CN111534806A - 一种硬质涂层及其制备方法与应用 - Google Patents
一种硬质涂层及其制备方法与应用 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 91
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 238000005516 engineering process Methods 0.000 claims abstract description 34
- 230000008021 deposition Effects 0.000 claims abstract description 29
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001771 vacuum deposition Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000007733 ion plating Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000010884 ion-beam technique Methods 0.000 abstract 1
- 150000001247 metal acetylides Chemical class 0.000 abstract 1
- 229910010037 TiAlN Inorganic materials 0.000 description 12
- 230000007547 defect Effects 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910008482 TiSiN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000942 confocal micrograph Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
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Abstract
本发明公开一种硬质涂层及其制备方法与应用。所述硬质涂层的制备技术为持续高功率磁控溅射技术;其中,平均功率密度>80W/cm2。本发明所述的镀膜技术为新型磁控溅射技术,具有高功率、高离化、高速沉积的特点。制备的涂层力学性能和沉积速率可以达到电弧离子镀水平,但离子束流中不含金属液滴,可有效降低涂层表面粗糙度,提高涂层致密度,进而大幅度提高其抗腐蚀和耐高温氧化性能。所述新型磁控溅射技术可以在基底表面制备多种二元或多元金属氮化物、氧化物、碳化物、硅化物以及硼化物等硬质涂层,具有广阔的应用价值。
Description
技术领域
本发明涉及真空涂层技术领域,尤其涉及一种硬质涂层及其制备方法与应用。
背景技术
精密模具、刀具具有广阔的应用市场,其表面一般附有硬质涂层以提高其使用寿命,但因其应用领域对尺寸精度要求高,故对其涂层表面粗糙度要求较高。此外,随着切削技术的发展,刀、模具的应用环境也发生着明显变化,其对耐腐蚀、耐高温的要求也逐渐提高,故硬质涂层也需要进一步提高致密度和涂层厚度,阻断腐蚀和氧化通道,并提高生产效率。
常规的硬质涂层制备技术是物理气相沉积(PVD)技术,根据辉光放电和弧光放电原理,分为磁控溅射技术和电弧离子镀,尤其是后者由于产生等离子体离化率高,配合偏压提高沉积离子能量,制备的硬质涂层力学性能远高于磁控溅射,故已被广泛应用,开发了TiN(C)、TiC、CrN(C)、TiAlN(C)、CrAlN(C)、TiSiN(C)、TiAlSiN、CrAlSiN、TiAlSiYN等数十种硬质涂层。然而,电弧放电区的高温会使来不及气化的金属液滴产生喷溅,沉积到涂层表面形成微米尺寸的“金属颗粒”,导致涂层表面粗糙度的增加,无法适应精密工件尺寸需求,同时涂层致密度明显下降,孔洞等宏观缺陷增加,影响力学性能和耐高温、腐蚀性能。1999年,高功率脉冲磁控溅射技术的提出使磁控溅射技术也实现了高比例离化,配合偏压后涂层力学性能得以明显提高,并达到甚至超越电弧离子镀涂层水平,但由于其不存在金属液滴喷溅,涂层表面粗糙度和致密度大大提高。但是由于其工作范围仍接近电弧放电区间,较高的峰值功率仍可能使放电出现“打弧”现象,且高于靶面高电位对金属离子的回吸现象,涂层沉积效率极低,不能满足生产需求。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种硬质涂层及其制备方法与应用,旨在解决现有采用高功率脉冲磁控溅射技术,其涂层沉积效率极低的问题。
本发明的技术方案如下:
一种硬质涂层的制备方法,其中,采用持续高功率磁控溅射技术制备得到涂层;其中,平均功率密度>80W/cm2。
可选地,所述的制备方法在真空镀膜系统中完成,具体包括:
步骤A、对基底进行等离子体清洗;
步骤B、在惰性气氛下,采用持续高功率磁控溅射技术对金属靶材进行辉光放电,在所述基底上沉积得到金属过渡层;
步骤C、向系统中通入反应性气体,在所述金属过渡层上沉积金属化合物涂层。
可选地,所述步骤A包括:
将系统抽至低于10-3Pa的压力,然后通入惰性气体,使系统获得0.1-2Pa的工作压力,通过等离子体放电产生等离子体对基底进行清洗刻蚀10-60min。
可选地,所述步骤B包括:
系统工作气压为0.1-2Pa,开启高功率磁控溅射电源对金属靶材进行辉光放电,并调整偏压对沉积离子进行加速,所述偏压为0.3-10kV,根据金属过渡层厚度调整沉积时间直至沉积完毕。
可选地,所述步骤C包括:
向系统中通入反应性气体,并降低偏压对金属化合物进行沉积,所述偏压为0.05-1kV,根据金属化合物涂层厚度调整沉积时间直至沉积完毕。
可选地,所述涂层材料为金属氮化物、金属氧化物、金属碳化物、金属硅化物、金属硼化物中的一种。
可选地,所述金属靶材选自Cr、Ti、Al、B、Y、Ta、Ni、V、Mo、Cu、Zn、Mg、Zr、C、Si中的任一金属材料或中的任两种以上金属材料组成的金属合金。
可选地,所述反应性气体选自氮气、氧气、乙炔、甲烷、硅烷、硼烷中的一种。
一种硬质涂层,其中,采用本发明所述的硬质涂层的制备方法制备得到。
一种本发明所述的硬质涂层在精密模具、刀具中的应用。
有益效果:本发明提供了一种硬质涂层的制备方法,所述硬质涂层制备方法为持续高功率磁控溅射技术,其具有沉积离子离化率高、沉积效率高的特点,其制备的硬质涂层力学性能达到甚至超过电弧离子镀制备硬质涂层,但表面粗糙度和涂层致密度远好于电弧离子镀技术,从而使得硬质涂层可以满足对尺寸精度要求更高的精密刀、模具领域,同时较高的涂层致密度还可以在腐蚀、高温环境中阻断腐蚀或氧化通道,提高这种特殊环境下的使用寿命。
附图说明
图1是实施例1中制备的TiAlN涂层的截面SEM图。
图2是实施例1中制备的TiAlN涂层的正面SEM图。
图3是实施例1中制备的TiAlN涂层的表面粗糙度。
图4是实施例1中制备的TiAlN涂层的硬度。
具体实施方式
本发明提供一种硬质涂层及其制备方法与应用,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。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。
本发明实施例提供一种硬质涂层的制备方法,其中,采用持续高功率磁控溅射技术制备得到涂层;其中,平均功率密度>80W/cm2。
本发明实施例提出一种新型的磁控溅射技术制备涂层,该新型磁控溅射技术为持续高功率磁控溅射技术,是一种高强度辉光放电技术。综合了磁控溅射表面光滑、无颗粒缺陷和电弧离子镀金属离化率高、膜基结合力强、力学性能好的优点,可在控制涂层微结构的同时获得优异的膜基结合力,在降低涂层内应力及提高涂层致密性、均匀性等方面具有显著的技术优势,能够满足沉积涂层在众多苛刻且复杂服役条件下长期稳定工作的性能要求。
本发明实施例采用新型的磁控溅射技术制备涂层,其具有沉积速率快、高离化、高功率的特点、且获得的涂层具有低表面粗糙度、高致密度的特点。与现有普遍采用的高功率脉冲磁控溅射技术不同,本发明实施例持续高功率磁控溅射技术的平均功率密度远高于高功率脉冲磁控溅射技术,其工作平均功率密度>80W/cm2,占空比不低于30%,远高于高功率脉冲磁控溅射的占空比(5%以下),其放电靶材可以选自Cr、Ti、Al、B、Y、Ta、Ni、V、Mo、Cu、Zn、Mg、Zr、C、Si等中的任一金属材料或中的任两种以上金属材料组成的金属合金,其放电时金属材料离化率与沉积速率根据材料不同而不同,一般分别>50%和>50nm/min。
在一种实施方式中,所述磁控溅射技术可以使用直流放电、脉冲放电、射频放电、中频放电等工作模式,可以是单极放电、双极放电。进一步地,在使用脉冲放电时,占空比不低于30%,远高于高功率脉冲脉冲磁控溅射的5%。
在一种实施方式中,所述的硬质涂层的制备方法,在真空镀膜系统中完成,具体包括:
步骤A、对基底进行等离子体清洗;
步骤B、在惰性气氛下,采用持续高功率磁控溅射技术对金属靶材进行辉光放电,在所述基底上沉积得到金属过渡层;
步骤C、向系统中通入反应性气体,在所述金属过渡层上沉积金属化合物涂层。
在一种实施方式中,所述步骤A包括:
将系统抽至低于10-3Pa的压力,然后通入惰性气体,使系统获得0.1-2Pa的工作压力,通过等离子体放电产生等离子体对基底进行清洗刻蚀10-60min。
在一种实施方式中,所述步骤B包括:
系统工作气压为0.1-2Pa,开启高功率磁控溅射电源对金属靶材进行辉光放电,并调整偏压对沉积离子进行加速,所述偏压可以是直流偏压、脉冲偏压、射频偏压等模式,其幅值为0.3-10kV(如1kV),根据金属过渡层厚度调整沉积时间直至金属过渡层沉积完毕,沉积所述金属过渡层可以使最终获得的涂层具有较高的结合力。在一种实施方式中,所述沉积的时间为2-10min。
在一种实施方式中,所述步骤C包括:
向系统中通入反应性气体,并降低偏压对金属化合物进行沉积,所述偏压可以是直流偏压、脉冲偏压、射频偏压等模式,其幅值为0.05-1kV,根据金属化合物涂层厚度调整沉积时间直至金属化合物涂层沉积完毕。在一种实施方式中,为了降低内应力,提高金属化合物涂层与基底的结合力,偏压降低到100V。
在一种实施方式中,所述反应性气体选自氮气、氧气、乙炔、甲烷、硅烷、硼烷等中的一种。对应的,最终溅射得到的所述涂层材料为由金属靶材或金属合金靶材和反应性气体中活性元素组合而成的二元或多元金属氮化物、二元或多元金属氧化物、二元或多元金属碳化物、二元或多元金属硅化物、二元或多元金属硼化物等中的一种。
本发明实施例提供一种硬质涂层,其中,采用本发明实施例所述的硬质涂层的制备方法制备得到。
本发明实施例提供一种如上所述的硬质涂层在精密模具、刀具中的应用。
本发明实施例所述涂层表面粗糙度<100nm,具有致密度高、孔洞等宏观缺陷少的特点,可应用于精密模具、刀具等高尺寸精度领域,并能进一步提高涂层使用寿命。
下面通过具体的实施例对本发明作详细说明。
实施例:TiAlN涂层制备
先在真空室内装上纯度高于99.9%的TiAl靶材,将真空室抽至低于10-4Pa的压力,然后通入惰性气体,使真空室获得0.1-2Pa的工作压力,通过等离子体放电产生等离子体对基体工件进行清洗刻蚀30min。随后采用持续高功率磁控溅射在平均功率密度140W/cm2情况下对TiAl靶材进行高强度辉光放电,并调整偏压对沉积离子进行加速,偏压为直流偏压,其幅值为1kV,调整沉积时间为3min。然后降低直流偏压至100V制备TiAlN层。随后通入氮气和惰性气体体积比例为1:5的混合气体进行反应溅射,整个涂层沉积时间为20min,即可完成厚度均一、高硬度的TiAlN硬质涂层的制备。
对实施例制备的TiAlN涂层进行表征测试,如图1截面SEM结果所示,获得的TiAlN涂层厚度约为9μm,具有明显的细化的致密结构,可计算出沉积速率高达450nm/min,这可归于电离速率和离子轰击效应的增加。图2中正面SEM形貌可以看出涂层表面呈现出更致密和波纹状的形貌,这主要是由持续高功率磁控溅射技术产生的高离子能量离子轰击和大电离速率引起的沉积造成的。由于晶体结构的致密化,涂层表面的高度差和表面粗糙度(Ra)分别为1.2μm和22.4nm,如图3中的3D共聚焦显微照片所示。对该涂层进行硬度测试,结果展示该技术制备的TiAlN涂层硬度可高达33.2GPa,可与目前常用的AIP方法相媲美,如图4所示。
综上所述,本发明提供了一种适用于精密模具的持续高功率磁控溅射技术。该技术溅射产生的离子沉积速率明显优于传统磁控溅射技术该技术,制备的硬质涂层具有优异的性能,表现出高硬度,低表面粗糙度,低残余应力,同时具有杰出的耐磨和耐腐蚀性能。对实现制备高质量高标准精密模具具有广阔的应用价值。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一种硬质涂层的制备方法,其特征在于,采用持续高功率磁控溅射技术制备得到涂层;其中,平均功率密度>80W/cm2。
2.根据权利要求1所述的硬质涂层的制备方法,其特征在于,所述的制备方法在真空镀膜系统中完成,具体包括:
步骤A、对基底进行等离子体清洗;
步骤B、在惰性气氛下,采用持续高功率磁控溅射技术对金属靶材进行辉光放电,在所述基底上沉积得到金属过渡层;
步骤C、向系统中通入反应性气体,在所述金属过渡层上沉积金属化合物涂层。
3.根据权利要求2所述的硬质涂层的制备方法,其特征在于,所述步骤A包括:
将系统抽至低于10-3Pa的压力,然后通入惰性气体,使系统获得0.1-2Pa的工作压力,通过等离子体放电产生等离子体对基底进行清洗刻蚀10-60min。
4.根据权利要求2所述的硬质涂层的制备方法,其特征在于,所述步骤B包括:
系统工作气压为0.1-2Pa,开启高功率磁控溅射电源对金属靶材进行辉光放电,并调整偏压对沉积离子进行加速,所述偏压为0.3-10kV,根据金属过渡层厚度调整沉积时间直至沉积完毕。
5.根据权利要求2所述的硬质涂层的制备方法,其特征在于,所述步骤C包括:
向系统中通入反应性气体,并降低偏压对金属化合物进行沉积,所述偏压为0.05-1kV,根据金属化合物涂层厚度调整沉积时间直至沉积完毕。
6.根据权利要求1所述的硬质涂层的制备方法,其特征在于,所述涂层材料为金属氮化物、金属氧化物、金属碳化物、金属硅化物、金属硼化物中的一种。
7.根据权利要求2所述的硬质涂层的制备方法,其特征在于,所述金属靶材选自Cr、Ti、Al、B、Y、Ta、Ni、V、Mo、Cu、Zn、Mg、Zr、C、Si中的任一金属材料或中的任两种以上金属材料组成的金属合金。
8.根据权利要求2所述的硬质涂层的制备方法,其特征在于,所述反应性气体选自氮气、氧气、乙炔、甲烷、硅烷、硼烷中的一种。
9.一种硬质涂层,其特征在于,采用权利要求1-8任一项所述的硬质涂层的制备方法制备得到。
10.一种权利要求9所述的硬质涂层在精密模具、刀具中的应用。
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