R. Balaji* and Malathy Pushpavanam Central Electrochemical Research Institute, Karaikudi ~ 630 006. India *For correspondence: E.mail: rbalas@yahoo.com R, Balaji and M. Pushpavanam, Trans inst Met Fin, 2003, 8115), 154 184 Methanesulphonic acid in electroplating related metal finishing industries SUMMARY ~ During the past ten years, methanesulphonic acid has largely replaced fluoobeé acid as the electrolite of choice forthe electradeposition of tn and tin-lead solder on elect: devices. Certain other electrochemical processes involving lead. most notably the electroeiy of lead by the Bets process, are currently carried out in fuorosiicc acid Based eleciraest those based on methanesulphonic acid (MSA) are being actively investigated as environnens superior alternatives 1 the currently used systems. lls, a number of commercial sri stlie plating operations have recently converted 1p methanesulphorc acid based tir plating elecrobit There are also developing markets for methanesifphonic acid in silver nickel, copper cadnat and zine electroplating. This paper reviews the chemical and physical proper q mmethanesulphonie acid and its current applications in the field of metal finishing and als Supertonity over other electrolytes especialy with respect o environmental pollution Keywords: Methanesulphonic acid, metal plating, waste disposal, environmental benefits, electronies. INTRODUCTION Electroplating processes typically involve electrolytic deposition of a thin coating of a ‘metal onto a conductive substrate. In this, acid based electrolytes are desirable in that they allow for very high solution conductivity and metal ion solubility. Though metal saks are generally soluble in acid electrolytes, some metal salts ie. silver and lead are soluble only 10a limited extent and solubility considerations are paramount in the design aspects of acid electrolytes of such metals, Methanesulphonic acid (MSA) based plating formulations have gained wider popularity over the past decade especially in the electroplating related to the electronic industry! They are replacing the conventional fuoroborate baths, are relatively tess harmful and their waste can be easily treated. In addition, they are stable in acidic, neutral and alkaline solutions and do not undergo any appreciable hydrolysis, regardless of the temperatures used. Since. MSA is less aggressive to the shop environment and equipment, no special requirements are necessary. The baths produce less wastage and sludge formation and cause less oxidation of the metallic species present in the solution. It is possible to use inert anodes and thus the initial investment or capital can be minimised. The baths are not aggressive to ceramic and lasses and produce nodular free deposits which are the main requirement for plating related to electronics. ‘Comparison of some of the properties of rmethanesulphonie acid with sulphuric acid, as given in Table 1, indicates that methanesulphonic acid is less oxidising in nature This property is very much desired in the case of plating of those metals which exist in multivalent states e.g. tin, iron efc., and those operating with additives. Hence, these baths offer the advantege of using insoluble ans ‘Metanesulphonic acid is a strong ax} (pK, = -2), which is completely ionise CHSO,- +H (1) most straightforward method for jucing the simple metal salt involves the tion OF stoichiometric amounts of a base salt with the acid form of the anion of wrest. Typical base metal salts include nates, hydroxides, and oxides. The tions for the preparation of lead and silver eanesulphionic acid are shown in equations and (3), 1022 MeSO,H —» PbYO,SMe)+H,0* CO, (2) 10 + 2 MeSO,H > 2AgO.SMe+H.0. (3) Iss common method of salt manufacture elves ligand metathesis between an acid and acid salt. This method is used in the yation of the silver salt, Inst Met Fin, 2003, 81(5) Metal sulphonates are prepared from their corresponding metal hydroxides. ‘Metal sulphonates are prepared from their corresponding metal carbonates, Metal suiphonates are prepated from their corresponding metal oxides. AgNO, + MeSO,H->AgO,SMe + HNO, (4) where HNO, produced is removed by distillation Another common method for preparation of salts involves chemical or anodic oxidation of the metal of interest in an electrolyte containing the acid form of the desied anion Methods of this type generally avoid the problems associated with the sluggish reaction ff the passive metal oxides, Many metal oxides (e.. precious metal oxides) dehydrate and become passive on standing; it is sometimes more convenient {0 react such oxides immediately. as they are formed For anodie oxidation of a metal in an acid medium, the process can be viewed most simply asthe introduction of the metal cation into solution. Anodic oxidation requires @ method for preventing the metal eation ofthe salt from re-depositing on the cathode. In zeneral. divided electrochemical cells are employed for this puspase, The cells can be divided by simple micropore frits oF more desirably, by anion exchange membranes Silver* and palladium’ methanesulphonates are produced using chemical methods equations (5) and (6) whereas tin and silver methanesulphonates are produced electrochemically, equations (7) and (8). 2ag + HO, + 2 MESO 2 AgOSMe +2 .0(5) 2Pd+ 2 HNO, = 4 MeSOH 2P4(OSMe).~2NO~",0," 30 6) Anode teacion Ag? Age (1) Cte reaton: MESO = @ 91, He» MeSO, (8) We should be noted that _siver ntethanesulphonate isa useful intermediate for the preparation of other metal methanesulphonic acid salts via silver chloride ‘precipitation driven reactions with appropriate metal chlorides, Preparation of tin methanesulphonate for laboratory scale preparations is done in this way", SnCl, + 2AgO,SMe > Sn {O,SMe), > 2AzCL (BY Table II summarises the chemical method of preparation of various sulphonates. Recovery of methanesulphonic acid An electrowinning acid recovery method which allows for the recovery of pure methanesuiphonic acid from corresponding ‘metal sulphonate salts has been developed The process is based on clectrowinning from an anion exchange membrane-divided cel. ‘The anade pracess is O/H’ generation and the cathode process is metal deposition. While similar processes are available for uoroborate and fluorosilicate based electrolytes, these have ‘4 number of practical problems. HBF, and H,SiF, tend to dissociate into BE WF and SiF /HE respectively during transport through ‘change membranes, Such dissociation results inthe formation of more mobile fluoride anions 38 compared t the bulkier luaraborate and fluorosilicate anions. In addition. luoroborate and fluorosilicate undergo hydrolysis reactions in alkaline solutions, and acid recovery catholyte Solutions often become alkaline during the recovery process, Al thinigs considered, the recovery of methanesulphonic acid from metal alkane sulphonates-based ‘wast, i easier than the recovery of fluoraboric acid oF flourosilicic acid from meta uoroncrate and mictal fuorosilicate wastes, respectively Application area Methanesuiphonie acid is an excellent catalyst for esterification’. condensation reactions, for alkylation, olefinic polymerisations and for curing fof conversion coatings. Methanesulphonic acid {is used in petealeum refining. textile treatment and as a solublising agent or as a combination catalyst for reaction mediums. A total of 70 % of methanesulphonic acid produced is used for electrochemical applications and those related to the metah finishing industry are given below: (i) replacement of fluoroboric acid and Tuoroborates in ved and tivlead alloy plating, Gi) wire and steel strip tin plating, 185Table II] Saturation Solubility of Some Lead Salts’ Lead Salts Lead methane sulphonate Pb(O,SMe) Lead fluoroborate, Pb(BF Lead fluorosilicate, PbSiF, 4,0 Lead nitrate, Pb(NO,), Lead perchlorate, Pb{CIO.), 2 Lead chlorate, Pb(CIO,),.H,0 2 Lead acetate, Pb(O,CMe, 5 Lead dithionate, PbS,0,4H,0 1 Aqueous saturation solubility 143 g per 100 g HO (25°C) 50 wt 69 wt. % (20°C) 37 wl % QC) @0'C) 16 g per 100 g H,O, (25°C) 25 g per 100 g H,0, 25°C) 5B per 100 g HO, (25°C) 15 g per 100 g F1,0, 20) Table IV MSA Based Bath Compositions and Operating Conditions" MSA Tin Lead —Silver—-Bismuth Temp — Current Fedm? —lgdm' Igdm! gdm’ Fg dm! 1g dm°C density TA dm? Tin 200-250 ——_ = 2-54 O.1-28 Tin-lead 200-250 61 — 21-29, 0.1-28 (69140) Tin-lead 200-250 24 = 0.1-28 (90/100) Tin-Bismuth 130 = ~ 0.5.2 Tin-Silver pH adjusted 05-1 05-3 to 5 Lead 30-50 36-72 = 21-38 O14 Silver pH adjusted — = —— 500.583 105 (iii) metal finishing of silver, copper, nickel barrelstll plating and high speed reel-to-reel and palladium, plating. iv) immersion and spray stripping of metals such as nickel, tin, lead, tin-lead and cadmiym from copper and its alloys or from zine and its alloys", (9) lead recovery from serap batteries, (vi) electropolishing, (vii) immersion plating, and (vii)regeneration of ion exchange resins, Tin Plating ‘The growing requirements of the electronic industry have prompted an increased interest in tin and tin-alloy plating. Tin plating is used in engineering, communications, military and consumer product applications such as in printed circuit boards, connectors. valves, bearings, semiconductors, transistors, wire and strips. ‘Two types of electrolytes have commonly been used. One is the phenolsulfonie acid based electrolyte popular in Japan, the other, the halide-based electrolyte! popular in the USA. The former generates no chloride or fluoride sludge but has the drawback of poor conductivity. The latter achieves high productivity due to excellent electrolysing properties. but requires the disposal of voluminous amounts of sludge accumulated in the bath. The new methenesulphonic acid bath with special additives enables uniform plating over a wide range of current densities, and achieves productivity equal or superior to that of the halide bath and generates virtually no fluoride sludge, In terms of the chemical ‘oxygen demand (COD) the methanesulphonic acid electrolyte reduced COD to one third that required by the phenolsulphonic acid electrolyte. The versatility of this bath allows the same bath composition and additives for 156 In the halide-tin process, the steel substrate corrosion by the bath and the resulting oxidation of Sn is intrinsic. The bath contains excess amounts of non-reactive ions in Na’. Ch and F>that carry the majority of the current in the bulk electrolyte. The two reactive species Sn and H, account for only 1.76 and 0.05 % of the total current respectively. Thus, the majority of currents are carried by diffusion of Sn® through the concentration sradient across the boundary layer. Since, the ‘migration current carries the negatively charged SnF,- complex away from the cathode, diffusion would be more ertical in the halide process. In the methanesulphonic acid bath, there are only three ionic species, unlike the halide process; 71.3 % of the current in the bulk electrolyte is carried by hydrogen ions migrating to the cathode while ony 3.5 % is carried by Sn?* ons, The remaining 25.2 % of the current is carried by methanesulphonic acid ions migrating to the anode. The conductivity is 176 mS em! for the ‘methanesulphonic acid bath and 129 mS em for halide bath. Smimov and Tyutina’* found ‘that tin reduction without any additive is mass transport controlled and the reaction becomes both mass transport and kinetically controlled ‘when using additives. ‘The Sn’ oxidation rate of the halide bath containing ferrocyanide is 0.45 g dm” hr and the corrosion of steel panels is 3.0 ¢ m? hr In the absence of ferrocyanide the oxidation Tate of steel increases to 4.4 g dar? h whereas that of Sn’ increases drastically to 3.3 g dmv" rl. This demonstrates the deleterious effect ‘of icon on the stability of the halide bath, and the importance of ferrocyanide, which removes all ferrous and ferric ions by forming precipitates of sodium ferrous ferroeati and sodium ferric ferrocyanide. Ths ferrocyanide precipitates and the prepa of sodium fluorostannate, generated y oxidation reaction of stannous ion, fom ha sludge at the bottom of the plating celal recirculation tank. Consequently a halide must be shut down approximately every cit Weeks to remove the accumulated sludge Fe the methanesulphonie acid bath, the oxi rate of the stannous ions is extremely ey, about 0.07 g dm” hr! This low oxidation allows the use of filtration to continuoa remove the precipitate of stannic oxide, ts eliminating the sludge removal operation. low oxidation rate in the methanesulphee| acid bath, however, requires the use of ved insoluble anodes insiead of the soluble anodes normally used in a halide fine ‘maintain the stannous ion eomcentration. Te high corrosiveness of halide baths to the st! substrate requires constant removal dissolved iron from the bath and protein of the structure and equipment in te production line, ‘The MSA baths offer a higher plang efficiency at current densities above 30, dn but a lower efficiency at lower cure densities, The morphology and prefem crystal orientation from the two baths ifferent, which could cause a differencin reflectance and reflow characteristics. Tk coating morphology in the MSA baths ae exhibits a greater variation with the opera, conditions especially below 6 A dmv? Rec of the above factors. the current densi the methanesulphonate bath should be ae 10.4 dm, In electronic applications, bright tn pag is not generally preferred since comnerid processes produce high intemal stress inte deposits along with high organic inclusis which affect the solderablity. Hence, snot satin deposits with good solderabilty andi resistivity and long life are mostly prefered So, research on additives methanesulphonic acid baths is conting Some work by producing large, we poligonised grains with minimum orga inclusions, which are believed to & instrumental in reducing the internal stress root cause of whisker formation. Additvestie catechol suppress the electrvciemical oxide ‘of Sn” ions and the precipitation of tin sbg consisting mostly of stannic compounds: ‘others help in reducing excessive foe formation in the bath!® "™ Itis known that additives can also beust to produce needle-like structures used 2s mo cathodes in the field of vacun microelectronics". Lead plating The design of acid electrolytes for th electroplating of lead and lead alloys, ms importantly tin/lead, is dominated by solubility, performance and environmett considerations. Two important moden technologies depend integrally on the aqueas electrochemistry of lead: these are the electrodeposition of tin/lead solder in th electronics industry and the production ofl acid batteries for the automotive industy. Trans Inst Met Fin, 2003, 815ition. the refining of enide lead obtained mining and/or recycling operations is times cartied out electrolytically. As of ay only fluoroboric acid, fluorosilicie acid methanesulphonic acid based electrolytes fused with commercial success Methanesulphonie acid is functionally and ironmentally superior to fluoroboric ac. lrosilicic avid and other HF complex acids, g. HPF,, HSbF,) as an electrolyte for ctrochemical “processing. In the itochemical cell, metals are electrolytically colved and simultaneously cathodically posited. in a purer form from fluorosiicie d based electrolytes. The substitution of anesulphonic aid for Nuorosicie acid in électroretining of lead offers 3 number of sional and environmental advantages. In i tinlead solder electroplating and lead rorefining, acidic aqueous solutions with Nigh concentration of Pb (II) ions are used. However. only certain acid electrotytes will ow for a high aqueous solubility of Pb (II) These electrolytes include hanesuiphonic acid, fluoroboric acid, silicic acid, nitric acid, perchloric acid brie acid, acetic acid and dithionic aci. The aqueous saturation solubilites of the vant lead salts are shown in Table IIL Various factors make the use of many of e solubility permissible lead electrolytes able. For instance the dithionate anion in i dithionate is unstable at low pH smposing into sulphate and sulphite juzous solutions of lead acetate in pbination with acetic acid have insufficient ctivity to allow for high-speed coplating operations. ead chlorate, lead chlorate and lead nitrate all tend to mpose cathodically and the corresponding isare very corrosive. The methanesulphonate ion forms less iclead complexes than do the fluoroborate, silicate and associated fluoride ions. The lxing nature of the aforementioned anions it difficult to efficiently remove lead ions in effluent streams. By far the most mon method of dealing with metal sining aqueous effluent solutions is by sic precipitation of the metal oxide owed by filtration. ‘The caustic iptation of lead, for instance, is shown uation (10). Pb" + 2X- + 2NaOH—> PhO +H,O + 2NaX, (10) insoluble lead oxide formed is removed 2 the aqueous effluent by filtration cally. the residual level of lead left in an ent after a caustic precipitation operation ireaty related to the complexing ability of ions present in the effluent. ‘The residual il of soluble Pb(II) in solution alter ised caustic precipitation of lead from tanesulphonic acid (aqueous) based lead or sin plating solutions is less than 1. ppm, ie the residual level of soluble Pb(II) left olution after caustic precipitation of lead fluoroborie acid (aqueous) based ions is typically more than ten times as (spelato ef al.', from their study on the fi dissolution of lead in MSA concluded Inst Met Fin, 2003, 81(5) that the later has a tendency to form stepwise complexes with lead (11) ions in moderate acid solutions, Three Yead—_(11) methanesulphonate complexes have been characterised as predominant species in the ligand concentration of range 0.2-2,0 M. In electroplating baths where the concentration levels are high, various soluble species are in equilibrium, Hsuen and Wan studied the anodic dissolution of lead in MSA and found that the reduetion of lead is diffusion controlled and there is no sulphonate ion involved in the charge transfer reaction, with the lead ion existing in the completely dissociated state Lead methanesulphonate baths are used in the plating of bearings, connectors, and as intemal and conforming anodes for chromium plating valves, and for parts of storage batteries", Leaditin Plating The advantages of methanesulphonic acid are evidenced by its recent substitution for Auorobori acid inthe commercially important electroplating of ivlead solder. In this process acidic aqueous solutions of Sn, Pb, free acid and surface-actve additives are employed. From these carefully formulated rmethanesulphonic acid based electroplating solutions itis possible to produce solderable Lin/lead coatings with specific properties (appearance, alloy content, thickness, ductility, eve.). Such engineered tin/lead coatings are for example. deposited on the connecting pins of electrical devices, where they function, among other things, to protect the connecting pins from oxidation and the associated loss of solderabiliny: Solderable tinvlead coatings are also sometimes electroplated onto printed circuit boards as part of the fabrication process. and tin or tin/lead is electroplated onto wire as @ solderable and corrosion inhibiting coating. A number of industrial electrochemical processes sill employ fhiroboric andr fuorosilci acid based electrolytes. For many of these applications, active research programs aimed at replacing the luoric acid complex acid with rwthanesulphonie acid are in place The main drawback of pure tin deposits is the formation of whisker growth that is normally controlled by alloying it with a small amount of lead. Alloys of lead with tn ranging in composition from 10-93 % lead, used for various purposes are produced from MSA baths: 60% fin and 40% lead alloys are used as solder on PCBs, connectors and other specialised devices. Deposits are ether dull or bright coatings according to the additive nature and concentration. The baths operate at lower additive concentration than fluoroboric acid baths. Methamesulphoniec acid solutions are similar tg HBF, in that on PCBs lowering the metal content ofthe solution and increwsing the acid content can augment throwing power ‘The latest flip chip technology relies on solder bumps produced on silicon chips for interconnection. Though solder bumps can be produced by vapour deposition and screen printing as well as by electroplating, only electroplating allows the manufacturing of fine- pitch small volume solder bumps. Solder plating needs to be controlled to produce uniform solder bumps. A chip may eontain hundreds of bump pads. Because a wafer contains tnndreds of chips, it ean be assumed that thousands of solder bumps willbe plated simultaneously during the plating process. It is reported that solder bumps produced from MSA baths have uniform bump height and are smooth®. It is also reported that laser enhanced electrodeposition of lead-tin Solder from MSA baths yield deposits with good surface morphology at a reduced overpotential. Use of pulse current yields ‘mote uniform and smooth deposits compared to the direct current process! *, Copper-lead-tin alloys These alloys. produced from MSA-based electrolytes are presently used as lubricating coatings in bearings but may find application in electronies in future, Some of the bath compositions used for depositing alloys are given in Table IV. Lead-free depository Tin Alloys The use of tin-lead solders for the formation of solder joints in the production of electronic equipment is a known technology, but the environmental risk resulting from the use of lead forces a substitution. There is a potential risk of environmental contamination when discarded electronic equipment with tin-lead solder joints is deposited in landiills. For this reason consideration is being given to substituting lead in this field ‘Any alternative for lead has to match the profile of requirements ofthe existing tin-lead solders and the technological properties of the interconnections must not be negatively influenced. It is also important that the alternative solders can be used with the existing assembly technologies, One important requirement in this connection is the melting point of the solder. Any alternative to lead should give a melting point or melting-range. which is similar to the existing tn-lead solders. High soldering temperatures are unsuitable, because they can cause an intolerable high ‘thermal stress on the component, Furthermore the search for lead-free solders has also to consider the availability and the costs of the possible alternatives, Possible candidates for soft-solders using a tin-base are those where tin is alloyed with the metals like bismuth, indium, silver, zine and antimony. Tin-bismuth” * and tin- silver” are the most preferred as copper-tin suffers from the problem that measuring the alloy composition on the actual parts by XRF is not possible for copper substrates because of the interference from the base metal. Both preferred alloys are being produced adopting MSA formulation” Immersion tin coatings Recently the immersion tinning of copper tubes for drinking water purposes, has been ziven special consideration because of copper contamination in water above the permissible limits. While the formation of immersion coating by conventional hydrochloric acid takes place semi-coherently, those formed 187from MSA baths are formed as nanocrystals showing preferred orientation, and have compact and regular surface morphology". ‘The maximum thickness that can be obtained is around 1.5 wm which also might have applications in electronics, Silver plating Silver plating is widely used in interconnector because it provides high electrical conductivit good corrasion resistance and good soldering properties. To dispense with the conventional cyanide baths, MSA base formulations are emerging With the help of additives, white silver deposits, comparable with those produced from eyanide bath in all respects has become possible”, CONCLUSIONS Meethanesulphonic acid hased formulations are finding increasing interest in plating especially in the area of electronics. 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