本文選題：HEDP + 孔隙率　； 參考：《南昌航空大學(xué)》2017年碩士論文

【摘要】：酸性硫酸鹽、焦磷酸鹽等鍍銅工藝由于鍍層結(jié)合力差、孔隙率高等缺點(diǎn),無法滿足航空企業(yè)對鍍銅層性能多樣化的要求,因此,我國航空企業(yè)鍍銅工藝目前依然以含劇毒氰化物的氰化鍍銅工藝為主,而HEDP鍍銅工藝能夠在鋼鐵件上直接電鍍,鍍液深鍍能力好,電流效率高而廣受關(guān)注。針對鍍銅層孔隙率高的缺點(diǎn),在HEDP鍍液中加入添加劑A、B,研究其陰極極化作用、潤濕作用、整平作用,確定添加劑的適宜濃度,同時輔助施加陰極移動降低鍍層孔隙率,并從鍍液和鍍層性能角度,將HEDP鍍銅與氰化鍍銅工藝進(jìn)行綜合比較;采用滴定分析方法測試了HEDP鍍銅液中Cu~(2+)、HEDP含量隨通電量的變化,并依據(jù)工藝要求進(jìn)行調(diào)整維護(hù);采用電化學(xué)等試驗(yàn)方法,比較不同鈍化工藝對HEDP鍍銅層耐蝕性的影響,并對其機(jī)理進(jìn)行初步探討。主要研究結(jié)果如下:在HEDP鍍銅基礎(chǔ)液中加入0.4 g/L添加劑A和2 mg/L添加劑B,添加劑的吸附作用使得極化電位提高,阻化銅的沉積并使晶粒得到細(xì)化,添加劑A能夠降低鍍液的表面張力和固液界面自由能,增強(qiáng)鍍液對陰極界面的潤濕能力,有利于鍍液在試樣表面的鋪展,從而有效抑制析氫反應(yīng),同時輔助施加3 cm/s的陰極移動,縮短了氫氣泡在試樣表面的滯留時間,加速氫氣泡的脫附逸出,避免了較大尺寸針孔和麻點(diǎn)的形成,鍍層內(nèi)部組織連續(xù)、結(jié)構(gòu)致密。當(dāng)鍍層厚度僅8μm時孔隙率便可為0,而在相同的鍍層厚度下,氰化鍍銅及其他無氰鍍銅工藝均有較高的孔隙率。HEDP鍍銅溶液的深鍍能力、分散能力均達(dá)到或超過氰化鍍銅工藝的水平,尤其陰極電流效率遠(yuǎn)高于氰化鍍銅工藝,此外,進(jìn)行滲碳熱處理時,HEDP鍍銅層厚度約15μm,便可有效防止碳的擴(kuò)散滲透,明顯優(yōu)于氰化鍍銅工藝,其根本原因在于鍍液電流效率高、鍍層孔隙率低且結(jié)合力好。30CrMnSiNi2A試樣經(jīng)HEDP鍍銅工藝處理后的氫脆性能合格;HEDP鍍銅工藝對30CrMnSi A試樣疲勞壽命的影響程度與氰化鍍銅工藝相當(dāng)。對于1 L的HEDP鍍銅溶液,隨著通電量的增大,鍍液中Cu~(2+)含量基本穩(wěn)定,絡(luò)合劑HEDP會發(fā)生水解導(dǎo)致含量下降,通電量增大約100 A·h需對HEDP進(jìn)行補(bǔ)加調(diào)整,鍍液性能穩(wěn)定,維護(hù)方便。因此,HEDP鍍銅工藝能夠用來替代現(xiàn)行氰化鍍銅工藝。采用HAD無鉻鈍化工藝,鍍銅層耐蝕性優(yōu)于六價鉻鈍化,其耐蝕性的提高與鈍化膜致密度提高、膜層結(jié)構(gòu)得到完善有關(guān)。
[Abstract]:Due to the poor adhesion and high porosity of copper plating process such as acid sulfate and pyrophosphate, it can not meet the requirements of aviation enterprises for the diversification of copper coating performance. At present, the copper plating process of aviation enterprises in China is still mainly cyanide copper plating process, while HEDP copper plating process can be directly electroplated on iron and steel parts, the deep plating ability of bath is good, and the current efficiency is high and widely concerned. Aiming at the disadvantage of high porosity of copper plating layer, the additive Abib was added to HEDP bath to study the effect of cathodic polarization, wetting and leveling, to determine the appropriate concentration of additives, and to apply cathodic movement to reduce the porosity of coating. From the point of view of bath and coating properties, the copper-plating process of HEDP was compared with that of cyanide, the content of Cu~(2 in HEDP copper plating bath was measured by titration analysis method, and the content of Cu~(2 was adjusted and maintained according to the requirements of the process. The effects of different passivation processes on the corrosion resistance of HEDP copper coating were compared by electrochemical and other experimental methods, and its mechanism was preliminarily discussed. The main results are as follows: when 0.4 g / L additive A and 2 mg/L additive B were added to the base solution of HEDP copper plating, the adsorption effect of the additive increased the polarization potential, prevented the deposition of copper and refined the grain size. Additive A can reduce the surface tension and the free energy of solid-liquid interface, enhance the wetting ability of the bath to the cathode interface, facilitate the spreading of the bath on the surface of the sample, thus effectively restrain the hydrogen evolution reaction. At the same time, the cathode movement of 3 cm/s can shorten the retention time of hydrogen bubble on the sample surface, accelerate the desorption escape of hydrogen bubble, avoid the formation of large size pinholes and pockmarks, the internal microstructure of the coating is continuous and the structure is dense. When the coating thickness is only 8 渭 m, the porosity can be 0. Under the same coating thickness, both cyanide copper plating and other cyanide copper plating processes have higher porosity. The dispersion ability of the copper plating process reached or exceeded the level of cyanide copper plating process, especially the cathodic current efficiency was much higher than that of the cyanide copper plating process. In addition, the thickness of copper coating of HEDP was about 15 渭 m during carburizing heat treatment, which could effectively prevent the diffusion and penetration of carbon. It is obviously superior to the cyanide copper plating process, and the fundamental reason is that the bath current efficiency is high. The hydrogen embrittlement properties of 30CrMnSiNi2A sample treated by HEDP copper plating process are equal to that of cyanide copper plating process. The effect of HEDP copper plating process on fatigue life of 30CrMnSi A specimen is equal to that of cyanide copper plating process. For 1 L HEDP copper plating solution, the content of Cu~(2 in the solution is basically stable with the increase of the amount of electricity, and the content of HEDP decreases due to the hydrolysis of the complex agent HEDP, and the increase of the current content of the solution is about 100A h, and the performance of the plating solution is stable. Maintenance is convenient. Therefore, HEDP copper plating process can be used to replace the current cyanide copper plating process. The corrosion resistance of copper coating is better than that of hexavalent chromium passivation by HAD without chromium passivation process. The improvement of corrosion resistance is related to the improvement of passivation film density and the perfection of film structure.
【學(xué)位授予單位】：南昌航空大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ153.14

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