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1. Ammonium hydroxide (NH4OH) acts as a complexing agent and holds copper in solution. 2. Ammonium chloride (NH4Cl) increases etch rate, copper-holding capacity, and solution stability. 3. Copper ion (Cu2+) is an oxidizing agent that reacts with and dissolves metallic copper. 4. Ammonium bicarbonate (NH4HCO3) is a buffer and as such retains clean solder holes and surface. 5. Ammonium phosphate [(NH4)3PO4] retains clean solder and plated through-holes. 6. Ammonium nitrate (NH4NO3) increases etch rate and retains clean solder. 7. Additional additives are included in most formulations to enhance speed and/or sidewall protection. Thiourea or its derivatives are often used, although a newer thiourea-free formulation with improved undercut protection is available. 8. Continuous operations consist of single-solution makeup buffered to a pH of 7.5 to 9.5. Alkaline etching solutions dissolve exposed field copper on printed boards by a chemical process of oxidation, solubilizing, and complexing. Ammonium hydroxide and ammonium salts combine with copper ions to form cupric ammonium complex ions [Cu(NH3)42+], which hold the etched and dissolved copper in solution at 18 to 30 oz/gal. Typical oxidation reactions for closed-loop systems are shown by the reaction of cupric ion on copper, and air (O2) oxidation of the cuprous complex ion: Cu + Cu(NH3)42+ 2Cu(NH3)2+ 2Cu(NH3)2+ + 2NH 4+ + 2NH3 + 1 2O2 2Cu(NH3) 42+ + H2O (34.1) (34.2)

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3) to write the last term as b c u a = c b u a + R a dbc u d to obtain D2 a = u b b c c u a + u b c c b u a + R a dbc u d 2 D = u b b c c u a + c u b c b u a + c u b u d R a dbc = b b u c c u a + c u b c b u a + c u b u d R a dbc Relabeling dummy indices, we set c u b c b u a = b u c b c u a and we have D2 a = b b u c c u a + b u c b c u a + c u b u d R a dbc D 2 Now the Leibniz rule b (u c c u a ) = b u c c u a + u c b c u a and so this becomes D2 a = b b u c c u a + b u c b c u a + c u b u d R a dbc D 2 = b ( b u c c u a + u c b c u a ) + c u b u d R a dbc = b ( b (u c c u a )) + c u b u d R a dbc.

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There is strong evidence that the etching rate is dependent on the diffusion of Cu(NH3)2+ from the copper surface (Eq. 34.1) into the bulk of the active solution, where oxidation per Eq. 34.2 occurs.3 Etching can be continued with the formation of Cu(NH3) 42+ oxidizer from air during spray etching and as long as the copper-holding capacity supported by Cl ions is not exceeded. 34.4.1.2 Properties and Control. Early versions of alkaline etchants were batch operated. They had a low copper capacity, and the etch rates dropped off rapidly as copper content increased.4,5,6 It was found to be necessary to add controlled amounts of dissolved oxidizing agents to speed up the rate and increase copper capacity at a constant temperature. Batch operation is no longer supported by commercial suppliers. Etching solutions are operated at 120 to 130 F and are well suited to spray etching. Efficient exhaust systems are required because ammonia fumes are released during operation.7 Etching machines must have a slight negative pressure and moderate exhausting to retain the ammonia necessary for holding dissolved copper in solution. Care must be taken that sufficient fresh air to supply needed O2 is introduced to balance the extraction. Currently available solutions offer constant etching of 1 oz (35 mm) copper in 1 min or less, with a dissolved copper content of 18 to 24 oz/gal.

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