CN111826620A - 抑制元素扩散、防黏着的玻璃模压模具梯度涂层 - Google Patents
抑制元素扩散、防黏着的玻璃模压模具梯度涂层 Download PDFInfo
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Abstract
本发明属于仅含无机材料的玻璃模具涂层技术领域,具体涉及一种抑制元素扩散、防黏着的玻璃模压模具梯度涂层。所述玻璃模压模具梯度涂层,包括与基体粘结Cr结合层、CrN中间过渡层及CrxWyN(1‑x‑y)表面层,且0.15<x<0.4,0.2≤y<0.45。该梯度涂层具有优异的抑制裂纹扩散性能及防黏着性能。
Description
技术领域
本发明属于仅含无机材料的玻璃模具涂层技术领域,具体涉及一种抑制元素扩散、防黏着的玻璃模压模具梯度涂层。
背景技术
玻璃精密模压成型是一种高效率、环保的先进光学元件制造技术,近年来得到了飞速发展(“玻璃精密模压成形的研究进展”,龚峰等,光学精密工程,2018年第26卷第6期,第1380页,摘要,公开日2018年06月30日)。光学玻璃模压成型技术利用的是玻璃从熔融态向固态转化中连续可逆的热加工性质,在玻璃的转变温度Tg附近,无氧条件下,对玻璃和模具进行加温加压,一次性将光学玻璃模压成型。由于光学玻璃模压成型法摒弃了传统的粗磨、精磨、抛光以及定心磨边等工序,直接一次成型,大大节省了材料、时间、设备及人力,且能模压出复杂形状的光学元件,尤其是在非球面光学玻璃零件和小型、微型光学元件制造方面,有着广阔的应用前景(“光学玻璃模压成型技术”,王丽荣,科技传播,2012年第7期,第105页,公开日2012年07月23日)。因此,光学玻璃模压成型技术特别适用于批量生产各种具有特殊结构的高精度中小口径透镜,尤其是那些用传统加工手段难以实现的光学玻璃元件,如小口径薄型透镜、高次非球面镜片、微透镜阵列、衍射光学元件和自由曲面光学元件等。由于光学玻璃模压成型技术能够大批量生产精密的非球面或自由曲面光学元件,推进了非球面玻璃光学元件的应用(“精密模压技术于光学玻璃的制造研究”,吴澄,市场周刊:理论研究,2012年第2期,第111页,公开日2012年06月01日)。
模具的使用寿命及表面质量一直限制着玻璃精密模压技术的发展。其主要原因在于,在玻璃制品的成型过程中,模具频繁的与高温的熔融玻璃接触,发生氧化反应、热疲劳、动态磨损、黏着等协同作用(“玻璃模具材料的发展和应用”,韦玉屏等,机械设计与制造,2008年第3期,第201页,公开日2008年03月31日;“新玻璃模具材料的开发与应用”,肖明,玻璃与搪瓷,2006年第34卷第2期,第19页,公开日2006年04月30日)。此外,模具表面质量对玻璃元件的成型质量息息相关。因此,玻璃模压模具需要具备优异的耐高温、抗氧化、抗黏着、抗热疲劳、耐腐蚀、耐磨损性能。
因此,为延长模具的使用寿命,改善光学元件的质量,应采用在模具表面镀膜的方式来提高玻璃模压模具的耐高温、抗氧化、抗黏着、抗热疲劳、耐腐蚀、耐磨损等方面的性能。但是,由于缺少模具涂层的使用,我国所用的加工方式依然以传统的数控切削、磨削、抛光等方法为主,急需寻找一种抑制元素扩散、防黏着的玻璃模压模具涂层。
发明内容
有鉴于此,本发明的目的在于提供一种玻璃模压模具梯度涂层,该梯度涂层在抑制元素扩散方面及防黏着性能方面优异,且成本低廉。
为实现上述目的,本发明的技术方案为:
玻璃模压模具梯度涂层,包括与基体链接的Cr结合层、CrN中间过渡层及表面CrxWyN(1-x-y)层,且0.15<x<0.4,0.2≤y<0.45。
进一步,所述Cr结合层的厚度为50-100nm,CrN中间过渡层厚度为150-300nm,表面CrxWyN(1-x-y)层厚度为1300-1500nm。
进一步,所述梯度涂层在1000℃的高温润湿角为125°。
进一步,所述基体为掺杂8%Co的碳化钨模具,以质量百分比计。
本发明的目的之二在于保护所述玻璃模压模具梯度涂层的制备方法,包括以下步骤:
A.在真空、惰性气体的气氛下,对待沉积基体和靶材进行溅射清洗;
B.在惰性气体、真空气氛下,采用Cr靶和W靶在经过步骤A处理的待沉积基体表面依次沉积Cr结合层、CrN中间过渡层和CrxWyN(1-x-y)层。
进一步,所述惰性气体为氩气、氮气或二者的混合物。
进一步,步骤A中,流量为100-180sccm,溅射时真空度为0.4-0.5Pa,基体预热至200-400℃,优选300-400℃,沉积偏压为-30~-70V,基体溅射清洗时间为30-120分钟,优选60-120分钟,靶材溅射清洗时间为1-5分钟,优选2-5分钟。
进一步,步骤B中,Cr结合层的沉积条件为:真空室基底真空度3×10-3-6×10-3Pa,工作气体为氩气,沉积处理时反应室真空度为0.4-0.5Pa,沉积偏压为-30~-70V,Cr靶功率为3-6kW,沉积温度为300-400℃,沉积时间为2-5分钟。
进一步,步骤B中,CrN中间过渡层的沉积条件为:工作气体为氩气、氮气混合气体,溅射时真空度为0.4-0.5Pa,沉积偏压为-30~-70V,Cr靶功率为3-6kW,沉积温度为300-400℃,沉积时间为20-40分钟。
进一步,步骤B中,CrxWyN(1-x-y)层的沉积条件为:工作气体为氩气、氮气混合气体,溅射时真空度为0.4-0.5Pa,沉积偏压为-30~-70V,Cr靶功率为3-6kW,W靶功率为4-6kW,沉积温度为300-400℃,沉积时间为60-100分钟。
进一步,所述沉积为等离子增强磁控溅射。
进一步,在步骤A之前,还包括以下步骤:
(1)对待沉积基体进行抛光处理;
(2)将经过抛光处理的待沉积基体在去离子水和/或丙酮和/或乙醇中进行超声清洗。
进一步,溅射清洗靶材时,靶材用衬板遮挡。
本发明的目的之三在于保护所述玻璃模压模具梯度涂层在制备玻璃模压模具中的应用。
本发明的目的还在于保护一种玻璃模压模具,所述模具包含玻璃模压模具梯度涂层,所述梯度涂层包括与基体链接的Cr结合层、CrN中间过渡层及表面CrxWyN(1-x-y)层,且0.15<x<0.4,0.2≤y<0.45。
进一步,所述基体为掺杂8%Co的碳化钨模具,以质量百分比计。
本发明的有益效果在于:
本发明的梯度涂层表面形貌呈现为大小不一的菜花状团簇,表面呈现细小裂纹及孔洞等缺陷。通过涂层断面可观察到涂层生长方式为柱状晶体结构;各层之间结合紧密。
本发明的梯度涂层表现出优异的机械性能,满足玻璃模压涂层硬度使用标准。
本发明的涂层表面粗糙低,具有优异的表面质量,满足精密玻璃模压涂层表面质量的使用要求。
本发明的梯度涂层具有优异的耐高温、防黏着特性,该梯度涂层经过热压成型后的玻璃及模具涂层表面无明显变化,玻璃体无变色反应、无气泡产生,表面未出现黏着现象,涂层表面与玻璃接触的部分未发生剥落。
本发明的梯度涂层抗高温及抗黏着性能优异。
本发明的梯度涂层抑制裂纹扩展方面性能优异。
本发明的梯度涂层成本低。
附图说明
图1为本发明的梯度涂层的结构示意图;
图2为实施例1制得的梯度涂层的SEM表面及断面图,其中,2A为涂层的表面图,2B为涂层的断面图;
图3为实施例1制得的梯度涂层的硬度测试结果;
图4为实施例1制得的梯度涂层的表面粗糙度测试结果;
图5为实施例1制得的梯度涂层的模压后梯度涂层及玻璃表面形貌图;
图6为实施例1制得的梯度涂层表面元素检测结果图(即能谱图);
图7为实施例1制得的梯度涂层的物相结构检测结果图;
图8为实施例1制得的梯度涂层的高温润湿性能检测结果图;
图9为梯度涂层的抑制裂纹扩展检测结果图;其中,9A为实施例1制得的梯度涂层的抑制裂纹扩展检测结果图;9B为对比例1制得的梯度涂层的抑制裂纹扩展检测结果图;9C为对比例2制得的涂层的抑制裂纹扩展检测结果图。
具体实施方式
所举实施例是为了更好地对本发明的内容进行说明,但并不是本发明的内容仅限于所举实施例。所以熟悉本领域的技术人员根据上述发明内容对实施方案进行非本质的改进和调整,仍属于本发明的保护范围。
实施例1
玻璃模压模具梯度涂层,其具体制备步骤为:
(1)镀前处理
对待沉积基体(掺杂8%Co的碳化钨模具,以质量百分比计)进行机械研磨抛光,然后依次在去离子水、丙酮、乙醇溶液中进行超声波震荡清洗,各20min,清洗后样品置于烘箱中于80℃烘干30min;
(2)溅射清洗
将经镀前处理的待沉积基体装入真空室,真空室进行预抽真空,基底真空度为5×10-3Pa,并在此过程中对真空室进行加热,加热温度至300℃。通入高纯氩气(纯度>99.99%,由外包装获知)对基体和靶材进行离子溅射刻蚀清洗,流量为120sccm,溅射时真空度为0.4Pa,沉积偏压为-70V,基体溅射清洗时间为60分钟,靶材溅射清洗时间为5分钟;溅射清洗靶材时,靶材用衬板遮挡;
(3)沉积Cr结合层
采用等离子增强磁控溅射系统,将上述待沉积基体预先沉积Cr结合层;真空室基底真空度5×10-3Pa,工作气体为高纯氩气(纯度>99.99%,由外包装获知),所用靶材为一块高纯Cr靶(纯度>99.9%,由外包装获知),溅射时真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为5kW,沉积温度为300℃,沉积时间为5分钟。
(4)沉积CrN中间过渡层
采用等离子增强磁控溅射系统,将上述沉积Cr结合层基体表面再沉积CrN过渡层;工作气体为高纯氩气(纯度>99.99%,由外包装获知)、高纯氮气(纯度>99.99%,由外包装获知)混合气体,所用靶材为一块高纯Cr靶(纯度>99.9%,由外包装获知),溅射时保持真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为5kW,沉积温度为300℃,沉积时间为20分钟。
(5)沉积CrxWyN(1-x-y)表面层
采用等离子增强磁控溅射系统,将上述沉积Cr结合层及CrN过渡层基体表面再沉积CrxWyN(1-x-y)表面层;工作气体为高纯氩气(纯度>99.99%,由外包装获知)、高纯氮气(纯度>99.99%,由外包装获知)混合气体,所用靶材为一块高纯Cr靶(纯度为99.9%,由外包装获知)和一块高纯W靶(纯度为99.6%,由外包装获知),溅射时保持真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为3kW,W靶功率为4kW,沉积温度为300℃,沉积时间为60分钟。
对比例1
玻璃模压模具梯度涂层,其具体制备步骤为:
(1)镀前处理
对待沉积基体(掺杂8%Co的碳化钨模具,以质量百分比计)进行机械研磨抛光,然后依次在去离子水、丙酮、乙醇溶液中进行超声波震荡清洗,各20min,清洗后样品置于烘箱中于80℃烘干30min;
(2)溅射清洗
将经镀前处理的待沉积基体装入真空室,真空室进行预抽真空,基底真空度为5×10-3Pa,并在此过程中对真空室进行加热,加热温度至300℃。通入高纯氩气(纯度>99.99%,由外包装获知)对基体和靶材进行离子溅射刻蚀清洗,流量为120sccm,溅射时真空度为0.4Pa,沉积偏压为-70V,基体溅射清洗时间为60分钟,靶材溅射清洗时间为5分钟;溅射清洗靶材时,靶材用衬板遮挡;
(3)沉积Cr结合层
采用磁控溅射系统,将上述待沉积基体预先沉积Cr结合层;真空室基底真空度5×10-3Pa,工作气体为高纯氩气(纯度>99.99%,由外包装获知),所用靶材为一块高纯Cr靶(纯度>99.9%,由外包装获知),溅射时真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为5kW,沉积温度为300℃,沉积时间为5分钟。
(4)沉积CrxWyN(1-x-y)表面层
采用磁控溅射系统,将上述沉积Cr结合层基体表面再沉积CrxWyN(1-x-y)表面层;工作气体为高纯氩气(纯度>99.99%,由外包装获知)、高纯氮气(纯度>99.99%,由外包装获知)混合气体,所用靶材为一块高纯Cr靶(纯度为99.9%,由外包装获知)和一块高纯W靶(纯度为99.6%,由外包装获知),溅射时保持真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为3kW,W靶功率为4kW,沉积温度为300℃,沉积时间为60分钟。
对比例2
玻璃模压模具涂层,其具体制备步骤为:
(1)镀前处理
对待沉积基体(掺杂8%Co的碳化钨模具,以质量百分比计)进行机械研磨抛光,然后依次在去离子水、丙酮、乙醇溶液中进行超声波震荡清洗,各20min,清洗后样品置于烘箱中于80℃烘干30min;
(2)溅射清洗
将经镀前处理的待沉积基体装入真空室,真空室进行预抽真空,基底真空度为5×10-3Pa,并在此过程中对真空室进行加热,加热温度至300℃。通入高纯氩气(纯度>99.99%,由外包装获知)对基体和靶材进行离子溅射刻蚀清洗,流量为120sccm,溅射时真空度为0.4Pa,沉积偏压为-70V,基体溅射清洗时间为60分钟,靶材溅射清洗时间为5分钟;溅射清洗靶材时,靶材用衬板遮挡;
(3)沉积CrxWyN(1-x-y)层
采用磁控溅射系统,将上述待沉积基体沉积CrxWyN(1-x-y)表面层;工作气体为高纯氩气(纯度>99.99%,由外包装获知)、高纯氮气(纯度>99.99%,由外包装获知)混合气体,所用靶材为一块高纯Cr靶(纯度为99.9%,由外包装获知)和一块高纯W靶(纯度为99.6%,由外包装获知),溅射时保持真空度为0.4Pa,沉积偏压为-30V,Cr靶功率为4kW,W靶功率为4kW,沉积温度为300℃,沉积时间为60分钟。
性能检测
对实施例1制得的涂层进行涂层表面及断面形貌、硬度、表面粗糙度、模压、涂层表面元素、涂层物相结构、高温润湿性能等性能检测,结果如图2-图8所示;
同时,对实施例1和对比例1制得的梯度涂层、对比例2制得的涂层进行抑制裂纹扩展方面性能检测,结果图9所示,其中图9A为实施例1制得的梯度涂层,图9B为对比例1制得的梯度涂层,图9C为对比例2制得的涂层;
其中,图2为实施例1所得梯度涂层的SEM表面及断面图,其中,2A为涂层的表面图,2B为涂层的断面图;图3为硬度测试结果,其中横坐标为压入深度,纵坐标为压入载荷;图4为表面粗糙度测试结果;图5为模压测试结果;图6为梯度涂层表面元素检测结果图(即能谱图);图7为梯度涂层的物相结构检测结果图;图8为高温润湿性能检测结果图;
其中,硬度的检测方法为:采用纳米压痕仪进行测试,测试模式为连续刚度法(CSM),其中,为排除基体对测量结果的影响,纳米压痕深度设定为100nm,为保证数据准确可靠,在样品上选择5个不同区域,对得到的硬度及弹性模量取平均值;
表面粗糙度的检测方法为:采用原子力显微镜进行测试,测试样品区域为2×2μm;
模压的检测方法为:利用自行设计的光学非球面玻璃模压成型设备(申请号:CN201710124489.7;公开号:CN106946441A),对BK7光学玻璃进行模压;其中,模压力为0.5kN,模压温度为650℃;对模压后模具涂层及BK7玻璃表面形貌颜色进行观察;
涂层表面元素的检测方法为:利用场发射扫描电子显微镜(FESEM)自带的X射线能谱仪(EDS)对涂层表面元素进行定性分析;
物相相结构的检测方法为:采用X射线衍射仪(XRD)进行检测,为避免基体因素的影响采用小角衍射的方式对涂层晶体结构进行分析;
高温润湿性能的检测方法为:采用通管滴落法在1000℃下进行高温润湿实验,真空度为5×10-3Pa,玻璃材料BK7光学玻璃;
抑制裂纹扩展性能的检测方法为:使用洛氏硬度仪对待测涂层抑制裂纹扩展的能力进行测试,采用圆锥角120°金刚石压头对涂层施加60N的载荷。对压后涂层表面使用超景深显微镜观察。
由图2可知,实施例1制得的梯度涂层表面形貌呈现为大小不一的菜花状团簇,表面呈现细小裂纹及等缺陷。通过涂层断面可观察到涂层生长方式为柱状晶体结构,Cr层厚度为96nm,CrN层厚度为297nm,CrxWyN(1-x-y)层厚度为1375nm;各层之间结合紧密。
由图3可知,实施例1制得的梯度涂层的硬度为16GPa。由此证明,本发明的梯度涂层表现出优异的机械性能,满足玻璃模压涂层使用标准。
由图4可知,实施例1制得的梯度涂层表面粗糙度为4nm,表现出优异的表面质量,可用于精密玻璃模压涂层使用。
由5可知,实施例1制得的梯度涂层经过热压成型后的玻璃及模具涂层表面无明显变化,玻璃体无变色反应、无气泡产生,表面未出现黏着现象,涂层表面与玻璃接触的部分未发生剥落。由此证明,本发明的梯度涂层具有优异的耐高温、防黏着特性。
由图6可知,实施例1制得的梯度涂层表面主要元素为Cr元素、W元素及N元素。
由图7可知,实施例1制得的梯度涂层表面层具有明显的CrN相,主要晶体取向为(111)、(200)、(220)、(311)、(222)取向,且表面层中Cr元素质量百分含量为35%,W元素的质量百分含量为20%,N元素质量百分含量为45%。
由图8可知,实施例1制得的梯度涂层在环境温度为1000度、真空度为5×10-3Pa时,熔融光学玻璃与梯度涂层表面未发生铺展,熔融玻璃与涂层的高温接触角为125°。由此证明,本发明的梯度涂层抗高温及抗黏着性能优异。
由图9可知,与对比例1的梯度涂层和对比例2的涂层相比,实施例1的梯度涂层的裂纹数量得到了显著降低。由此证明,本发明的梯度涂层对抑制裂纹扩展方面性能得到了显著提高。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.玻璃模压模具梯度涂层,其特征在于,包括与基体粘结的Cr结合层、CrN中间过渡层及CrxWyN(1-x-y)表面层,且0.15<x<0.4,0.2≤y<0.45。
2.根据权利要求1所述的玻璃模压模具梯度涂层,其特征在于,所述Cr结合层的厚度为50-100nm,CrN中间过渡层厚度为150-300nm,表面CrxWyN(1-x-y)层厚度为1300-1500nm。
3.根据权利要求1或2所述的玻璃模压模具梯度涂层,其特征在于,所述梯度涂层在1000℃的高温润湿角为125°。
4.权利要求1-3任一项所述玻璃模压模具梯度涂层的制备方法,其特征在于,包括以下步骤:
A.在真空、惰性气体的气氛下,对待沉积基体和靶材进行溅射清洗;
B.在惰性气体、真空气氛下,采用Cr靶和W靶在经过步骤A处理的待沉积基体表面依次沉积Cr结合层、CrN中间过渡层和CrxWyN(1-x-y)层。
5.根据权利要求4所述制备方法,其特征在于,所述惰性气体为氩气、氮气或二者的混合物。
6.根据权利要求4或5所述制备方法,其特征在于,步骤A中,流量为100-180sccm,溅射时真空度为0.4-0.5Pa,基体预热至200-400℃,沉积偏压为-30~-70V,基体溅射清洗时间为30-120分钟,靶材溅射清洗时间为1-5分钟。
7.根据权利要求4或5所述制备方法,其特征在于,步骤B中,Cr结合层的沉积条件为:真空室基底真空度3×10-3~6×10-3Pa,工作气体为氩气,沉积处理时反应室真空度为0.4-0.5Pa,沉积偏压为-30~-70V,Cr靶功率为3-6kW,沉积温度为300-400℃,沉积时间为2-5分钟。
8.根据权利要求4、5或6所述制备方法,其特征在于:步骤B中,CrN中间过渡层的沉积条件为:工作气体为氩气、氮气混合气体,溅射时真空度为0.4-0.5Pa,沉积偏压为-30~-70V,Cr靶功率为3-6kW,沉积温度为300-400℃,沉积时间为20-40分钟。
9.权利要求1-3任一项所述玻璃模压模具梯度涂层在制备玻璃模压模具中的应用。
10.玻璃模压模具,其特征在于,包含玻璃模压模具梯度涂层,所述梯度涂层包括与基体粘结的Cr结合层、CrN中间过渡层及CrxWyN(1-x-y)表面层,且0.15<x<0.4,0.2≤y<0.45。
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