木材非电解镀铜工艺及其镀层表征
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摘要
木材具有自然美观的纹理,而铜具有光亮的金属色泽,将铜附着于木材表面上不仅可以使木材在保持自身纹理的同时兼具铜的光泽,具备良好的装饰性,而且还能使木材的表面具备铜的物理性质,从而能够采用十分成熟的以铜为基体的金属表面镀技术使木材表面另外附着上其他金属,产生更多样的金属表面效果。本研究的主要目的就是研发出木材专用的非电解镀铜液及施镀工艺,并对其镀层做一系列的分析研究以判定镀铜层的物理性质及其在木材表面的分布情况。
本研究的结果归纳如下:
1.研发出一套针对木材的非电解镀铜液及工艺,包括预处理方法,镀液的配方以及工艺条件的控制。同时,这一套工艺还可以在较大范围内适应多种木材表面的非电解镀铜,具有较灵活的适应性。镀液的最佳配方为:铜盐8 g/L,络合剂20 g/L,甲醛10 ml/L,温度50℃,针对不同的树种调节pH在12.4至13之间。
2.镀铜层的厚度可通过施镀时间的变化在一定范围内调节,施镀时间越长,镀铜层的厚度就越大,但超过了一定的时间,镀铜层的厚度就几乎不再增加,没有必要在基材表面继续施镀。另外,根据试验所取的七个树种的镀铜层厚度与施镀时间的关系趋势图可以得出在前10min内镀层厚度增加最快,施镀效果最好。
3.随着镀铜层厚度的增加,木材表面的导电性有明显的提高,同时不同切面各方向上的表面电阻率的值也趋于一致。当达到一定的厚度时,木材表面铜层的导电性能够接近于铜箔的导电性;同时,随着厚度的增加,镀铜层在木材表面的附着强度也有很大的提高。
4.通过X射线衍射图像分析可知,采用此工艺进行非电解镀铜所生成的镀铜层具有十分好的纯度,就表层来说其各项性质已经十分接近于铜箔。
5.从扫描电镜得出的图像来看,木材表面的纹理是影响镀铜层导电性以及表面附着强度的主要因素,可以通过适当增加施镀时间从而增加镀铜层在其内部的积聚量来解决。
With the shining cooper on the surface, wood will appear beautiful grains that have the luster of copper. If the copper is adhered on the wood surface, the surface will have the physical ability of the copper, thereby we could cover more metal on wood surface by more common metal-plating technologies and make the wood surface appear various metal effect. The purpose of this study is to develop electroless copper plating technology which is especially used on the wood surface. In addition, electroless copper plating was analysed to judge its physical character and how it is distributed on the wood surface.Research results are summed up as follows:1. An electroless copper plating technology has been developed. It includes pretreatment means, prescription of plating liquid and processing craft. This processing craft could be used on different wood, so it has good adaptability. The best description of the plating liquid is composed of copper-salt (8g/L), complex (20g/L) and HCHO (10ml/L). The temperature should better be kept by 50℃ and pH is between 12.4 and 13.2. The thickness of copper layer could be adjusted by means of changing plating time. More time is used, more copper is plated, but when plating time is over the limit, the thickness of copper layer will not increase. In addition, according to the trend of relationship between thickness of copper layer and plating time of seven species, the thickness of copper layer increase fastest in the first 10 minutes.3. With the increasing of the thickness of copper layer, the electric ability of the surface is also improved and the exterior resistivity of different surface is also more identical. When the thickness of copper layer is over some value, the electric ability of wood surface is close to that of copper foil and the adhesive intensity is also been improved.4. According to the images of XRD, the copper layer will have great pure degree and the character of it will be close to copper toil if using this craft.5. According to the graph of SEM, the grains on wood surface is main factor that affect the electric ability and the adhesive intensity of copper layer on wood, which could be
resolved by increasing plating time.
本研究的结果归纳如下:
1.研发出一套针对木材的非电解镀铜液及工艺,包括预处理方法,镀液的配方以及工艺条件的控制。同时,这一套工艺还可以在较大范围内适应多种木材表面的非电解镀铜,具有较灵活的适应性。镀液的最佳配方为:铜盐8 g/L,络合剂20 g/L,甲醛10 ml/L,温度50℃,针对不同的树种调节pH在12.4至13之间。
2.镀铜层的厚度可通过施镀时间的变化在一定范围内调节,施镀时间越长,镀铜层的厚度就越大,但超过了一定的时间,镀铜层的厚度就几乎不再增加,没有必要在基材表面继续施镀。另外,根据试验所取的七个树种的镀铜层厚度与施镀时间的关系趋势图可以得出在前10min内镀层厚度增加最快,施镀效果最好。
3.随着镀铜层厚度的增加,木材表面的导电性有明显的提高,同时不同切面各方向上的表面电阻率的值也趋于一致。当达到一定的厚度时,木材表面铜层的导电性能够接近于铜箔的导电性;同时,随着厚度的增加,镀铜层在木材表面的附着强度也有很大的提高。
4.通过X射线衍射图像分析可知,采用此工艺进行非电解镀铜所生成的镀铜层具有十分好的纯度,就表层来说其各项性质已经十分接近于铜箔。
5.从扫描电镜得出的图像来看,木材表面的纹理是影响镀铜层导电性以及表面附着强度的主要因素,可以通过适当增加施镀时间从而增加镀铜层在其内部的积聚量来解决。
With the shining cooper on the surface, wood will appear beautiful grains that have the luster of copper. If the copper is adhered on the wood surface, the surface will have the physical ability of the copper, thereby we could cover more metal on wood surface by more common metal-plating technologies and make the wood surface appear various metal effect. The purpose of this study is to develop electroless copper plating technology which is especially used on the wood surface. In addition, electroless copper plating was analysed to judge its physical character and how it is distributed on the wood surface.Research results are summed up as follows:1. An electroless copper plating technology has been developed. It includes pretreatment means, prescription of plating liquid and processing craft. This processing craft could be used on different wood, so it has good adaptability. The best description of the plating liquid is composed of copper-salt (8g/L), complex (20g/L) and HCHO (10ml/L). The temperature should better be kept by 50℃ and pH is between 12.4 and 13.2. The thickness of copper layer could be adjusted by means of changing plating time. More time is used, more copper is plated, but when plating time is over the limit, the thickness of copper layer will not increase. In addition, according to the trend of relationship between thickness of copper layer and plating time of seven species, the thickness of copper layer increase fastest in the first 10 minutes.3. With the increasing of the thickness of copper layer, the electric ability of the surface is also improved and the exterior resistivity of different surface is also more identical. When the thickness of copper layer is over some value, the electric ability of wood surface is close to that of copper foil and the adhesive intensity is also been improved.4. According to the images of XRD, the copper layer will have great pure degree and the character of it will be close to copper toil if using this craft.5. According to the graph of SEM, the grains on wood surface is main factor that affect the electric ability and the adhesive intensity of copper layer on wood, which could be
resolved by increasing plating time.
引文
1.成俊卿主编.木材学.北京:中国林业出版社,1985:380
2.方晓,宋元伟,赵斌.铜镍复合化学镀.华东理工大学学报,1998,24(1):112～115
3.黄金田,赵广杰.木材的化学镀研究.北京林业大学学报,2004,26(3):88-92
4.黄树坤,邝少林.化学镀铜液中铜离子存在的形式[J].电镀与精饰,1987,9(5):9～11
5.李坚.木材波谱学.北京:科学技术出版社,2002:1～20
6.李宁.化学镀实用技术.北京:化学工业出版社,2004:1～30
7.刘忠传.木制品生产工艺学.北京:中国林业出版社,1993:111～119
8.罗朝晖,朱家琪,黄泽恩.木材/金属复合材料的研究.木材工业,2000,14(6):25～27
9.罗杰·罗维尔主编.实木化学.北京:中国林业出版社,1988:1～60
10.毛尚良,黄杜森.现代表面处理新技术.上海:科学技术出版社,1994:22
11.南京林业大学主编.木材热解工艺学.北京:中国林业出版社,1981:4～23
12.水本省三,绳舟秀美,川崎元雄.无电解铜皮膜机械的性质及热处理影响.金属表面技术,1988,39(6):301
13.王洁瑛,赵广杰.木材变定的产生、回复及其永久固定.北京林业大学学报,1999,21(3):71～77
14.王丽丽编译.化学镀铜工艺.电镀与精饰,2002,24(2):42～43
15.吴宜勇,李桂芝,姚枚等.多元化学镀镍.电镀与环保,1993,13(1):10～13
16.伍学高等.化学镀技术.成都:四川科学技术出版社,1985:52
17.熊海平,萧以德,伍建华等.化学镀铜的进展表面技术,2002,31(6):5～7
18.尹思慈主编.木材学.北京:中国林业出版社,1996:200
19.曾为民,吴纯素,吴荫顺等.化学镀铜.南昌航空工业学院学报,1998,(1):83～93
20.张道礼,龚树萍.化学镀铜中离子型体分布和络合剂的作用[J].材料保护,2000,33(4):3～4
21.张天胜主编.表面活性剂应用技术.北京:化学工业出版社,1985:55
22.赵斌,方晓,毛德芳.化学镀铜新工艺.华东理工大学学报,1997,23(3):367～371
23.長澤長八郎,梅原博行.木材小片無電解前处理工程皮膜析出状態变化.木材学会誌,1992,38(11):1010～1016
24.長澤長八郎,梅原博行.無電解單板導電性、電磁波遮蔽特性及樹種影響.木材学会誌,1991,40(10):1092～1099
25.長澤長八郎,熊谷八百三.Ni木片成形体電磁波特性評価.木材学会誌,1990,36(7):531～537
26.長澤長八郎,熊谷八百三,部啟.Ni单板導電性及電磁波特性.木材学会誌,1991,37(2):158～163
27.長澤長八郎,熊谷八百三.Ni木片用木質系電磁波材.木材学会誌,1989,35(12):1092～1099
28.長澤長八郎,熊谷八百三.前处理工程被覆木材小片用電磁波一材特性变化.木材学会誌,1992,38(3):256～263
29. A. E. Cahill. AESProc., 1957, (44): 130
30. Brenner. A, Riddell. G. E.. Nickel plating on steel by chemical reduction. J. Res. Nat. Bu. Stds, 1946, 37:31～34
31. Brenner A, Riddell G E.. Proc. Am. Electroplater'Soc. 1946, 33:16
32. Brenner A. Met. Finishing., 1954,52(11 ):68
33. Brenner A., Riddell G.E. Proc.AES Annual Tech.Conf., 1946, 33: 16
34. Brenner A., Riddell G.E. Proc.AES Annual Tech.Conf., 1947, 34: 156
35. Brenner A., Riddell G.E. AES Annual Tech.Conf., 1950, 38: 156
36. C.A.Deckert. PlatandSurf. Finish., 1995, 82: 48
37. C.R.Shipley. U.S.Patent3011920. Plating, 1961, 85: 50
38. E.D.Ottavio. U.S. Patent3532518. Plating, 1970, 60: 25
39. F.Pearlstein. Modern Electroplating. Plating, 1974, 20: 12
40. H.Nircus. MetFinish. Plating, 1947, 45: 64
41. M.Gulla, O.B.DutKewych.U.S.patent4, 482,596(1984)
42. M.Gulla, O.B.DutKewych. U.S.patent4, 482,596(1984)
43. Mandich N.V, Krulik G.R. Metal Finishing, 1992, (5) 25
44. Marton J.P., Schlesinger M.J.. Electrochem. Soc, 115,16 (1968)
45. Matsuoka M, Imanishi S. Haysho T.. Plat. Surf. Finish, 1989,76(11): 54
46. NakaharaS,OkinakaY. Experimental Techniques for Studying Physical Aspectsof Electroless Copper Deposits. Proceedings of The Symposiumon Electroless Depositionof Met-alsand Alloys, 1988,18:8-12
47. NakaharaS, OkinakaY. Microstriicture and Mechanical Proper-ties of Electroless Copper Deposits [A]. Annu Rev Mater.Sci[M], 1991, 38: 66
48. P.E.Kukanskis, J.J.Grundwald, D.R.Ferrierand. U.S.Patent4.290331. Plating, 1980, 90: 27
49. R.Goldstein, P.E.Kukanskisand. J.J.Grundwald, U.S.Patent4.265934. Plating, 1981, 100: 33
50. R.L.Coombes. Proc.ASEP. Plating, 1970, 57: 675
51. R.GWedel. Wedel.ibid. Plating, 1975, (62): 40
52. R.M.Lukes. U.S.patent2. Plating, 1964, (51): 1066
53. R.M.Lukes. U.S.patent2.996408. Plating, 1961, (35): 980
2.方晓,宋元伟,赵斌.铜镍复合化学镀.华东理工大学学报,1998,24(1):112～115
3.黄金田,赵广杰.木材的化学镀研究.北京林业大学学报,2004,26(3):88-92
4.黄树坤,邝少林.化学镀铜液中铜离子存在的形式[J].电镀与精饰,1987,9(5):9～11
5.李坚.木材波谱学.北京:科学技术出版社,2002:1～20
6.李宁.化学镀实用技术.北京:化学工业出版社,2004:1～30
7.刘忠传.木制品生产工艺学.北京:中国林业出版社,1993:111～119
8.罗朝晖,朱家琪,黄泽恩.木材/金属复合材料的研究.木材工业,2000,14(6):25～27
9.罗杰·罗维尔主编.实木化学.北京:中国林业出版社,1988:1～60
10.毛尚良,黄杜森.现代表面处理新技术.上海:科学技术出版社,1994:22
11.南京林业大学主编.木材热解工艺学.北京:中国林业出版社,1981:4～23
12.水本省三,绳舟秀美,川崎元雄.无电解铜皮膜机械的性质及热处理影响.金属表面技术,1988,39(6):301
13.王洁瑛,赵广杰.木材变定的产生、回复及其永久固定.北京林业大学学报,1999,21(3):71～77
14.王丽丽编译.化学镀铜工艺.电镀与精饰,2002,24(2):42～43
15.吴宜勇,李桂芝,姚枚等.多元化学镀镍.电镀与环保,1993,13(1):10～13
16.伍学高等.化学镀技术.成都:四川科学技术出版社,1985:52
17.熊海平,萧以德,伍建华等.化学镀铜的进展表面技术,2002,31(6):5～7
18.尹思慈主编.木材学.北京:中国林业出版社,1996:200
19.曾为民,吴纯素,吴荫顺等.化学镀铜.南昌航空工业学院学报,1998,(1):83～93
20.张道礼,龚树萍.化学镀铜中离子型体分布和络合剂的作用[J].材料保护,2000,33(4):3～4
21.张天胜主编.表面活性剂应用技术.北京:化学工业出版社,1985:55
22.赵斌,方晓,毛德芳.化学镀铜新工艺.华东理工大学学报,1997,23(3):367～371
23.長澤長八郎,梅原博行.木材小片無電解前处理工程皮膜析出状態变化.木材学会誌,1992,38(11):1010～1016
24.長澤長八郎,梅原博行.無電解單板導電性、電磁波遮蔽特性及樹種影響.木材学会誌,1991,40(10):1092～1099
25.長澤長八郎,熊谷八百三.Ni木片成形体電磁波特性評価.木材学会誌,1990,36(7):531～537
26.長澤長八郎,熊谷八百三,部啟.Ni单板導電性及電磁波特性.木材学会誌,1991,37(2):158～163
27.長澤長八郎,熊谷八百三.Ni木片用木質系電磁波材.木材学会誌,1989,35(12):1092～1099
28.長澤長八郎,熊谷八百三.前处理工程被覆木材小片用電磁波一材特性变化.木材学会誌,1992,38(3):256～263
29. A. E. Cahill. AESProc., 1957, (44): 130
30. Brenner. A, Riddell. G. E.. Nickel plating on steel by chemical reduction. J. Res. Nat. Bu. Stds, 1946, 37:31～34
31. Brenner A, Riddell G E.. Proc. Am. Electroplater'Soc. 1946, 33:16
32. Brenner A. Met. Finishing., 1954,52(11 ):68
33. Brenner A., Riddell G.E. Proc.AES Annual Tech.Conf., 1946, 33: 16
34. Brenner A., Riddell G.E. Proc.AES Annual Tech.Conf., 1947, 34: 156
35. Brenner A., Riddell G.E. AES Annual Tech.Conf., 1950, 38: 156
36. C.A.Deckert. PlatandSurf. Finish., 1995, 82: 48
37. C.R.Shipley. U.S.Patent3011920. Plating, 1961, 85: 50
38. E.D.Ottavio. U.S. Patent3532518. Plating, 1970, 60: 25
39. F.Pearlstein. Modern Electroplating. Plating, 1974, 20: 12
40. H.Nircus. MetFinish. Plating, 1947, 45: 64
41. M.Gulla, O.B.DutKewych.U.S.patent4, 482,596(1984)
42. M.Gulla, O.B.DutKewych. U.S.patent4, 482,596(1984)
43. Mandich N.V, Krulik G.R. Metal Finishing, 1992, (5) 25
44. Marton J.P., Schlesinger M.J.. Electrochem. Soc, 115,16 (1968)
45. Matsuoka M, Imanishi S. Haysho T.. Plat. Surf. Finish, 1989,76(11): 54
46. NakaharaS,OkinakaY. Experimental Techniques for Studying Physical Aspectsof Electroless Copper Deposits. Proceedings of The Symposiumon Electroless Depositionof Met-alsand Alloys, 1988,18:8-12
47. NakaharaS, OkinakaY. Microstriicture and Mechanical Proper-ties of Electroless Copper Deposits [A]. Annu Rev Mater.Sci[M], 1991, 38: 66
48. P.E.Kukanskis, J.J.Grundwald, D.R.Ferrierand. U.S.Patent4.290331. Plating, 1980, 90: 27
49. R.Goldstein, P.E.Kukanskisand. J.J.Grundwald, U.S.Patent4.265934. Plating, 1981, 100: 33
50. R.L.Coombes. Proc.ASEP. Plating, 1970, 57: 675
51. R.GWedel. Wedel.ibid. Plating, 1975, (62): 40
52. R.M.Lukes. U.S.patent2. Plating, 1964, (51): 1066
53. R.M.Lukes. U.S.patent2.996408. Plating, 1961, (35): 980