CN104451560A - Preparation method of (TiAlZrNb)N nitrogen gradient imitation gold decorative film - Google Patents
Preparation method of (TiAlZrNb)N nitrogen gradient imitation gold decorative film Download PDFInfo
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- CN104451560A CN104451560A CN201410659353.2A CN201410659353A CN104451560A CN 104451560 A CN104451560 A CN 104451560A CN 201410659353 A CN201410659353 A CN 201410659353A CN 104451560 A CN104451560 A CN 104451560A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010931 gold Substances 0.000 title claims abstract description 57
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 9
- -1 titanium-aluminum-zirconium-niobium-nitrogen Chemical compound 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 230000008021 deposition Effects 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 238000005137 deposition process Methods 0.000 claims abstract description 14
- 239000013077 target material Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 56
- 238000000151 deposition Methods 0.000 claims description 34
- 229910052786 argon Inorganic materials 0.000 claims description 28
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 27
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 claims description 25
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 16
- 238000007733 ion plating Methods 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000010849 ion bombardment Methods 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 46
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 4
- 230000035939 shock Effects 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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Abstract
一种氮化钛铝锆铌氮梯度仿金装饰膜层的制备方法，其制备方法依次包括：1、沉积技术及靶材成分的确定；2、工件的选择与前处理；3、预轰击工艺的确定；4、沉积工艺的确定；5、真空加热处理；6、工件旋转。本发明相比于TiN等传统仿金装饰薄膜，氮化钛铝锆铌氮梯度仿金装饰膜层颜色更加趋近于黄金，氮化钛铝锆铌氮梯度仿金装饰膜的耐用性远远超过传统的仿金装饰图层，并且所镀膜层工艺简单，工艺参数范围比较大，更能很好的控制所镀膜层的颜色。与此同时，该方法降低了镀膜成本，保证了膜层高硬度及高附着力的同时实现，减小了膜层内应力，且具有良好的稳定性和可重复性。A method for preparing a titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film, the preparation method sequentially includes: 1. Deposition technology and determination of target material components; 2. Selection and pretreatment of workpieces; 3. Pre-bombardment process 4. Determination of deposition process; 5. Vacuum heat treatment; 6. Workpiece rotation. Compared with traditional gold-imitation decorative films such as TiN, the color of the titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film layer of the present invention is closer to gold, and the durability of the titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film is much higher. It surpasses the traditional imitation gold decorative layer, and the process of the coating layer is simple, the range of process parameters is relatively large, and the color of the coating layer can be better controlled. At the same time, the method reduces the coating cost, ensures the realization of high hardness and high adhesion of the film layer at the same time, reduces the internal stress of the film layer, and has good stability and repeatability.
Description
技术领域 technical field
本发明涉及一种氮梯度仿金装饰膜层的制备方法，特别是采用不同合金靶制备多弧离子镀氮梯度仿金装饰膜层的方法，比如氮化钛铝锆铌﹝（TiAlZrNb）N﹞氮梯度仿金装饰膜层的制备方法。 The present invention relates to a method for preparing a nitrogen gradient imitation gold decorative film, especially a method for preparing a multi-arc ion nitrogen-plated gradient imitation gold decorative film by using different alloy targets, such as titanium aluminum zirconium niobium nitride (TiAlZrNb)N ﹞ A method for preparing a nitrogen gradient imitation gold decorative film layer.
背景技术 Background technique
多弧离子镀是一种设有多个可同时蒸发的阴极弧蒸发源的真空物理沉积技术，具有沉积速度快、膜层组织致密、附着力强、均匀性好等显著特点。该技术适用于装饰膜层的制备，并在氮化钛，氮化锆，氮化钛铝，以及更多元的仿金装饰膜层的制备方面获得成功应用。氮化钛, 氮化锆，氮化钛铝等钛基仿金装饰膜层由于生产效率高、工艺成本低、膜层性能稳定，颜色接近黄金等各自特性具有广泛的开发应用前景。 Multi-arc ion plating is a vacuum physical deposition technology with multiple cathode arc evaporation sources that can be evaporated simultaneously. It has the remarkable characteristics of fast deposition speed, dense film structure, strong adhesion, and good uniformity. This technology is suitable for the preparation of decorative film layers, and has been successfully applied in the preparation of titanium nitride, zirconium nitride, titanium aluminum nitride, and more imitation gold decorative film layers. Titanium nitride, zirconium nitride, titanium aluminum nitride and other titanium-based imitation gold decorative films have broad development and application prospects due to their high production efficiency, low process cost, stable film performance, and color close to gold.
对于单层的以钛为基的氮化物仿金装饰膜层而言，主要存在以下缺点：1、传统仿金装饰膜一般容易出现膜层硬度与膜层附着力之间的矛盾，即硬度与附着力难以同时满足；2、传统仿金装饰膜膜层的颜色只在很小的工艺参数范围内能达到所需效果，膜层的颜色不容易控制。 For the single-layer titanium-based nitride imitation gold decorative film, there are mainly the following disadvantages: 1. Traditional gold imitation decorative films are generally prone to contradictions between film hardness and film adhesion, that is, hardness and film adhesion. Adhesion is difficult to meet at the same time; 2. The color of the traditional imitation gold decorative film layer can only achieve the desired effect within a small range of process parameters, and the color of the film layer is not easy to control.
发明内容 Contents of the invention
本发明的目的是提供一种氮化钛铝锆铌氮梯度仿金装饰膜层的制备方法，相比于TiN等传统仿金装饰薄膜，氮化钛铝锆铌氮梯度仿金装饰膜层颜色更加趋近于黄金，氮化钛铝锆铌氮梯度仿金装饰膜的耐用性远远超过传统的仿金装饰图层，并且所镀膜层工艺简单，工艺参数范围比较大，更能很好的控制所镀膜层的颜色。与此同时，该方法降低了镀膜成本，保证了膜层高硬度及高附着力的同时实现，减小了膜层内应力，且具有良好的稳定性和可重复性。 The purpose of the present invention is to provide a method for preparing a titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film. Closer to gold, the durability of the titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film is far superior to that of the traditional imitation gold decorative layer, and the coating process is simple, and the range of process parameters is relatively large, which is better Controls the color of the coated layer. At the same time, the method reduces the coating cost, ensures the realization of high hardness and high adhesion of the film layer at the same time, reduces the internal stress of the film layer, and has good stability and repeatability.
本发明的技术方案是：一种氮化钛铝锆铌氮梯度仿金装饰膜层的制备方法依次包括： The technical scheme of the present invention is: a method for preparing a titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film layer sequentially comprises:
1、沉积技术及靶材成分的确定：确定多弧离子镀作为氮化钛铝锆铌氮梯度仿金装饰膜层的制备技术，选用两个不同方位且成90度配置的弧源同时起弧沉积，其中一个弧源为纯度99.9%的商用钛铌合金靶，钛铌合金靶的原子比为Ti:Nb=75:25；另一个弧源为纯度99.9%的商用钛铝锆合金靶，钛铝锆合金靶的原子比为Ti:Al:Zr=71:18:11。 1. Deposition technology and determination of target material composition: determine multi-arc ion plating as the preparation technology for titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, and select two arc sources with different orientations and arranged at 90 degrees to start the arc at the same time Deposition, one of the arc sources is a commercial titanium-niobium alloy target with a purity of 99.9%, the atomic ratio of the titanium-niobium alloy target is Ti:Nb=75:25; the other arc source is a commercial titanium-aluminum-zirconium alloy target with a purity of 99.9%, titanium The atomic ratio of the aluminum-zirconium alloy target is Ti:Al:Zr=71:18:11.
2、工件的选择与前处理：选择商用高速钢作为工件材料，在放入镀膜室进行镀膜前，使用金属洗涤剂对工件进行常规去油、去污处理并进行表面抛光处理，最后分别用丙酮和乙醇进行超声波清洗，电吹风吹干以备用。 2. Selection and pre-treatment of workpieces: commercial high-speed steel is selected as the workpiece material, and before being put into the coating chamber for coating, the workpiece is routinely degreased, decontaminated, and surface-polished with metal detergent, and finally treated with acetone Ultrasonic cleaning with ethanol and drying with a hair dryer for later use.
3、预轰击工艺的确定：指为获得多弧离子镀氮化钛铝锆铌氮梯度仿金装饰膜层而在沉积之前进行的离子轰击工艺，当镀膜室背底真空度达到8.0′10-3帕、温度达到180°C时充入氩气，使镀膜室真空度达到2.5′10-1 帕，开启两弧源，分别保持弧电流在50安培和58安培，进行离子轰击8~10分钟，轰击偏压从300伏逐渐增加到350伏。 3. Determination of the pre-bombardment process: refers to the ion bombardment process before deposition in order to obtain the multi-arc ion plating titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, when the vacuum degree of the back of the coating chamber reaches 8.0′10 - 3 Pa, when the temperature reaches 180°C, fill in argon gas to make the vacuum of the coating chamber reach 2.5′10 -1 Pa, turn on the two arc sources, keep the arc current at 50 amps and 58 amps respectively, and carry out ion bombardment for 8~10 minutes , the bombardment bias was gradually increased from 300 V to 350 V.
4、沉积工艺的确定：指为获得多弧离子镀技术制备氮化钛铝锆铌氮梯度仿金装饰膜层而采用的沉积工艺，镀膜过程分为四个阶段，第一步，将镀膜室内的氩气压强保持在2.0′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于50安培和58安培，工件偏压为150~200伏，沉积时间5~8分钟；第二步，向镀膜室内通入氮气，使其分压强达到0.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间10分钟；第三步，向镀膜室内继续通入氮气，使其分压强达到1.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟；第四步，关闭氩气入口，使氩气流量为0，氩气分压为0，并继续增加氮气流量，使其压强达到2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟。 4. Determination of the deposition process: refers to the deposition process used to obtain the multi-arc ion plating technology to prepare the titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer. The coating process is divided into four stages. The argon pressure is maintained at 2.0′10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 50 amperes and 58 amperes, the workpiece bias is 150~200 volts, and the deposition time is 5~8 minutes ; In the second step, nitrogen gas is introduced into the coating chamber to make the partial pressure reach 0.5′10 -1 Pa, and then the flow rate of argon gas is adjusted to keep the total pressure of the mixed gas at 2.5′10 -1 Pa. The titanium-aluminum-zirconium alloy target and The arc current of the titanium-niobium alloy target is set at 52 amperes and 60 amperes respectively, the bias voltage of the workpiece is 150-200 volts, and the deposition time is 10 minutes; the third step is to continue to feed nitrogen gas into the coating chamber to make the partial pressure reach 1.5′10 -1 Pa, then adjust the argon flow to keep the total pressure of the mixed gas at 2.5'10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 52 amperes and 60 amperes, and the workpiece bias is 150~200 volts, the deposition time is 20 minutes; the fourth step is to close the argon inlet, make the argon flow rate 0, argon partial pressure 0, and continue to increase the nitrogen flow rate to make the pressure reach 2.5′10 -1 Pa, The arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target were set at 52 amperes and 60 amperes respectively, the workpiece bias voltage was 150-200 volts, and the deposition time was 20 minutes.
5、真空加热处理：包括工件加热和膜层烘烤，工件加热方式采用电热体烘烤加热，在镀膜室背底真空达到3.0′10-2帕时开始工件加热，升温速度保持在3~5°C /分钟，一小时后可以达到180°C；膜层烘烤是指沉积过程结束后对所沉积的氮化钛铝锆铌氮梯度仿金装饰膜层进行后加热烘烤，采用小电流进行微加热10~15分钟，电流逐渐从70安培降低到50安培。 5. Vacuum heating treatment: including workpiece heating and film layer baking. The workpiece heating method adopts electric heating body baking heating. The workpiece heating starts when the vacuum at the back and bottom of the coating chamber reaches 3.0′10 -2 Pa, and the heating rate is kept at 3~5 °C/minute, and it can reach 180°C after one hour; film layer baking refers to post-heating and baking of the deposited titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer after the deposition process, using a small current Gently heat for 10 to 15 minutes, gradually reducing the current from 70 amps to 50 amps.
6、工件旋转：在工件加热、离子轰击、膜层沉积、膜层烘烤的整个过程中一直保持工件旋转，转速为4~6转/分钟。 6. Workpiece rotation: During the whole process of workpiece heating, ion bombardment, film deposition, and film baking, the workpiece is kept rotating at a speed of 4~6 rpm.
按照本发明所提出的采用钛铌合金靶和钛铝锆合金靶组合靶制备多弧离子镀氮化钛铝锆铌氮梯度仿金装饰膜层的方法，可以获得上述的氮化钛铝锆铌氮梯度仿金装饰膜层，与TiN 仿金装饰膜相比，氮化钛铝锆铌氮梯度仿金装饰膜层颜色更加趋近于黄金颜色，所镀膜层颜色均匀、光亮。 According to the method proposed by the present invention for preparing a multi-arc ion-plated titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film layer using a titanium-niobium alloy target and a titanium-aluminum-zirconium alloy target combination target, the above-mentioned titanium, aluminum, zirconium, niobium, and niobium nitride can be obtained Nitrogen gradient imitation gold decorative film layer, compared with TiN imitation gold decorative film, the color of titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer is closer to gold color, and the color of the coating layer is uniform and bright.
同现有技术相比，本发明确定了常规通用的多弧离子镀作为氮化钛铝锆铌氮梯度仿金装饰膜层的制备技术，确定了商用钛铌合金靶和钛铝锆合金靶作为电弧源，避免了专门冶炼、制备钛铝锆铌合金靶的局限性，降低了镀膜成本；本发明确定了靶材成分、数量及配置方位，确定了商用高速钢作为工件材料，确定了工件前处理工艺和沉积工艺。与TiN 仿金装饰膜相比，氮化钛铝锆铌氮梯度仿金装饰膜层颜色更接近黄金颜色，并且所镀膜层颜色均匀、光亮，在保证膜层颜色的前提下，同时也保证了膜层高附着力、较高硬度和较高抗热震性，工艺简单，可操作工艺参数范围广，具有良好的稳定性和可重复性，从而更加有利于提高氮化钛铝锆铌氮梯度仿金装饰膜层的使用寿命，更适合于在装饰行业上的应用。 Compared with the prior art, the present invention determines the conventional general-purpose multi-arc ion plating as the preparation technology of the titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film layer, and determines the commercial titanium-niobium alloy target and the titanium-aluminum-zirconium alloy target as The arc source avoids the limitations of special smelting and preparation of titanium-aluminum-zirconium-niobium alloy targets, and reduces the cost of coating; the invention determines the target material composition, quantity and configuration orientation, and determines the commercial high-speed steel as the workpiece material, and determines the treatment process and deposition process. Compared with the TiN imitation gold decorative film, the color of the titanium-aluminum-zirconium-niobium-nitrogen gradient imitation gold decorative film is closer to the gold color, and the color of the coated film is uniform and bright. On the premise of ensuring the color of the film, it also ensures The film layer has high adhesion, high hardness and high thermal shock resistance, simple process, wide range of operable process parameters, good stability and repeatability, which is more conducive to improving the gradient of titanium nitride, aluminum, zirconium, niobium and nitrogen The service life of the imitation gold decorative film layer is more suitable for application in the decoration industry.
具体实施方式 Detailed ways
实施例1Example 1
在商用高速钢（W18Cr4V）上制备氮化钛铝锆铌氮梯度仿金装饰膜层，其方法是： Preparation of titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer on commercial high speed steel (W18Cr4V), the method is:
1、沉积技术及靶材成分的确定：确定多弧离子镀作为氮化钛铝锆铌氮梯度仿金装饰膜层的制备技术，选用两个不同方位且成90度配置的弧源同时起弧沉积，其中一个弧源为纯度99.9%的商用钛铌合金靶，钛铌合金靶的原子比为Ti:Nb=75:25；另一个弧源为纯度99.9%的商用钛铝锆合金靶，钛铝锆合金靶的原子比为Ti:Al:Zr=71:18:11。 1. Deposition technology and determination of target material composition: determine multi-arc ion plating as the preparation technology for titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, and select two arc sources with different orientations and arranged at 90 degrees to start the arc at the same time Deposition, one of the arc sources is a commercial titanium-niobium alloy target with a purity of 99.9%, the atomic ratio of the titanium-niobium alloy target is Ti:Nb=75:25; the other arc source is a commercial titanium-aluminum-zirconium alloy target with a purity of 99.9%, titanium The atomic ratio of the aluminum-zirconium alloy target is Ti:Al:Zr=71:18:11.
2、工件的选择与前处理：选择商用高速钢（W18Cr4V）作为工件材料，在放入镀膜室进行镀膜前，使用金属洗涤剂对工件进行常规去油、去污处理并进行表面抛光处理，最后分别用丙酮和乙醇进行超声波清洗，电吹风吹干以备用。 2. Selection and pre-treatment of workpieces: commercial high-speed steel (W18Cr4V) is selected as the workpiece material, and before being put into the coating chamber for coating, the workpiece is routinely degreased, decontaminated and surface polished with metal detergent, and finally Ultrasonic cleaning was performed with acetone and ethanol respectively, and dried with a hair dryer for later use.
3、预轰击工艺的确定：指为获得多弧离子镀氮化钛铝锆铌氮梯度仿金装饰膜层而在沉积之前进行的离子轰击工艺，当镀膜室背底真空度达到8.0′10-3帕、温度达到180°C时充入氩气，使镀膜室真空度达到2.5′10-1 帕，开启两弧源，分别保持弧电流在50安培和58安培，进行离子轰击10分钟，轰击偏压从300伏逐渐增加到350伏。 3. Determination of the pre-bombardment process: refers to the ion bombardment process before deposition in order to obtain the multi-arc ion plating titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, when the vacuum degree of the back of the coating chamber reaches 8.0′10 - 3 Pa, when the temperature reaches 180°C, fill in argon gas to make the vacuum of the coating chamber reach 2.5′10 -1 Pa, turn on the two arc sources, keep the arc current at 50 amps and 58 amps respectively, carry out ion bombardment for 10 minutes, and bombard The bias voltage was gradually increased from 300 volts to 350 volts.
4、沉积工艺的确定：指为获得多弧离子镀技术制备氮化钛铝锆铌氮梯度仿金装饰膜层而采用的沉积工艺，镀膜过程分为四个阶段，第一步，将镀膜室内的氩气压强保持在2.0′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于50安培和58安培，工件偏压为150~200伏，沉积时间5~8分钟；第二步，向镀膜室内通入氮气，使其分压强达到0.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间10分钟；第三步，向镀膜室内继续通入氮气，使其分压强达到1.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟；第四步，关闭氩气入口，使氩气流量为0，氩气分压为0，并继续增加氮气流量，使其压强达到2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟。 4. Determination of the deposition process: refers to the deposition process used to obtain the multi-arc ion plating technology to prepare the titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer. The coating process is divided into four stages. The argon pressure is maintained at 2.0′10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 50 amperes and 58 amperes, the workpiece bias is 150~200 volts, and the deposition time is 5~8 minutes ; In the second step, nitrogen gas is introduced into the coating chamber to make the partial pressure reach 0.5′10 -1 Pa, and then the flow rate of argon gas is adjusted to keep the total pressure of the mixed gas at 2.5′10 -1 Pa. The titanium-aluminum-zirconium alloy target and The arc current of the titanium-niobium alloy target is set at 52 amperes and 60 amperes respectively, the bias voltage of the workpiece is 150-200 volts, and the deposition time is 10 minutes; the third step is to continue to feed nitrogen gas into the coating chamber to make the partial pressure reach 1.5′10 -1 Pa, then adjust the argon flow to keep the total pressure of the mixed gas at 2.5'10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 52 amperes and 60 amperes, and the workpiece bias is 150~200 volts, the deposition time is 20 minutes; the fourth step is to close the argon inlet, make the argon flow rate 0, argon partial pressure 0, and continue to increase the nitrogen flow rate to make the pressure reach 2.5′10 -1 Pa, The arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target were set at 52 amperes and 60 amperes respectively, the workpiece bias voltage was 150-200 volts, and the deposition time was 20 minutes.
5、真空加热处理：包括工件加热和膜层烘烤，工件加热方式采用电热体烘烤加热，在镀膜室背底真空达到3.0′10-2帕时开始工件加热，升温速度保持在3~5°C /分钟，一小时后达到180°C；膜层烘烤是指沉积过程结束后对所沉积的氮化钛铝锆铌氮梯度仿金装饰膜层进行后加热烘烤，采用小电流进行微加热12分钟，电流逐渐从70安培降低到50安培。 5. Vacuum heating treatment: including workpiece heating and film layer baking. The workpiece heating method adopts electric heating body baking heating. The workpiece heating starts when the vacuum at the back and bottom of the coating chamber reaches 3.0′10 -2 Pa, and the heating rate is kept at 3~5 °C/minute, reaching 180°C after one hour; film layer baking refers to the post-heating and baking of the deposited titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer after the deposition process, using a small current for Gently heat for 12 minutes, gradually reducing the current from 70 amps to 50 amps.
6、工件旋转：在工件加热、离子轰击、膜层沉积、膜层烘烤的整个过程中一直保持工件旋转，转速为5转/分钟。 6. Workpiece rotation: During the whole process of workpiece heating, ion bombardment, film deposition, and film baking, the workpiece is kept rotating at a speed of 5 rpm.
对使用上述方法制备的氮化钛铝锆铌氮梯度仿金装饰膜层进行观察与测试，与TiN 仿金装饰膜相比，氮化钛铝锆铌氮梯度仿金膜层具有黄金颜色，并且膜层颜色均匀，色泽光亮。与此同时，氮化钛铝锆铌氮梯度仿金装饰膜层附着力达到200N，硬度达到HV2900，抗650°C热震循环次数达到8次。 The titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer prepared by the above method was observed and tested. Compared with the TiN imitation gold decorative film, the titanium aluminum zirconium niobium nitrogen gradient imitation gold film layer has a golden color, and The color of the film layer is uniform and the color is bright. At the same time, the adhesion of titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film reaches 200N, the hardness reaches HV2900, and the number of thermal shock resistance cycles at 650°C reaches 8 times.
实施例2 Example 2
在商用高速钢（W6Mo5Cr4V2）上制备氮化钛铝锆铌氮梯度仿金装饰膜层，其方法是： Preparation of titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer on commercial high-speed steel (W6Mo5Cr4V2), the method is:
1、沉积技术及靶材成分的确定：确定多弧离子镀作为氮化钛铝锆铌氮梯度仿金装饰膜层的制备技术，选用两个不同方位且成90度配置的弧源同时起弧沉积，其中一个弧源为纯度99.9%的商用钛铌合金靶，钛铌合金靶的原子比为Ti:Nb=75:25；另一个弧源为纯度99.9%的商用钛铝合金靶，钛铝锆合金靶的原子比为Ti:Al:Zr=71:18:11。 1. Deposition technology and determination of target material composition: determine multi-arc ion plating as the preparation technology for titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, and select two arc sources with different orientations and arranged at 90 degrees to start the arc at the same time Deposition, one of the arc sources is a commercial titanium-niobium alloy target with a purity of 99.9%, the atomic ratio of the titanium-niobium alloy target is Ti:Nb=75:25; the other arc source is a commercial titanium-aluminum alloy target with a purity of 99.9%, titanium-aluminum The atomic ratio of the zirconium alloy target is Ti:Al:Zr=71:18:11.
2、工件的选择与前处理：选择商用高速钢（W6Mo5Cr4V2）作为工件材料，在放入镀膜室进行镀膜前，使用金属洗涤剂对工件进行常规去油、去污处理并进行表面抛光处理，最后分别用丙酮和乙醇进行超声波清洗，电吹风吹干以备用。 2. Selection and pre-treatment of the workpiece: select commercial high-speed steel (W6Mo5Cr4V2) as the workpiece material, and use metal detergent to perform routine degreasing, decontamination and surface polishing on the workpiece before putting it into the coating chamber for coating, and finally Ultrasonic cleaning was performed with acetone and ethanol respectively, and dried with a hair dryer for later use.
3、预轰击工艺的确定：指为获得多弧离子镀氮化钛铝锆铌氮梯度仿金装饰膜层而在沉积之前进行的离子轰击工艺，当镀膜室背底真空度达到8.0′10-3帕、温度达到180°C时充入氩气，使镀膜室真空度达到2.5′10-1 帕，开启两弧源，分别保持弧电流在50安培和58安培，进行离子轰击10分钟，轰击偏压从300伏逐渐增加到350伏。 3. Determination of the pre-bombardment process: refers to the ion bombardment process before deposition in order to obtain the multi-arc ion plating titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer, when the vacuum degree of the back of the coating chamber reaches 8.0′10 - 3 Pa, when the temperature reaches 180°C, fill in argon gas to make the vacuum of the coating chamber reach 2.5′10 -1 Pa, turn on the two arc sources, keep the arc current at 50 amps and 58 amps respectively, carry out ion bombardment for 10 minutes, and bombard The bias voltage was gradually increased from 300 volts to 350 volts.
4、沉积工艺的确定：指为获得多弧离子镀技术制备氮化钛铝锆铌氮梯度仿金装饰膜层而采用的沉积工艺，镀膜过程分为四个阶段，第一步，将镀膜室内的氩气压强保持在2.0′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于50安培和58安培，工件偏压为150~200伏，沉积时间5~8分钟；第二步，向镀膜室内通入氮气，使其分压强达到0.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间10分钟；第三步，向镀膜室内继续通入氮气，使其分压强达到1.5′10-1 帕，然后调整氩气流量，使混合气体总压强保持在2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟；第四步，关闭氩气入口，使氩气流量为0，氩气分压为0，并继续增加氮气流量，使其压强达到2.5′10-1 帕，钛铝锆合金靶和钛铌合金靶的弧电流分别置于52安培和60安培，工件偏压为150~200伏，沉积时间20分钟。 4. Determination of the deposition process: refers to the deposition process used to obtain the multi-arc ion plating technology to prepare the titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer. The coating process is divided into four stages. The argon pressure is maintained at 2.0′10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 50 amperes and 58 amperes, the workpiece bias is 150~200 volts, and the deposition time is 5~8 minutes ; In the second step, nitrogen gas is introduced into the coating chamber to make the partial pressure reach 0.5′10 -1 Pa, and then the flow rate of argon gas is adjusted to keep the total pressure of the mixed gas at 2.5′10 -1 Pa. The titanium-aluminum-zirconium alloy target and The arc current of the titanium-niobium alloy target is set at 52 amperes and 60 amperes respectively, the bias voltage of the workpiece is 150-200 volts, and the deposition time is 10 minutes; the third step is to continue to feed nitrogen gas into the coating chamber to make the partial pressure reach 1.5′10 -1 Pa, then adjust the argon flow to keep the total pressure of the mixed gas at 2.5'10 -1 Pa, the arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target are respectively set at 52 amperes and 60 amperes, and the workpiece bias is 150~200 volts, the deposition time is 20 minutes; the fourth step is to close the argon inlet, make the argon flow rate 0, argon partial pressure 0, and continue to increase the nitrogen flow rate to make the pressure reach 2.5′10 -1 Pa, The arc currents of the titanium-aluminum-zirconium alloy target and the titanium-niobium alloy target were set at 52 amperes and 60 amperes respectively, the workpiece bias voltage was 150-200 volts, and the deposition time was 20 minutes.
5、真空加热处理：包括工件加热和膜层烘烤，工件加热方式采用电热体烘烤加热，在镀膜室背底真空达到3.0′10-2帕时开始工件加热，升温速度保持在3~5°C /分钟，一小时后达到180°C；膜层烘烤是指沉积过程结束后对所沉积的氮化钛铝锆铌氮梯度仿金装饰膜层进行后加热烘烤，采用小电流进行微加热10分钟，电流逐渐从70安培降低到50安培。 5. Vacuum heating treatment: including workpiece heating and film layer baking. The workpiece heating method adopts electric heating body baking heating. The workpiece heating starts when the vacuum at the back and bottom of the coating chamber reaches 3.0′10 -2 Pa, and the heating rate is kept at 3~5 °C/minute, reaching 180°C after one hour; film layer baking refers to the post-heating and baking of the deposited titanium nitride aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer after the deposition process, using a small current for Gently heat for 10 minutes, gradually reducing the current from 70 amps to 50 amps.
6、工件旋转：在工件加热、离子轰击、膜层沉积、膜层烘烤的整个过程中一直保持工件旋转，转速为5转/分钟。 6. Workpiece rotation: During the whole process of workpiece heating, ion bombardment, film deposition, and film baking, the workpiece is kept rotating at a speed of 5 rpm.
对使用上述方法制备的氮化钛铝锆铌氮梯度仿金装饰膜层进行观察与测试，与TiN 仿金装饰膜相比，氮化钛铝锆铌氮梯度仿金膜层具有黄金颜色，并且膜层颜色均匀，色泽光亮。与此同时，氮化钛铝锆铌氮梯度仿金装饰膜层附着力达到200N，硬度达到HV2800，抗650°C热震循环次数达到9次。 The titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film layer prepared by the above method was observed and tested. Compared with the TiN imitation gold decorative film, the titanium aluminum zirconium niobium nitrogen gradient imitation gold film layer has a golden color, and The color of the film layer is uniform and the color is bright. At the same time, the adhesion of titanium aluminum zirconium niobium nitrogen gradient imitation gold decorative film reaches 200N, the hardness reaches HV2800, and the number of thermal shock resistance cycles at 650°C reaches 9 times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726823A (en) * | 2015-04-14 | 2015-06-24 | 沈阳大学 | Method for preparation of titanium aluminum zirconium niobium/titanium aluminum zirconium niobium nitride quaternary-nitrogen gradient films |
| CN106926629A (en) * | 2017-03-02 | 2017-07-07 | 西藏中艺金像科技股份有限公司 | A kind of golden film prepares the method that golden book gold is drawn |
| CN108950488A (en) * | 2018-08-03 | 2018-12-07 | 河北工程大学 | TiAl/TiAlN/TiZrAlN composite coating and preparation method thereof |
| CN116815139A (en) * | 2023-07-31 | 2023-09-29 | 宁波江丰电子材料股份有限公司 | Titanium-niobium alloy sputtering target material and preparation method and application thereof |
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2014
- 2014-11-18 CN CN201410659353.2A patent/CN104451560A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726823A (en) * | 2015-04-14 | 2015-06-24 | 沈阳大学 | Method for preparation of titanium aluminum zirconium niobium/titanium aluminum zirconium niobium nitride quaternary-nitrogen gradient films |
| CN106926629A (en) * | 2017-03-02 | 2017-07-07 | 西藏中艺金像科技股份有限公司 | A kind of golden film prepares the method that golden book gold is drawn |
| CN108950488A (en) * | 2018-08-03 | 2018-12-07 | 河北工程大学 | TiAl/TiAlN/TiZrAlN composite coating and preparation method thereof |
| CN116815139A (en) * | 2023-07-31 | 2023-09-29 | 宁波江丰电子材料股份有限公司 | Titanium-niobium alloy sputtering target material and preparation method and application thereof |
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