洞后，即得到该多孔的陶瓷材料骨架。
b)在多孔陶瓷材料骨架内浸渍金属材料。将步骤a)得到的多孔陶瓷材料骨架放入浸渍炉内，加入需要浸渍的合金材料，加压加温直至金属完全填充到多孔陶瓷材料骨架内，随后随炉冷却得到复合陶瓷；
c)将复合陶瓷CNC铣或者其他现有技术的加工方式去除表面多余的金属层，露出陶瓷层与金属材料的浸渍层，即得到了该双色陶瓷。
在本实施例中优选的浸渍温度为高于合金熔点温度30～50℃，压力为0.5MPa～5MPa，其中加压所采用的的气氛为氮气气氛。在本实施例中优选的合金优选的合金材料为金属材料为熔点小于1100℃的合金材料，例如锡合金、铝合金等，更进一步优选的金属材料为铝合金，其中铝合金为铝硅合金、铝镁硅合金、铝镁合金。
本实施例中的双色手机外壳、手表外壳，使用上述的双色陶瓷电子外观结构件制备得到。
以下是本发明的实施例：
实施例1
称取市售D50约为0.06mm的石墨造孔剂2500g，投入1200g石蜡含量为30％重量比石蜡煤油溶液中球磨4h后出料在110℃烘干备用。
称取中值粒径D50约为0.8um的α相含量＞90％氮化硅4000g，称取1000g中值粒径D50约为1um的硅粉，再次称取经过处理的石墨造孔剂1050g，全部投入带有氧化锆球的搅拌磨中，再次再加入2kg乙醇和1kg去离子水后球磨搅拌3h后得到改性混合料。
称取350g高流动聚甲醛，30g聚丙烯和20g高密度聚乙烯加入密炼机中升温至165℃使其融化后将4000g改性混合料分多次加入密炼机中，然后闭合密炼机在165℃密炼3h后降温出料并将其粉碎得到喂料。将喂料注塑机的料斗内，设定5寸手机模具模温70℃，注塑机炮筒温度为180℃，注塑压力为110MPa注塑，高速注入模腔中，待模腔注满后保压1s，得到氮化硅注塑件。将该注塑件放置催化脱脂炉中0.8℃/min升温至120℃以硝酸蒸汽速率为0.20ml/min通入硝酸氮气混合气氛保温5h后降温完成脱脂。
将脱脂后的毛坯放入烧结炉中，从室温以1℃/min升温至255℃保温3h，再次以1℃/min升温至460℃保温5h，再次以1℃/min升温至650℃保温5h，以2℃/min升温速率升至1400℃，保温时间1h，得到致密度为55.8％的孔径约为0.05mm的氮化硅多孔陶瓷手机外壳毛坯。
将上述氮化硅多孔陶瓷手机外壳毛坯与Al-9Mg合金一起放入N2气氛保护熔渗炉中，设置压力1.5MPa，3℃/min升温速率升温至970℃，浸渍2h后随炉冷却得到铝镁氮化硅复合陶瓷，使用CNC铣刀工序将复合陶瓷表面的金属铝镁合金层去除，即得到该具有小斑点炫光效果的双色复合陶瓷(小斑点亮银色与陶瓷色结合)，为了达到更好的表面效果，采用金刚石抛光液粗抛、结合氧化硅抛光液精抛对其表面进行抛光处理，得到镜面效果双色手机外壳，该双色手机外壳由随机排列的金属点与围绕金属点周围的的陶瓷组成，具有非对称的炫光双色美感。
实施例2
称取市售D50约为0.6mm的聚甲醛微粒造孔剂100g，投入300g石蜡含量为30％重量比石蜡煤油溶液中球磨3h，加入后中值粒径D50约为1.1um的碳化硅2000g，700g煤油，再次球磨12h出料在90℃烘干得到造粒粉。
将造粒粉加入1.5寸手表外壳模具中，按1100kgf/cm2的压力压制15s后脱模，采用橡胶模具防水包装放入冷等静压机中80MPa压制40s后得到该双色手表外壳生坯。
从室温以1℃/min升温至230℃保温3h，再次以1℃/min升温至350℃保温5h，再次以1℃/min升温至460℃保温5h，再次以1℃/min升温至650℃保温5h，以2℃/min升温速率升至1410℃，保温时间2h，得到致密度为65.4％的碳化硅多孔陶瓷手机外壳毛坯。
将上述氮化硅多孔陶瓷手表外壳毛坯与Al-13Si-9Mg合金一起放入N2气氛保护熔渗炉中，设置压力0.8MPa，3℃升温至920℃，浸渍2h后随炉冷却得到铝镁硅碳化硅复合陶瓷，使用CNC铣刀工序将复合陶瓷表面的金属铝镁硅合金层去除，即得到该双色复合陶瓷(小斑点亮银色与陶瓷色结合)，为了达到更好的表面效果，采用金刚石抛光液粗抛、结合氧化硅抛光液精抛，对其表面进行抛光处理，得到镜面效果的双色手表外壳。
实施例3
称取中值粒径D50约为0.5um的氧化铝2000g，称取中值粒径D50约为0.6um的氧化镁15g，再称取150g石蜡含量为30％重量比石蜡煤油溶液，全部加入球磨罐中，然后再次加入800g煤油中球磨24h，出料在90℃烘干得到造粒粉。
将造粒粉加入6.7寸手机外壳模具中，该模具的凹面规则排列24mm直径圆柱形模针，模针高度为模具深度的2/3，模针与模针间隔36mm，模针的拔模斜度4°按800kgf/cm2的压力压制20s后脱模，采用橡胶模具防水包装放入冷等静压机中80MPa压制40s后得到该双色手表外壳生坯。
从室温以1℃/min升温至230℃保温3h，再次以1℃/min升温至350℃保温5h，再次以1℃/min升温至460℃保温5h，再次以1℃/min升温至650℃保温5h，以2℃/min升温速率升至1650℃，保温时间2h，得到氧化铝陶瓷手机外壳毛坯。
将上述氮化硅多孔陶瓷手表外壳毛坯与Al-12.6Si合金一起放入N2气氛保护熔渗炉中，设置压力3MPa，3℃/min升温至1050℃，浸渍2h后随炉冷却得到铝镁硅碳化硅复合陶瓷，使用CNC铣刀工序将复合陶瓷表面的金属铝硅合金层去除，即得到该圆形双色复合陶瓷(大斑点亮银色与陶瓷色结合)，为了达到更好的表面效果，采用金刚石结合氧化硅抛光液对其表面进行抛光处理，得到镜面效果的双色手机外壳，该双色手机外壳由规则的圆形金属与围绕金属的陶瓷组成，具有对称的双色美感。
实施例4
称取中值粒径D50约为0.35um的氧化锆1650g，称取中值粒径D50约为0.5um的氧化铝340g，再称取150g石蜡含量为30％重量比石蜡煤油溶液，全部加入球磨罐中，然后再次加入800g煤油中球磨24h，其中压力为1200kgf/cm2，时间为30s，压制完成后脱模，然后采用橡胶模具防水包装放入冷等静压机中85MPa压制30s后得到生坯，将生坯采用0.2mm的CNC铣刀加工规则排列的正六边形型盲孔，其中盲孔直径(正六边形外接圆)为0.6mm，孔深为0.8mm，孔与孔的边距离在0.6mm，加工完成后，该双色手机外壳生毛坯。
将生毛坯放入烧结炉中，从室温以1℃/min升温至230℃保温3h，再次以1℃/min升温至350℃保温5h，再次以1℃/min升温至460℃保温5h，再次以1℃/min升温至650℃保温5h，以2℃/min升温速率升至1600℃，保温时间2h，得到氧化锆氧化铝复合陶瓷手机外壳毛坯。
将上述氧化锆氧化铝复合陶瓷手机外壳毛坯与Sn-3Ag-0.5Cu合金一起放入N2气氛保护熔渗炉中，设置压力0.2MPa，3℃/min升温至300℃，浸渍1h后随炉冷却得到锡合金的氧化锆复合陶瓷，使用CNC铣刀工序将复合陶瓷表面的金属锡合金去除，即得到该正六边形双色复合陶瓷(大斑点亮银色与陶瓷色结合)，为了达到更好的表面效果，采用金刚石结合氧化硅抛光液对其表面进行抛光处理，得到镜面效果的双色手表外壳。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解，本申请中所涉及的发明范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离所述发明构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (10)

1.双色陶瓷电子外观结构件，其特征在于：包括由陶瓷材料构成的多于一个孔的多孔陶瓷材料骨架，和填充在孔内的金属材料，其中陶瓷材料与金属材料在可见光范围内颜色不同。
2.根据权利要求1所述的双色陶瓷电子外观结构件，其特征在于：陶瓷材料骨架的孔径在0.05mm～0.5mm之间。
3.根据权利要求2所述的双色陶瓷电子外观结构件，其特征在于：陶瓷材料骨架的孔采用造孔剂制备得到。
4.根据权利要求1所述的双色陶瓷电子外观结构件，其特征在于：陶瓷材料骨架的孔径在0.5mm～20mm之间。
5.根据权利要求4所述的双色陶瓷电子外观结构件，其特征在于：孔深小于孔深度方向的陶瓷材料骨架厚度的2/3。
6.根据权利要求1所述的双色陶瓷电子外观结构件，其特征在于：陶瓷材料为氧化铝、氧化锆、碳化硅、氮化硅中一种或一种以上组合，金属材料为熔点小于1100℃的合金材料。
7.根据权利要求6所述的双色陶瓷电子外观结构件，其特征在于：金属材料为铝合金。
8.双色陶瓷电子外观结构件制备方法，其特征在于，包括以下步骤：
a)制备多于一个孔的多孔陶瓷材料骨架；
b)在多孔陶瓷材料骨架内浸渍金属材料；
c)去除表面多余的金属层。
9.根据权利要求8所述的双色陶瓷电子外观结构件制备方法，其特征在于步骤b)中的浸渍为加压浸渍。
10.一种双色手机外壳、手表外壳，其特征在于：使用权利要求1～7所述的任一权利要求的双色陶瓷电子外观结构件制备得到。
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