CN107937876A - 一种具有硬度梯度层支撑的TiAlN复合超硬涂层及其制备方法 - Google Patents
一种具有硬度梯度层支撑的TiAlN复合超硬涂层及其制备方法 Download PDFInfo
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- 229910010037 TiAlN Inorganic materials 0.000 title claims abstract description 44
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- 239000011248 coating agent Substances 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 19
- 238000005516 engineering process Methods 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 8
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- 229910000851 Alloy steel Inorganic materials 0.000 claims description 4
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- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
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- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910010038 TiAl Inorganic materials 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 3
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- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明公开一种具有硬度梯度层支撑的TiAlN复合超硬涂层及其制备方法，所述超硬涂层为自下到上分别为基体材料、扩伸层及沉积层的三层结构；所述基体材料为导电材料；所述的扩伸层为等离子氮碳共渗层；所述的沉积层为氮铝钛涂层。致密TiAlN超硬膜层赋予基材充分的耐磨能力；等离子氮碳共渗层具有硬度梯度，可显著增强对表面硬脆层的支撑，有效地提升TiAlN超硬膜层的承载能力。并且，氮碳还增大了零件表层的残余应力值，赋予了其更大的疲劳抗力。同时，氮碳共渗层的氮化物、碳化物在热物理性能上与TiAlN膜层更匹配，膜/基界面更融合，因而使膜层具有更牢固、可靠的结合力，也具有更高的抗热疲劳性能。
Description
技术领域
本发明涉及复合超硬涂层的技术领域，特别是涉及一种具有硬度梯度层支撑的TiAlN复合超硬涂层及其制备方法。
背景技术
随着现代航空技术不断发展，为提高发动机推重比，其工作温度也逐步升高，目前先进军用发动机的压气机出口温度已达到700℃，燃烧室及加力燃烧室的工作温度接近2000℃,涡轮进口温度超过1700℃。图1是航空发动机涡轮叶片工作温度演变曲线图。然而，发动机热端部位的零件所用的基体材料的性能和所能承受的温度有限，不可能完全满足要求，为了提高其寿命、可靠性和抗疲劳等性能，使用多种涂层是种有效方法。从外部到内部设置低温端到高温端，各层分别发挥着防护、密封、抗磨、抗冲击、减震、隔热等作用，共同提高发动机工作温度，减少燃油消耗，提高发动机效率，延长热端部件使用寿命，保障发动机安全可靠的工作。
涂布耐磨涂层是提高零件的抗摩擦磨损性能和冲蚀磨损性能的有效手段。空气中的尘埃、水滴和沙粒等在高速气流作用下对风扇/压气机叶片的冲蚀导致其过早损毁失效，采用硬质涂层防护可显著地提高其寿命，而耐冲刷涂层与基材的结合强度必须充分可靠，否则剥离物会产生的磨粒磨损，磨损严重的话甚至可能会酿成停机事故。
授权公告号为CN 104520472B的中国发明专利公开了一种TiAlN-涂层工具，该工具具有基体和PVD工艺施加至所述主体的单层或多层的耐磨保护性涂层，所述基体由硬质金属、金属陶瓷、陶瓷、钢或高速钢制成，其中所述耐磨保护性涂层中至少一层是其中x+y＝1的钛铝氮层，该层取决于使用的工艺可含有最高达5wt％的其它金属，所述TiAlN层为具有多个周期性交替的Tix(A)Aly(A)N涂层(A)和Tix(B)Aly(B)N涂层(B)的多涂层亚结构。该发明提供的涂层主要用于刀具，使其具有高硬度、高弹性模量，同时具有可接受的残余应力和切削刃的改进的稳定性。
授权公告号为CN 103469154B的中国发明专利公开了一种TiAlN多层涂层，该涂层是以“Ti1-xAlxN到Ti1-yAlyN到Ti1-zAlzN”为一个周期的多层涂层。制备方法为：采用物理气相沉积的方法沉积一层TiAl过渡层，然后沉积一层Ti1-xAlxN的基底层，再在Ti1-xAlxN的基底层上循环沉积以“Ti1-xAlxN到Ti1-yAlyN到Ti1-zAlzN”为周期的多层涂层，直至复合涂层的总厚度达到1μm～10μm，其中，0.5≤x<y<z≤1。该发明的多层涂层与基体结合紧密、具有高硬度、高强度、特别是高的抗氧化能力。
磨损现象大都发生在材料表面，因此采用表面涂层技术改善金属材料表面的磨损和腐蚀性能，对提高其使用的安全可靠性以及延长使用寿命是非常有效的。当前，世界各国对于提高金属材料耐磨和减摩性的研究都比较积极，如美、俄、中、日等航空航天大国，近年来发表了大量的专利技术与研究报道。针对航空发动机不同部件由于工作环境的差别需要，采用的技术主要有：激光熔覆、物理气相沉积(PVD)、化学气相沉积(CVD)、热喷涂等。
目前成功应用于航空发动机制造的各种耐磨类涂层主要分类、功能、性能要求、制备方法与典型应用部件如表1所示。
表1.航空发动机耐磨类涂层技术及应用部件
先进军机对发动机推重比提升的需求日益迫切，由此带来的极大的扭矩将使各种摩擦副的承载条件更为苛刻。采用传统的磁控溅射、多弧离子镀技术制备的硬质膜层因其与基材晶体学结构、热物理性能差异大而常存在结合力不牢固、服役期间易产生疲劳剥离的缺陷。另外，对于较软的基材，仅数微米的膜层的承载能力明显不足，基材与膜层弹性模量有较大差异，与膜层接触的区域将产生更大的微变形，在很大的接触应力作用下也将产生膜层的破损和接触疲劳。目前，国内航空发动机产商尚无有效解决这一问题的涂层技术方案。随着我国大推重比航空发动机制造工程的快速推进，提供一种具有充分的承载能力的抗磨、减摩涂层制备技术支持已成为迫在眉睫的需求。
发明内容
针对新一代航空发动机和船用柴油机内重载、高速工作条件下摩擦副零件的耐摩擦磨损性能亟待提升的需求，有机结合电子束物理气相沉积技术(EB-PVD)和等离子碳氮共渗技术(PNC)，提供一种具有硬度梯度层支撑的TiAlN复合超硬涂层，突破传统PVD硬质薄膜结合力不可靠、摩擦系数高、耐温性能差和承载能力不足的技术瓶颈。
实现本发明目的的技术解决方案为：一种具有硬度梯度层支撑的TiAlN复合超硬涂层，所述超硬涂层为自下到上分别为基体材料、扩伸层及沉积层的三层结构；所述基体材料为导电材料；所述的扩伸层为等离子氮碳共渗层；所述的沉积层为氮铝钛涂层。
进一步的，所述等离子氮碳共渗层的硬度自下到上逐渐增加。
进一步的，所述等离子氮碳共渗层的厚度≥100μm；所述氮铝钛涂层的厚度为3-6μm。
进一步的，所述导电材料为普通碳钢、高强钢、合金钢、镍基合金、钛和钛合金、铜及铜基合金。
具有硬度梯度层支撑的TiAlN复合超硬涂层的制备方法，步骤如下：
1)、于导电材料上层表面通过空心阴极效应和场致放电增强的等离子氮碳共渗技术制备得到等离子氮碳共渗层；
2)、于所述等离子氮碳共渗层表面通过离子源辅助电子束物理气相沉积技术制备得到氮铝钛涂层。
相对于现有技术本发明的主要优点是：
如图2所示，本图显示了Ti1-xAlxN涂层的硬度与弹性模量随Al含量的变化图，Al原子可以取代TiN面心立方结构中部分Ti原子形成TiAlN相。由于原子半径RAl<RTi,Al，原子部分取代Ti原子后造成TiN相结构畸变，晶格常数减小。同时随涂层中Al含量的变化，涂层的相结构和硬度也发生变化。Ti-Al-N涂层在使用中可以在外表面自动形成抗磨的Al2O3，从而提高了其寿命。Al的摩尔百分比含量小于70％时，TiAlN涂层热硬度超过TiN涂层。
如图3所示，Al的加入还显著提高了涂层的抗高温氧化性，其TiN的最高抗氧化温度高于600℃，TiAlN的最高抗氧化温度高于800℃。原因在于氧化初期Al离子向外扩散，在Ti-Al-N表面形成了Al2O3氧化层，对O的扩散起到障碍层的作用。
①在基材表面形成的复合耐磨涂层，具有沉积层加扩散层的结构，其氮碳扩散层具有硬度梯度，可显著增强对表面硬脆层的支撑，有效地提升TiAlN超硬膜层的承载能力；
②氮碳扩散层显著增大了零件表层的残余应力值，赋予了复合涂层更大的疲劳抗力；
③氮碳渗层的氮化物、碳化物在热物理性能上与TiAlN膜层更匹配，膜/基界面更融合，因而使膜层具有更牢固、可靠的结合力，也具有更高的抗热疲劳性能；
④将辅助离子源与EB-PVD有机结果起来，提高了氮气离子的电离效率和注入效率；单纯的将氮气通入真空腔体内，无法获得足够数量有活性的氮离子，无法形成超硬的AlTiN化合物；通过辅助离子源可以有效提高氮离子的浓度，在蒸发过程中与Al、Ti原子形成稳定的化合物，同时还能有效提高膜层附着力，改善涂层的微观结构和性质。
附图说明
图1为航空发动机涡轮叶片工作温度演变曲线图；
图2为Ti1-x-AlxN涂层的硬度、杨氏弹性模量随Al含量的变化曲线；
图3为TiN与Ti-Al-N氧化速率对照图；
图4为本发明的具有硬度梯度层支撑的TiAlN复合超硬涂层的结构示意图。
1-氮铝钛涂层；2-等离子氮碳共渗层；3-导电材料。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
实施例1
如图4所示，一种具有硬度梯度层支撑的TiAlN复合超硬涂层，所述超硬涂层为自下到上分别为基体材料、扩伸层及沉积层的三层结构；所述基体材料为300M高强钢；所述的扩伸层为等离子氮碳共渗层；所述的沉积层为氮铝钛涂层1。
所述等离子氮碳共渗层的硬度自下到上逐渐增加。
所述等离子氮碳共渗层的厚度为100μm；所述氮铝钛涂层的厚度为3μm。
具有硬度梯度层支撑的TiAlN复合超硬涂层的制备方法，步骤如下：
1)、于300M高强钢上层表面通过空心阴极效应和场致放电增强的等离子氮碳共渗技术制备得到等离子氮碳共渗层；
2)、于所述等离子氮碳共渗层表面通过离子源辅助电子束物理气相沉积技术制备得到氮铝钛涂层。
根据标准ISO 14577-1(Annex A)，制得TiAlN复合超硬涂层表面硬度为3000HV。
纳米压入方法结合纳米压入载荷-位移曲线图测得TiAlN复合超硬涂层的膜/基结合力为70N。
接触应力与合金钢渗碳或轴承钢相比提高500MPa。
球-盘摩擦磨损实验测得，无润滑条件下，TiAlN复合超硬涂层摩擦系数为0.25，无TiAlN膜层摩擦系数为0.63，相对无TiAlN膜层时摩擦系数降低60％；TiAlN复合超硬涂层磨损率13％，TiN硬质膜磨损率63％，TiN硬质膜相比，相同摩擦条件下，复合涂层的磨损率下降50％。
依据《钢及高温合金的抗氧化性测定试验方法》(中华人民共和国航空工业标准，HB5258-2000)测得，TiAlN复合超硬涂层的严重氧化温度为800℃，TiN硬质膜严重氧化温度为600℃，较于TiN硬质膜TiAlN复合超硬涂层的严重氧化温度提高200℃。
实施例2
如图4所示，一种具有硬度梯度层支撑的TiAlN复合超硬涂层，所述超硬涂层为自下到上分别为基体材料、扩伸层及沉积层的三层结构；所述基体材料为镍基合金；所述的扩伸层为等离子氮碳共渗层；所述的沉积层为氮铝钛涂层。
所述等离子氮碳共渗层的硬度自下到上逐渐增加。
所述等离子氮碳共渗层的厚度为200μm；所述氮铝钛涂层的厚度为6μm。
具有硬度梯度层支撑的TiAlN复合超硬涂层的制备方法，步骤如下：
1)、于基体材料表面通过空心阴极效应和场致放电增强的等离子氮碳共渗技术制备得到等离子氮碳共渗层；
2)、于所述等离子氮碳共渗层表面通过离子源辅助电子束物理气相沉积技术制备得到氮铝钛涂层。
根据标准ISO 14577-1(Annex A)，制得TiAlN复合超硬涂层表面硬度为3500HV。
纳米压入方法结合纳米压入载荷-位移曲线图测得TiAlN复合超硬涂层的膜/基结合力为75N。
接触应力与合金钢渗碳或轴承钢相比提高500MPa。
摩擦磨损性能采用球-盘摩擦磨损实验测得，无润滑条件下，TiAlN复合超硬涂层摩擦系数为0.20，无TiAlN膜层摩擦系数为0.50，相对无TiAlN膜层时摩擦系数降低60％；TiAlN复合超硬涂层磨损率15％，TiN硬质膜磨损率65％，TiN硬质膜相比，相同摩擦条件下，复合涂层的磨损率下降50％。
依据《钢及高温合金的抗氧化性测定试验方法》(中华人民共和国航空工业标准，HB5258-2000)测得，TiAlN复合超硬涂层的严重氧化温度为750℃，TiN硬质膜严重氧化温度为500℃，较于TiN硬质膜TiAlN复合超硬涂层的严重氧化温度提高250℃。
致密TiAlN超硬膜层赋予基材充分的耐磨能力；等离子氮碳共渗层具有硬度梯度，可显著增强对表面硬脆层的支撑，有效地提升TiAlN超硬膜层的承载能力。并且，氮碳还增大了零件表层的残余应力值，赋予了其更大的疲劳抗力。同时，氮碳共渗层的氮化物、碳化物在热物理性能上与TiAlN膜层更匹配，膜/基界面更融合，因而使膜层具有更牢固、可靠的结合力，也具有更高的抗热疲劳性能。
上述仅为本发明两个具体实施方式，但本发明的设计构思并不局限于此，凡利用此构思对本发明进行非实质性的改动，均应属于侵犯本发明保护的范围的行为。但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何形式的简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (5)
1.一种具有硬度梯度层支撑的TiAlN复合超硬涂层，其特征在于：所述超硬涂层为自下到上分别为基体材料、扩伸层及沉积层的三层结构；所述基体材料为导电材料；所述的扩伸层为等离子氮碳共渗层；所述的沉积层为氮铝钛涂层。
2.根据权利要求1所述的具有硬度梯度层支撑的TiAlN复合超硬涂层，其特征在于：所述等离子氮碳共渗层的硬度自下到上逐渐增加。
3.根据权利要求1所述的具有硬度梯度层支撑的TiAlN复合超硬涂层，其特征在于：所述等离子氮碳共渗层的厚度≥100μm；所述氮铝钛涂层的厚度为3-6μm。
4.根据权利要求1所述的具有硬度梯度层支撑的TiAlN复合超硬涂层，其特征在于：所述导电材料为普通碳钢、高强钢、合金钢、镍基合金、钛和钛合金、铜及铜基合金。
5.制备如权利要求1所述的具有硬度梯度层支撑的TiAlN复合超硬涂层的方法，其特征在于：步骤如下：
1）、于导电材料上层表面通过空心阴极效应和场致放电增强的等离子氮碳共渗技术制备得到等离子氮碳共渗层；
2）、于所述等离子氮碳共渗层表面通过离子源辅助电子束物理气相沉积技术制备得到氮铝钛涂层。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277324A (zh) * | 2018-04-20 | 2018-07-13 | 安徽省宁国市亚晨碾磨铸件有限责任公司 | 一种挖掘机斗齿齿尖的表面耐磨处理工艺 |
| CN108754406A (zh) * | 2018-06-25 | 2018-11-06 | 宁波中材钰翔新材料科技有限公司 | 一种模具表面复合处理方法 |
| CN109338319A (zh) * | 2018-11-02 | 2019-02-15 | 太原理工大学 | 一种提高硬质合金表面钛铝氮涂层强韧性的方法 |
| CN109913796A (zh) * | 2019-03-29 | 2019-06-21 | 长安大学 | 一种钛合金表面的TiAlN复合涂层及其制备方法 |
| CN113278954A (zh) * | 2021-05-25 | 2021-08-20 | 南京邮电大学 | 一种复合涂层及其制备方法与应用和制备系统 |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6338880B1 (en) * | 1998-09-04 | 2002-01-15 | Micron Technology, Inc. | Chemical vapor deposition process for depositing titanium nitride films from an organometallic compound |
| KR20040060562A (ko) * | 2002-12-30 | 2004-07-06 | 동부전자 주식회사 | 반도체 소자 제조시 배리어 메탈 산화방지방법 |
| JP2004283995A (ja) * | 2003-03-25 | 2004-10-14 | Nachi Fujikoshi Corp | 高機能ハイス工具 |
| JP2005153126A (ja) * | 2003-11-28 | 2005-06-16 | Nachi Fujikoshi Corp | プラズマ窒化セラミック硬質膜被覆工具 |
| CN1776015A (zh) * | 2005-11-28 | 2006-05-24 | 吴大维 | 具有高附着力的纳米超硬复合膜刀具及其沉积方法 |
| JP2011080099A (ja) * | 2009-10-02 | 2011-04-21 | Kobe Steel Ltd | 肌焼鋼部品およびその製造方法 |
| CN102168269A (zh) * | 2011-03-16 | 2011-08-31 | 广州有色金属研究院 | 一种催渗等离子氮碳共渗与氮碳化钛复合膜层的制备方法 |
| CN103160797A (zh) * | 2013-04-09 | 2013-06-19 | 东莞市浩瀚纳米科技有限公司 | 纳米陶瓷涂层、沉积有该涂层的压铸模具及其制备方法 |
| CN103334106A (zh) * | 2013-05-21 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | 一种钛及钛合金球阀密封副和摩擦副的表面硬化处理方法 |
| US20140050932A1 (en) * | 2011-03-29 | 2014-02-20 | Schaeffler Technologies AG & Co. KG | Method for producing a hardened, coated metal component |
| CN103775634A (zh) * | 2014-02-21 | 2014-05-07 | 四川金星压缩机制造有限公司 | 复合涂层活塞杆及其制造方法 |
| CN103805996A (zh) * | 2014-01-16 | 2014-05-21 | 中国科学院金属研究所 | 一种金属材料表面先镀膜再渗氮的复合处理方法 |
| CN103952660A (zh) * | 2014-05-16 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | 具有氮化物膜的复合材料及其制法和应用 |
-
2017
- 2017-12-29 CN CN201711476458.4A patent/CN107937876A/zh active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6338880B1 (en) * | 1998-09-04 | 2002-01-15 | Micron Technology, Inc. | Chemical vapor deposition process for depositing titanium nitride films from an organometallic compound |
| KR20040060562A (ko) * | 2002-12-30 | 2004-07-06 | 동부전자 주식회사 | 반도체 소자 제조시 배리어 메탈 산화방지방법 |
| JP2004283995A (ja) * | 2003-03-25 | 2004-10-14 | Nachi Fujikoshi Corp | 高機能ハイス工具 |
| JP2005153126A (ja) * | 2003-11-28 | 2005-06-16 | Nachi Fujikoshi Corp | プラズマ窒化セラミック硬質膜被覆工具 |
| CN1776015A (zh) * | 2005-11-28 | 2006-05-24 | 吴大维 | 具有高附着力的纳米超硬复合膜刀具及其沉积方法 |
| JP2011080099A (ja) * | 2009-10-02 | 2011-04-21 | Kobe Steel Ltd | 肌焼鋼部品およびその製造方法 |
| CN102168269A (zh) * | 2011-03-16 | 2011-08-31 | 广州有色金属研究院 | 一种催渗等离子氮碳共渗与氮碳化钛复合膜层的制备方法 |
| US20140050932A1 (en) * | 2011-03-29 | 2014-02-20 | Schaeffler Technologies AG & Co. KG | Method for producing a hardened, coated metal component |
| CN103160797A (zh) * | 2013-04-09 | 2013-06-19 | 东莞市浩瀚纳米科技有限公司 | 纳米陶瓷涂层、沉积有该涂层的压铸模具及其制备方法 |
| CN103334106A (zh) * | 2013-05-21 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | 一种钛及钛合金球阀密封副和摩擦副的表面硬化处理方法 |
| CN103805996A (zh) * | 2014-01-16 | 2014-05-21 | 中国科学院金属研究所 | 一种金属材料表面先镀膜再渗氮的复合处理方法 |
| CN103775634A (zh) * | 2014-02-21 | 2014-05-07 | 四川金星压缩机制造有限公司 | 复合涂层活塞杆及其制造方法 |
| CN103952660A (zh) * | 2014-05-16 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | 具有氮化物膜的复合材料及其制法和应用 |
Non-Patent Citations (7)
| Title |
|---|
| GUNDIS SACHER等: "Duplex Treatment of Tools and Components: Previous or Subsequent Electron Beam Hardening of Thermochemically-Treated and PVD Hard-Coated Steels for Tools and Components" * |
| O. SALAS等: "Tribological behavior of candidate coatings for Al die casting dies" * |
| 刘蜀等: "刀具用硬质合金刀片表面等离子渗氮涂层制备及其耐磨性能研究" * |
| 张高会等: "钛合金双层辉光离子无氢碳氮共渗摩擦性能研究" * |
| 牛瑞丽等: "钛合金表面渗氮层与TiAlN耦合涂层的结构及性能" * |
| 王亮等: "离子氮碳共渗与离子镀TiN复合处理研究" * |
| 魏仕勇等: "渗氮/PVDTiN涂层对42CrMo钢组织和性能的影响" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277324A (zh) * | 2018-04-20 | 2018-07-13 | 安徽省宁国市亚晨碾磨铸件有限责任公司 | 一种挖掘机斗齿齿尖的表面耐磨处理工艺 |
| CN108277324B (zh) * | 2018-04-20 | 2019-06-18 | 安徽省宁国市亚晨碾磨铸件有限责任公司 | 一种挖掘机斗齿齿尖的表面耐磨处理工艺 |
| CN108754406A (zh) * | 2018-06-25 | 2018-11-06 | 宁波中材钰翔新材料科技有限公司 | 一种模具表面复合处理方法 |
| CN109338319A (zh) * | 2018-11-02 | 2019-02-15 | 太原理工大学 | 一种提高硬质合金表面钛铝氮涂层强韧性的方法 |
| CN109913796A (zh) * | 2019-03-29 | 2019-06-21 | 长安大学 | 一种钛合金表面的TiAlN复合涂层及其制备方法 |
| CN113278954A (zh) * | 2021-05-25 | 2021-08-20 | 南京邮电大学 | 一种复合涂层及其制备方法与应用和制备系统 |
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