PL109855B1 - Bath for electro-galvanizing and polishing - Google Patents

Bath for electro-galvanizing and polishing Download PDF

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Publication number
PL109855B1
PL109855B1 PL20287177A PL20287177A PL109855B1 PL 109855 B1 PL109855 B1 PL 109855B1 PL 20287177 A PL20287177 A PL 20287177A PL 20287177 A PL20287177 A PL 20287177A PL 109855 B1 PL109855 B1 PL 109855B1
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Poland
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formula
ch2oh
bath
zinc
sodium hydroxide
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PL20287177A
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Polish (pl)
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Publication of PL109855B1 publication Critical patent/PL109855B1/en

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Description

Przedmiotem wynalazku jest kapiel do galwa¬ nicznego cynkowania z polyskiem. Przeznaczona jest do wytwarzania blyszczacych powlok cynko¬ wych w urzadzeniach stacjonarnych i obrotowych.W celu ochrony srodowiska oraz poprawy wa¬ runków BHP pracowników galwanizerni bada sie mozliwosci wyeliminowania soli cyjankowych w procesach elektrolitycznych. Znane bezcyjankowe kapiele do galwanicznego cynkowania z polyskiem " zawieraja cynk, wodorotlenek sodowy i wyblysz- czacz.Znane kapiele alkaliczne nie dzialaja korodu- jaco na urzadzenia i nie daja silnie toksycznych scieków, ale charakteryzuja sie nizsza wglebnos- cia, mniejsza szybkoscia nakladania, a otrzymy¬ wane powloki sa bardziej kruche.Kapiele kwasne oparte na siarczanie cynkowym charakteryzuja sie mala wglebnoscia i stosowane sa glównie do cynkowania prostych powierzchni.Kapiele pirofosforanowe, ze wzgledu na trudna do¬ stepnosc surowców maja ograniczone zastosowanie.Kapiele amonowe ze wzgledu na duze stezenie chlorków posiadaja silne wlasnosci korozyjne.Znane, na przyklad z opisów patentowych PRL nr 87369 i Stanów Zjednoczonych Ameryki nr 3841982, kapiele zawieraja jako wyblyszczacze zwiazki heterocykliczne takie jak furfurol czy zwiazki heterocykliczne typu pirolu z azotem w piecioczlonowym pierscieniu.Znane wyblyszczacze typu zwiazków heterocy- 15 20 25 30 klicznych daja dosc waski zakres polysku powlok i sa nietrwale w srodowisku kapieli alkalicznej.Znane, na przyklad z opisu patentowego RFN nr 1771371, kapiele zawieraja jako wyblyszczacze aldehydy aromatyczne taikie jak wanilina lub al¬ dehyd anyzowy. Znane wyblyszczacze typu alde¬ hydów aromatycznych zapewniaja szeroki zakres polysku ale wbudowuja sie silnie w powloke cyn¬ kowa i zwiekszaja jej kruchosc.Znane, na przyklad z opisu patentowego RFN nr 2628563, kapiele zawieraja jako wyblyszczacze estry kwasu fosforowego.Znane wyblyszczacze typu estrów kwasu fosfo¬ rowego bardzo utrudniaja obróbke scieków.Celem wynalazku jest opracowanie kapieli bez- cyjnakowej do galwanicznego cynkowania z po¬ lyskiem charakteryzujacej sie duzym zakresem po¬ lysku powlok, nie powodowaniem kruchosci po¬ wloki, zapewniajaca latwa obróbke scieków i wy¬ starczajaca trwalosc substancji blaskotwórczej w kapieli.Kapiel do galwanicznego cynkowania z polys¬ kiem wedlug wynalazku stanowi roztwór wodny wodorotlenku sodowego w ilosci 60—150 g/l, cyn¬ ku w ilosci 5—30 g/l i zwiazków o wzorze 1 i o wzorze 2 w stosunku molowym od 2:1 do 10:1 i lacznym stezeniu w kapieli od 0,1 g/l do 6 g/l, zwiazek o wzorze 1 ma budowe polietylenopolia- miny, przy czym n oznacza liczbe od 3 do 10, Ri oznacza NH — CH2OH, NH — CH-jCHsOH lub 109 855109 855 NH — CH2 — CH(OH) — CH2OH zas R2 i R3 oznaczaja ,H albo* CH^OH lub CH2CH2OH albo CH2CH(OH) — CHzOH, zwiazek o wzorze 2 ma strukture polimetylenotiomocznika, przy czym n oznacza liczbe od 1 do 10, podstawnik R4 oznacza jedna ze struktur przedstawionych we wzorze 3, zas podstawnik R5, R8 i R7 oznaczaja niezaleznie od siebie H albo CH2OH lub CH2 — CHgOH albo CH2 — CH(OH) — CH2OH.Stosunek molowy dodatków zwiazków o wzorze 1 i o wzorze 2 korzystnie wynosi okolo 8:1 przy lacznym stezeniu w kapiela 0,1^-6 &AL Doda,tefc przed¬ stawiony wzorem 1 spelnia role nosnika polysku — dziala wyrównujaco i zwieksza wglebnosc ka¬ pieli.Zwiazek o wzorze 2 stanowi zasadniczy dodatek blaskotwórczy i powoduje silnie wyblyszczanie po¬ wloki. Korzystny zakres gestosci pradu miesci sie w granicach od 1—4 A/dim2, a temperatura pracy kapieli od 20 do 35°C.Korzystny sklad i dzialanie kajpdeli wedlug wy¬ nalazku jest wyjasnione blizej w nizej podanych przykladach stosowania.Przyklad I. Sporzadzono kapiel galwaniczna wprowadzajac 15 g/l tlenku cynku, 120 g/l wodo¬ rotlenku sodowego, 4 g/l zwiazku o wzorze 1: HOCHa-NH-CCHsCHsNH^-CHzOH i 0,5 g/l zwiazku o wzorze 2: C8H5-CH=N-(CH2NHCS- -NH)2CH2CH20H.W kapieli umieszczono stalowe obudowy kon¬ densatorów i przeprowadzono proces galwaniczny przy gestosci pradu 3 A/dim2 w ciagu 20 minut.Stwierdzono, ze detale zostaly pokryte na calej 10 15 25 powierzchni powloka cynkowa o wysokim polysku i przecietnej grubosci 12 ^m.Przyklad II. Sporzadzono kapiel zawieraja¬ ca przeliczeniowo 12 g/l tlenku cynkowego, 100 g/l wodorotlenku sodu, 3 g/l zwiazku o wzorze HOCH2CH2NH-(CH2CH2NH)3-CH2CH2OH, i 0,4 g/l zwiazku o wzorze HO-C6H4CH=N-(CH2-NH-CS- -NH)4-CH2OH. Do kapieli wprowadzono sruby w bebnie skosnym. Przepuszczono prad o gestosci 1 A/dm2 w ciagu 45 minut. # Stwierdzono, ze nalozona powloka, o przecietnej grubosci 12 u.m wykazywala wysoki polysk.Zastrzezenie patentowe Kapiel do galwanicznego cynkowania z polys¬ kiem, zawierajaca cynk, wodorotlenek sodowy i wyblyszczacz, znamienna tym, ze zawiera od 5 g/l do 30 g/l cynku, 60—150 g/l wodorotlenku sodo¬ wego, oraz dodatek wyblyszczajacy w postaci zwiazków o wzorze 1 i o wzorze 2 w stosunku molowym od 2:1 do 10:1 i lacznym stezeniu w kapieli od 0,1 g/l do 6 g/l, przy czym podstawniki we wzorach oznaczaja: Ri oznacza — NH-CH2OH lub -NH-CHaCHjPH albo — NH-CH2-CH(OH) — CHgOH, R2 i R3 oznaczaja — H albo — CH2OH lub — CHgCHjjOH albo — CH2CH(OH)CH2OH przy czym n moze wynosic od 3 do '10, R4 oznacza je¬ den z rodników o wzorze 3, a R5, R6 i R7 oznacza¬ ja wodór albo — CHjOH lub — CHgCHgOH albo — CH2-CH(OH)-CH2OH,* przy czym n oznacza licz¬ by od 1 do 10.V CHf CH£- Ijl wzórl HJn R3 CHrN-C-N wzór 2 R. -n=chO ~n=ch~G3"oh ~N=CH-( ^0^ -N-CH-CH-CH-f ) -N=CH^~y0CH8 OH .wzór 3 a b c d PZGraf. Koszalin D-136 90 egz. A-4 Cena 45 zl PLThe subject of the invention is a bath for electroplating with a gloss. It is intended for the production of shiny zinc coatings in stationary and rotary devices. In order to protect the environment and improve the health and safety conditions of electroplating plant workers, the possibility of eliminating cyanide salts in electrolytic processes is being investigated. Known non-cyanide polished zinc plating baths "contain zinc, sodium hydroxide and bleach. Known alkaline baths do not corrode equipment and do not produce highly toxic wastewater, but are characterized by lower depth, lower application speed, and Acid coatings are more brittle. Acid drips based on zinc sulphate are characterized by low depth and are mainly used for galvanizing simple surfaces. Pyrophosphate drips, due to the difficult availability of raw materials, have limited use. Ammonium drips due to the high concentration of chlorides have strong corrosive properties. Baths, known, for example from the patents of the People's Republic of Poland No. 87369 and the United States of America No. 3,841,982, contain heterocyclic compounds such as furfurol or heterocyclic compounds of the type of pyrrole with nitrogen in the five-membered ring. 30 clones give up to Some of the narrow range of gloss of the coatings and they are unstable in the environment of an alkaline bath. Known, for example, from the German patent specification No. 1771371, the baths contain aromatic aldehydes such as vanillin or anisic aldehyde as polishing agents. Known aromatic aldehyde polishers provide a wide range of gloss, but they strongly build into the zinc coating and increase its brittleness. Known, for example, from German patent specification No. 2,628,563, baths contain esters of phosphoric acid as polishing agents. The purpose of the invention is to develop a cyanide-free bath for electroplating with a gloss that has a high gloss range, does not make the coating brittle, ensures easy treatment of the sewage and sufficient durability of the emollient in The bath for electroplating with a gloss according to the invention is an aqueous solution of sodium hydroxide in the amount of 60-150 g / l, zinc in the amount of 5-30 g / l of compounds of formula 1 and formula 2 in a molar ratio of 2: 1 to 10: 1 and a total bath concentration of 0.1 g / l to 6 g / l, the compound of formula 1 has the structure of polyethylene polyamine, where n is from 3 to 10, Ri is NH - CH2OH, NH - CH-CHsOH or 109 855 109 855 NH - CH2 - CH (OH) - CH2OH and R2 and R3 are H or * CH ^ OH or CH2CH2OH or CH2CH (OH) - CHzOH, the compound of formula 2 has the structure of polymethylene thiourea, where n is a number from 1 to 10, R4 is one of the structures shown in formula 3, and R5, R8 and R7 are independently H or CH2OH or CH2 - CHgOH or CH2 - CH (OH) - CH2OH. The molar ratio of the additives of the compounds of formula I and formula 2 is preferably about 8: 1 with a total concentration in the drip of 0.1-6% Al Adda, the tefc represented by formula 1 acts as the gloss carrier. - it has a leveling effect and increases the depth of the bath. The compound of formula 2 is the essential brightening additive and causes a strong shine of the coating. The preferred range of the current density ranges from 1 to 4 A / dim2, and the operating temperature of the bath is from 20 to 35 ° C. The favorable composition and operation of the bath according to the invention is explained in more detail in the application examples below. Example I. A bath was prepared. electroplating with 15 g / l of zinc oxide, 120 g / l of sodium hydroxide, 4 g / l of the compound of formula 1: HOCHa-NH-CCHsCHsNH4 -CH2OH and 0.5 g / l of the compound of formula 2: C8H5-CH = N- (CH2NHCS- -NH) 2CH2CH2OH. In the bath, the steel housing of the capacitors was placed and the electroplating process was carried out at a current density of 3 A / dim2 for 20 minutes. It was found that the details were covered with a zinc coating on the entire surface of high gloss and an average thickness of 12 µm. Example II. A bath was made containing 12 g / l of zinc oxide, 100 g / l of sodium hydroxide, 3 g / l of a compound of formula HOCH2CH2NH- (CH2CH2NH) 3-CH2CH2OH, and 0.4 g / l of a compound of formula HO-C6H4CH = N- (CH2-NH-CS-NH) 4-CH2OH. Screws in the oblique drum were introduced into the bath. A current of 1 A / dm2 was passed in 45 minutes. # It was found that the applied coating, with an average thickness of 12 µm, exhibited a high gloss. Patent Claim. Plaster electroplating bath containing zinc, sodium hydroxide and a rinse aid, characterized by a content of 5 g / l to 30 g / l zinc, 60-150 g / l of sodium hydroxide, and a polishing additive in the form of compounds of formula 1 and formula 2 in a molar ratio from 2: 1 to 10: 1 and a total bath concentration from 0.1 g / l to 6 g / l, where the substituents in the formulas are: Ri is - NH-CH2OH or -NH-CHaCHjPH or - NH-CH2-CH (OH) - CHgOH, R2 and R3 are - H or - CH2OH or - CHgCHjOH or - CH2CH (OH) CH2OH, where n may be from 3 to 10, R4 is one of the radicals of formula III, and R5, R6 and R7 are hydrogen or - CHiOH or - CHgCHgOH or - CH2-CH (OH) -CH2OH, * with n representing a number from 1 to 10.V CHf CH2 - Ij1 formula HJn R3 CHrN-CN formula 2 R. -n = ChO ~ n = Ch ~ G3 "oh ~ N = CH- ( ^ 0 ^ -N-CH-CH-CH-f) -N = CH ^ ~ y0CH8 OH. Formula 3 abcd PZ Graph. Koszalin D-13 6 90 copies A-4 Price PLN 45 PL

Claims (1)

1. Zastrzezenie patentowe Kapiel do galwanicznego cynkowania z polys¬ kiem, zawierajaca cynk, wodorotlenek sodowy i wyblyszczacz, znamienna tym, ze zawiera od 5 g/l do 30 g/l cynku, 60—150 g/l wodorotlenku sodo¬ wego, oraz dodatek wyblyszczajacy w postaci zwiazków o wzorze 1 i o wzorze 2 w stosunku molowym od 2:1 do 10:1 i lacznym stezeniu w kapieli od 0,1 g/l do 6 g/l, przy czym podstawniki we wzorach oznaczaja: Ri oznacza — NH-CH2OH lub -NH-CHaCHjPH albo — NH-CH2-CH(OH) — CHgOH, R2 i R3 oznaczaja — H albo — CH2OH lub — CHgCHjjOH albo — CH2CH(OH)CH2OH przy czym n moze wynosic od 3 do '10, R4 oznacza je¬ den z rodników o wzorze 3, a R5, R6 i R7 oznacza¬ ja wodór albo — CHjOH lub — CHgCHgOH albo — CH2-CH(OH)-CH2OH,* przy czym n oznacza licz¬ by od 1 do 10. V CHf CH£- Ijl wzórl HJn R3 CHrN-C-N wzór 2 R. -n=chO ~n=ch~G3"oh ~N=CH-( ^0^ -N-CH-CH-CH-f ) -N=CH^~y0CH8 OH .wzór 3 a b c d PZGraf. Koszalin D-136 90 egz. A-4 Cena 45 zl PLClaim 1. A hot dip for electroplating with a gloss, containing zinc, sodium hydroxide and a rinse aid, characterized in that it contains from 5 g / l to 30 g / l of zinc, 60-150 g / l of sodium hydroxide, and polishing additive in the form of compounds of formula 1 and formula 2 in a molar ratio from 2: 1 to 10: 1 and a total bath concentration from 0.1 g / l to 6 g / l, with the substituents in the formulas representing: NH-CH2OH or -NH-CHaCHjPH or - NH-CH2-CH (OH) - CHgOH, R2 and R3 are - H or - CH2OH or - CHgCHjjOH or - CH2CH (OH) CH2OH where n can be from 3 to '10 , R4 is one of the radicals of formula III, and R5, R6 and R7 are hydrogen or - CHiOH or - CHgCHgOH or - CH2-CH (OH) -CH2OH, where n is from 1 to 10.V CHf CH £ - Ijl formula 1 HJn R3 CHrN-CN formula 2 R. -n = chO ~ n = ch ~ G3 "oh ~ N = CH- (^ 0 ^ -N-CH-CH-CH-f) -N = CH ^ ~ y0CH8 OH. Formula 3 abcd PZGraf. Koszalin D-136 90 copies A-4 Price PLN 45 PL
PL20287177A 1977-12-12 1977-12-12 Bath for electro-galvanizing and polishing PL109855B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491849B2 (en) 2001-10-16 2009-02-17 Progen Pharmaceuticals, Inc. Oligoamine compounds and derivatives thereof for cancer therapy

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491849B2 (en) 2001-10-16 2009-02-17 Progen Pharmaceuticals, Inc. Oligoamine compounds and derivatives thereof for cancer therapy

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