| This article use the SP-0707type mid frequency reactive magnetron sputtering deposition equipment to prepare ZrN, TiN, TiCN color nanomemter thin film in aluminum alloy surface, which can overcome the traditional disadvantages of aluminum alloy surface treatment process, such as anodic oxidation, electroplating,micro-arc oxidation,laser cladding. This method can solve and improve the surface decoration and surface function of aluminum alloy, expand the application range and delay the using life of aluminum alloy. The highest vacuum degree of SP-0707equipment is better than8×10-4Pa, the furnace vacuum chamber size was Φ700×700mm, the target to substrate distance was120mm, the argon gas flow rate was70sccm, use the flat twin targets, the process parameters of nitrogen flow rate, the sputtering time, sputtering power, substrate bias voltage and duty cycle can adjust. The whole process was carried out in the vacuum furnace, has the advantages of no pollution, high efficiency advantages of sputtering, stable operation. This article use the orthogonal experiment, CM2600d spectrophotometer, PCQC optical analysis software, the German Zeiss Ultra55field emission scanning electron microscopy, American ED AX type GENESIS X ray spectrometer, Japan science instrument of X ray diffraction,6JA interference microscope, YWX/Q-250salt fog corrosion test box, JGW-360A wetting angle measurement instrument, GB/T9286-1998film adhesion test method to research the influence of process parameters to ZrN, TiN, TiCN film color mechanism, optical properties, formation mechanism, growth principle, microstructure, grain size, the diffraction peak intensity, phase diffraction angle, crystal face index (hkl), film thickness, adhesion strength, corrosion resistance, hydrophobic and oleophobic properties.The results shows that, the main parameters to influence the ZrN film color was the nitrogen flow rate, with the increasing of nitrogen flow rate, the ZrN film color difference AE*decreases and then increases, the reflectivity R first increase and then decreases, and the reflectivity R abide by normal distribution function: distribution interval (0,30), distribution center was the μ=15, peak was45.91%, ZrN film in color from light to light yellow to deep yellow to golden yellow to red yellow. The best process parameters to prepare the ZrN film on the aluminum alloy surface are: nitrogen flow rate was15SCCM, the sputtering time was10min, target power was5kW, the bias voltage was-250V, the duty cycle was80%. At this time, L*=82.6, a*=1.3, b*=29.5, color difference△E*is0.84, the reflectance R is45.68; The main parameters to influence the TiN film color were the nitrogen flow rate and sputtering bias voltage, with the nitrogen flow rate increases, TiN film color difference AE*decrease and then increases, reflectivity R increase and then decreases, color from light yellow to deep yellow to golden yellow to red yellow. With the increasing of sputtering bias voltage, TiN film color difference AE*decreases gradually, reflectivity R gradually increases, color from light yellow to golden yellow to red yellow. The good process to prepare the TiN film on the aluminum alloy surface:A2D3B1E4C2, A2D1B4E2C5, A2D2B5E3C1. The color aberration A E*were1.38,1.09,1.29, the AE*of A2D1B4E2C5process was minimum: the nitrogen flow rate was15sccm, the sputtering time was20Min, the sputtering power was8kW,the substrate bias voltage was-150V, the duty cycle was50%; The main parameters to influence the TiCN film color were the nitrogen flow rate and methane gas flow rate, with the increasing of nitrogen flow rate, the film color from light to gun black to light red to matte red. With the increasing of methane gas flow rate, the color from light red to deep red to matte red to dark red. The best process parameters to prepare the TiCN film on the aluminum alloy surface are:the nitrogen flow rate was20sccm, the methane gas flow rate was10sccm, the sputtering time was lOMin, the sputtering power was5kW,the substrate bias voltage was-150V, the duty cycle was80%,△E*=[(△L*)2+((△a*)2+(△b*)2]1/2was0.75.The process parameters influence the color mechanism and optical properties of ZrN, TiN, TiCN film, the color difference AE*of ZrN, TiN, TiCN film was decreases with the increase of reflectivity R, the reflectivity R was proportional to δ=4π/λnhcosi, which directly proportional to the film thickness h. With the film thickness changes, the film color indexes of L*, a*, b*, color difference A E*will be change. The preferred orientation, the diffraction peak intensity, film thickness will be influence the optical properties of film. When the substrate bias voltage was-250V, the diffraction peak is the most intense of (101),(111) crystal plane, has preferred orientation, L*=82.5, a*=2.3, b*=29.6, the film thickness was223nm, the film adhesion was0degree, the corrosion resistance degree was9.3, the film color was golden yellow; when the substrate bias voltage was-150V, the TiN film (111) diffraction peak was most intense, the (111) crystal plane has preferred orientation, L*=82.1, a*=1.5, b*=30.2, the film thickness is254nm, the film adhesion was0degree, the corrosion resistance degree was9.3, the film color was golden yellow; when the substrate bias voltage was-100V, TiCN film (111) diffraction peak was most intense, the (111) crystal plane has preferred orientation, L*=45.56, a*=19.50, b*=2.62, the film thickness is368nm, the film adhesion was0degree, the corrosion resistance degree was9.1, the film color was matte red.Research the film formation mechanism and film growth pattern, which have the relationship with the substrate temperature Ts and the material melting point Tm, when Ts/Tm<0.3, the film show the columnar structures, the intensity of internal defects in fiber structures was very high, or it may be the amorphous structures, the loose structure is obvious present in fiber structures, and exist the much nano size holes; when the Ts/Tm=0.3-0.5, the diameter of columnar crystal was increased with the deposition temperature increasing, the intensity of internal defects was decreased. The compactness in crystal grain boundary was good, and the film has good mechanical properties, and grain surface show the appearance of crystallographic plane at the same time; when the Ts/Tm>0.5, it will present the recrystallization in the film inside, the grain began to grow, the film inside will present the equiaxed grain. The film microstructure is related to the sputtering bias, when the substrate have the different bias and it will have the different preferred orientation, the different preferred orientation will have the different performance. When the bias voltage was-250V, the ZrN film have the (101),(111) preferred orientation, which has good adhesion, high corrosion resistance, with golden yellow color; when thebias voltage was-150V, the TiN film have the (111) preferred orientation, which has goodadhesion,high corrosion resistance, with golden yellow color; when the bias voltage was-100V, the TiCN film have the (111) preferred orientation, which has good adhesion, highcorrosion resistance, with matte color.Study on the influence of the process parameters on the film thickness, film adhesion,film corrosion resistance, film hydrophobic properties. The research shows that, the maininfluence factors on the ZrN, TiN, TiCN film thickness was the sputtering time, followedby substrate bias voltage; the main influence factors on the ZrN, TiN, TiCN film adhesionwere the substrate bias voltage and sputtering power; the main influence factors on the ZrN,TiN, TiCN film corrosion resistance were the substrate bias voltage and sputtering power.The study shows that, the different process parameters can be obtained with ZrN, TiN,TiCN thin films with different wetting angle. According to the Young’s equation, the solidsurface wetting angle has the relation with surface free energy, when the free energy is low,the wetting angle was great, whereas the wetting angle is small. The ZrN film use theprocess to prepare the film:A4B5C4D5E3,A4B5C4D2E7,A5B5C4D2E7, A6B5C4D2E7,film thickness was200-260nm, the grain size was70-90nm, the film adhesion degree was0-1, the corrosion resistance of9.1,9,9.1,9.3which were the good degree and best degree,the wetting angle θ>120°. The TiN film use the process to prepare the film:A2B3C2D1E5, A2B3C2D1E5, film thickness was about255nm, the film adhesion degreewas0, the corrosion resistance of9.1,9.3which were the best degree, the wetting anglewere123°,128°.The TiCN film use the process to prepare the film: A3B4C5D4E2F7,A3B2C5D6E2F6, film thickness was about280nm, the film adhesion degree was0, thecorrosion resistance of9.1,9.3which were the super degree, the wetting angle were131°,123°and the TiCN film has excellent hydrophobic properties. |
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