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31.6.3 Surfactant Reduction in surface tension assures that the plating solution is in intimate contact with the catalyst nuclei and permits thorough surface solution interaction. For this reason, a wetting agent or surfactant is included in bath formulations. Polyethelene oxide, polyethelene glycol (PEG), etc., are popular surfactants. Proper usage of surfactants also prevents the accumulation of gaseous material (air and hydrogen bubbles) on the surface of the board, particularly around the entrances of holes, which would also tend to lower the surface-solution interaction and thus seriously impair proper metal deposition.
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Reliability of Deposited Copper and Inorganic Compounds Generally, copper film with high elongation and reasonable tensile strength is preferred for through-hole reliability, although the relation between through-hole reliability and ductility and tensile strength is still not understood clearly. The use of inorganic compounds containing vanadium or germanium as a part of chemical ingredients in plating baths enhances the quality of deposited copper.13 Most full-build electroless baths used today contain either V2O5 or G2O5 to improve the physical properties of deposited copper. 31.6.4.1 Typical Copper Properties. Typical physical properties of reliable electrolessly plated copper are (as plated): Elongation Tensile strength 8 to 10 percent 35 to 45 kg/mm2
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After annealing the copper, elongation increases to 12 to 18 percent and tensile strength decreases slightly. These properties are equivalent to the ones resulting from acid copper. Since all panels are baked at about 140 to 160 C for 30 to 60 min during the course of the production process after plating, deposited copper gets annealed, thus assuring high through-hole reliability.
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Removal of Impurities Use of continuous filtering has been mentioned to remove some of the impurities. In addition there are other methods. 31.6.5.1 Electrodialysis. Electrodialysis26,27 is effective to remove formate ions, sulfate ions, and carbonate ions which are by-products of reactions defined in Eqs. (31.1), (31.2), (31.3), and (31.5). 31.6.5.2 Overflow Method. Another very effective way to remove these unwanted byproducts is the overflow method. Since essential components of the plating solution are consumed continuously, they must be replenished to maintain desirable plating conditions. In so doing, a considerable amount of the solution overflows because of the addition of water. The overflow also contains the reaction by-products as well as chelated copper ions. After a certain amount of overflow solution is accumulated, sodium hydroxide and formaldehyde are added to the overflow solution and heated to promote spontaneous decomposition of the plating solution to precipitate copper metal. Addition of copper powder accelerates the precipitation. This so-called chemical bomb-out recovery method can be operated in bulk or continuously. The remaining solution can be treated with sulfuric acid to
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recover over 95 percent of the EDTA in the solution. Usually, the purity of EDTA thus recovered is higher than that of purchased EDTA. Ninety-eight percent of the solution is recovered as permeate and is used in such processes as rinsing. The concentrate, the other two percent, is high in salt content (Na2SO4 and HCOONa) and may be evaporated to produce a small amount of solid waste or discharged into the ocean, if the plant is located near the ocean and locally approved.6 This chemical bomb-out method can achieve two objectives at once: removal of unwanted impurities and recovery of chemicals. With this system, it is easy to maintain Baume at the desired 9 . 31.6.6 Environmental Issues of Formaldehyde Formaldehyde is considered to be a carcinogen. If exposed to formaldehyde fumes of certain concentration for a long time, it can cause allergy conditions and perhaps cancer, although cancer due to long-time exposure to formaldehyde in the PWB industry has never been reported. With a good exhaust system and scrubbing through water and peroxide solution, formaldehyde can be made quite harmless. It is a matter of economy. EDTA can be treated as previously mentioned. Reducing agents alternative to formaldehyde such as glyoxylic acid27 and hypophosphite (M3PO2)28 have been suggested and tried, but they have not been able to replace formaldehyde as an effective reducing agent at this stage.
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