RS20090102A - A novel additive for chromium electrolytes - Google Patents

A novel additive for chromium electrolytes

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Publication number
RS20090102A
RS20090102A RSP-2009/0102A RSP20090102A RS20090102A RS 20090102 A RS20090102 A RS 20090102A RS P20090102 A RSP20090102 A RS P20090102A RS 20090102 A RS20090102 A RS 20090102A
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RS
Serbia
Prior art keywords
additive
chromic acid
chromium
acid solution
application
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RSP-2009/0102A
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Serbian (sr)
Inventor
Lorenz Läser
Matthias Weiss
Frank Honselmann
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Tib Chemicals Ag.
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Publication date
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Publication of RS20090102A publication Critical patent/RS20090102A/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Primary Cells (AREA)

Abstract

The fluoride surfactant-free, long-term stable and biodegradable additive for chromic acid solutions lowers the surface tension and thus enhances the separation process of the chromium, particularly when used with electrolytic chroming. Preferred additives are CH3(CH2)nSO3H and the salts thereof wherein n = 10 to 18.

Description

NOVI ADITIV ZA HROMNE ELEKTROLITENEW ADDITIVE FOR CHROMIC ELECTROLYTES

Ovaj pronalazak se odnosi na oblast aditiva za hromne elektrolite, naročito na oblast aditivnih površinski aktivnih materija za hromne elektrolite kao i na oblast aditiva za polimerna metaliziranja. This invention relates to the field of additives for chromium electrolytes, especially to the field of additive surfactants for chromium electrolytes, as well as to the field of additives for polymer metallization.

Za elektrolitičko hromno prevlačenje (hromiranje) koje se tipično vrši u hromnim elektrolitima pri visokoj koncentraciji agresivne hromne kiseline, predložen je širok izbor različitih aditiva u cilju sprečavanja formiranja agresivnih raspršenih (sprejnih) magli. Međutim, nađeno je da je u praksi teško naći jedinjenja, koja, s jedne strane imaju povoljne osobine (karakteristike), ali se, s druge strane, održavaju pod ovim agresivnim uslovima u hromnom prevlačenju (hromiranju). For electrolytic chromium plating (chroming), which is typically performed in chromium electrolytes with a high concentration of aggressive chromic acid, a wide variety of different additives have been proposed in order to prevent the formation of aggressive spray mists. However, it was found that in practice it is difficult to find compounds, which, on the one hand, have favorable properties (characteristics), but, on the other hand, are maintained under these aggressive conditions in chrome plating (chroming).

Naročito pogodni za smanjenje raspršene (sprejne) magle su agensi za kvašenje koji formiraju penu i koji, smanjenjem površinskog napona, ne samo da smanjuju sprejne (raspršene) gubitke već takođe u velikoj meri smanjuju unošenje (povlačenje za sobom) hromnog elektrolita. Za ovu svrhu je predložen širok izbor (niz) različitih produkata, na primer, perfluoralkilsulfonske kiseline (PFOAs). Ovi produkti su takođe stabilni prema visoko oksidativnim osobinama hromne kiseline. Međutim, njihova upotreba je problematična i već je zabranjena u mnogim aplikacijama (primenama). Ove fluorne površinski aktivne materije nisu biološki razgradijive, jer ne podležu ma kakvoj fotolitičkoj, hidrolitičkoj, oksidativnoj ili reduktivnoj transformaciji. One se biološki ne razgrađuju bilo aerobno niti anaerobno. Zahvaljujući njihovim fizikohemijskim osobinama, perfluoralkilsulfonske kiseline ostaju kao krajnji metaboliti i dalje se ne razgrađuju. Especially suitable for reducing spray mist are wetting agents which form foam and which, by lowering the surface tension, not only reduce spray losses but also greatly reduce entrainment (entrainment) of chromium electrolyte. A wide variety of different products have been proposed for this purpose, for example, perfluoroalkylsulfonic acids (PFOAs). These products are also stable to the highly oxidizing properties of chromic acid. However, their use is problematic and is already prohibited in many applications. These fluorine surfactants are not biologically degradable, because they do not undergo any photolytic, hydrolytic, oxidative or reductive transformation. They are not biologically degraded either aerobically or anaerobically. Thanks to their physicochemical properties, perfluoroalkylsulfonic acids remain as final metabolites and are not further degraded.

DE 1034945 je predložila alkilmetilsulfonate kao aditive, za koje je rečeno da imaju osobine kao neka površinski aktivna materija i simultano proizvode uticaje koji unapređuju postupak sa aspekta glačanja (poliranja) hromnog sloja. Međutim, ovi aditivi su nepogodni u praksi, jer se razlažu u toku hromnog prevlačenja (hromiranja) u vrlo kratkom vremenskom periodu. DE 1034945 proposed alkylmethylsulfonates as additives, which were said to have surfactant-like properties and simultaneously produce process-enhancing effects from the aspect of polishing the chrome layer. However, these additives are unsuitable in practice, because they break down during chrome plating (chroming) in a very short period of time.

Otuda je zadatak ovog pronalaska da pronađe aditiv za hromne elektrolite koji smanjuje gore detaljno navedene nedostatke. Hence, it is the object of the present invention to find an additive for chromium electrolytes which reduces the disadvantages detailed above.

Ovaj zadatak je postignut sa aditivom prema zahtevu 1. Prema tome, dat je aditiv, naročito polirajući (glačajući) aditiv za hromne elektrolite, naznačen time, što rastvor hromne kiseline koji sadrži 0,1 g/l aditiva i 250 g/l hromne kiseline ima površinski napon š 30 mN/m i 0,1 g/l aditiva pri 45°C i 6000 Ah protoka naelektrisanja u rastvoru hromne kiseline koji sadrži 270 g/l hromne kiseline, ima stabilnost od > 4 h. This task is achieved with the additive according to claim 1. Therefore, an additive is provided, in particular a polishing (ironing) additive for chromic electrolytes, characterized in that a chromic acid solution containing 0.1 g/l of the additive and 250 g/l of chromic acid has a surface tension of 30 mN/m and 0.1 g/l of the additive at 45°C and 6000 Ah charge flow in the chromic acid solution containing 270 g/l chromic acid, has a stability of > 4 h.

Treba primetiti da se termin „aditiv" u okviru ovog pronalaska može odnositi bilo na pojedinačnu supstancu ili na smešu supstanci; međutim, zbog razloga čitljivosti i jasnoće, u okviru ovog pronalaska, termin „aditiv" se samo odnosi na aditiv u jednini. Ako je upotrebijeni aditiv smeša supstanci, što znači u svakom slučaju da ova smeša supstanci ima opisane osobine, ali ove pojedinačne komponente ove smeše takođe mogu imati opisane osobine. It should be noted that the term "additive" within the scope of this invention may refer either to a single substance or to a mixture of substances; however, for reasons of readability and clarity, within the scope of this invention, the term "additive" only refers to additive in the singular. If the additive used is a mixture of substances, which means in any case that this mixture of substances has the described properties, but these individual components of this mixture can also have the described properties.

U kontekstu ovog pronalaska, termin „stabilnost" naročito označava trajnu efikasnost aditiva u pogledu površinskog napona pod hemijski zahtevnim uslovima nekog hromnog elektrolita. In the context of the present invention, the term "stability" particularly means the continued effectiveness of the additive in terms of surface tension under the chemically demanding conditions of a chromium electrolyte.

Naročito, u kontekstu ovog pronalaska, termin „stabilnost" u toku nekog perioda znači da se površinski napon povećava za ne više od 5 mN/m u toku tog vremena. In particular, in the context of the present invention, the term "stability" over a period means that the surface tension increases by no more than 5 mN/m during that time.

Naročito, u kontekstu ovog pronalaska, pod terminima „hromni elektroliti" i/ili „operacije rastvora hromne kiseline" se podrazumeva da označavaju hromne elektrolite ili rastvore hromne kiseline koji sadrže katalizatore i/ili dalje kiseline. In particular, in the context of the present invention, the terms "chromic electrolytes" and/or "chromic acid solution operations" are understood to mean chromic electrolytes or chromic acid solutions containing catalysts and/or further acids.

Neočekivano je nađeno da kada se takav jedan aditiv doda rastvorima hromne kiseline u operacijama hromnog prevlačenja (hromiranja), u većini aplikacija ovog pronalaska, može se postići najmanje jedna, obično više nego jedna od sledećih prednosti: - Upotreba pronalazačkog aditiva poboljšava (unapređuje) operaciju hromnih elektrolita na trajan način. - Upotreba ovog aditiva vodi do formiranja značajno manjih gasnih mehura, što je povezano sa drastičnim smanjenjem u štetnoj emisiji. - Takođe je moguće da se značajno smanje gubici unošenja (povlačenja za sobom). - U zavisnosti od ovog postupka, kada se upotrebljava ovaj aditiv, poboljšava se disperzibilnost elektrolita u mnogim aplikacijama. - Ovaj aditiv ne deluje štetno na osobine ovog sloja, čak ni u pogledu karakteristika sloja kao što su tvrdoća, međuprostor (pukotina) mreže, struktura, itd. It has unexpectedly been found that when such an additive is added to chromic acid solutions in chromium plating (chroming) operations, in most applications of the present invention, at least one, usually more than one, of the following advantages can be achieved: - The use of the inventive additive improves (improves) the chromium electrolyte operation in a permanent manner. - The use of this additive leads to the formation of significantly smaller gas bubbles, which is associated with a drastic reduction in harmful emissions. - It is also possible to significantly reduce entrainment losses (withdrawal). - Depending on this procedure, when this additive is used, the dispersibility of the electrolyte is improved in many applications. - This additive does not adversely affect the properties of this layer, even with regard to the characteristics of the layer such as hardness, interspace (crack) network, structure, etc.

Rastvor hromne kiseline koji sadrži 0,1 g/l aditiva i 250 g/l hromne kiseline pogodno ima površinski napon od £ 28 mN/m, čak pogodnije £ 25 mN/m. A chromic acid solution containing 0.1 g/l additive and 250 g/l chromic acid conveniently has a surface tension of £28 mN/m, even more suitably £25 mN/m.

Rastvor hromne kiseline koji sadrži 0,1 g/l aditiva i 400 g/l hromne kiseline pogodno ima površinski napon od £ 35 mN/m, čak pogodnije ^ 30 mN/m. A chromic acid solution containing 0.1 g/l additive and 400 g/l chromic acid conveniently has a surface tension of £ 35 mN/m, even more suitably ^ 30 mN/m.

0,1 g/l aditiva pri 45°C u hromnom elektrolitu koji sadrži 270 g/l hromne kiseline pogodno ima stabilnost od ^ 8 h, čak pogodnije od ^ 12 h. 0.1 g/l additive at 45°C in a chromic electrolyte containing 270 g/l chromic acid conveniently has a stability of ^ 8 h, even more conveniently of ^ 12 h.

U jednom pogodnom oličenju ovog pronalaska, ovaj aditiv je bez fluornih površinski aktivnih materija. Ovo podrazumeva da znači naročito da ovaj aditiv ne sadrži bilo koje organofluorno jedinjenje ili da je proporcija organofluornih jedinjenja u ovom aditivu ispod granice detekcije. In one preferred embodiment of the present invention, this additive is free of fluorine surfactants. This implies that it means in particular that this additive does not contain any organofluorine compounds or that the proportion of organofluorine compounds in this additive is below the detection limit.

U jednom pogodnom oličenju ovog pronalaska, ovaj aditiv je biološki razgradljiv. Ovo podrazumeva da znači naročito da, prema kriterijumima OECD, ^ 99,5%, pogodno ^ 99,8% ovog aditiva se degradira (razgrađuje) u testu sortiranja (klasifikovanja) posle 8 dana. U mnogim aplikacijama, takav jedan aditiv doprinosi da se minimizira trošak (rashod) u pogledu sprečavanja kontaminacije životne okoline, ili čak da ga učini potpuno suvišnim. In one preferred embodiment of the present invention, this additive is biodegradable. This implies that it means in particular that, according to the OECD criteria, ^ 99.5%, suitable ^ 99.8% of this additive is degraded (decomposed) in the sorting (classification) test after 8 days. In many applications, such an additive contributes to minimize the cost (expenditure) in terms of preventing environmental contamination, or even to make it completely redundant.

Hromni elektrolit koji sadrži 0,1 g/l aditiva i 250 g/l hromne kiseline pogodno ima gustinu struje od ^ 30 A/dm<2>do £ 60A/dm<2>, čak pogodnije ^ 40 A/dm2 do ^ 50 A/dm<2>. The chromium electrolyte containing 0.1 g/l additive and 250 g/l chromic acid suitably has a current density of ^ 30 A/dm<2> to £ 60 A/dm<2>, even more suitably ^ 40 A/dm2 to ^ 50 A/dm<2>.

Hromni elektrolit koji sadrži 0,2 g/l aditiva i 350 do 400 g/l hromne kiseline pogodno ima gustinu struje od ^ 5 A/dm<2>do ^ 25 A/dm<2>, čak pogodnije ^ 8 A/dm2 do £ 20 A/dm<2.>Chromic electrolyte containing 0.2 g/l additive and 350 to 400 g/l chromic acid conveniently has a current density of ^ 5 A/dm<2> to ^ 25 A/dm<2>, even more suitably ^ 8 A/dm2 to £ 20 A/dm<2>.

U jednom pogodnom oličenju ovog pronalaska, ovaj aditiv sadrži materijal odabran iz grupe dugolančanih In one preferred embodiment of the present invention, this additive comprises a material selected from the group of long chain

alkilmonosulfonskih kiselina, dugolančanih alkildisulfonskih kiselina, dugolančanih alkilpolisulfonskih kiselina, soli dugolančanih alkilmonosulfonskih kiselina, soli dugolančanih alkildisulfonskih kiselina, soli dugolančanih alkylmonosulfonic acids, long-chain alkyldisulfonic acids, long-chain alkylpolysulfonic acids, salts of long-chain alkylmonosulfonic acids, salts of long-chain alkyldisulfonic acids, salts of long-chain

alkilpolisulfonskih kiselina i njihovih smeša. alkyl polysulfonic acids and their mixtures.

U ovom kontekstu, pod terminom „dugolančani" se podrazumeva da označava C4i veće (lance). Dugolančani alkil-radikali su pogodno neračvasti, ali je takođe moguće da se upotrebe račvaste alkilmono-, -di- i -polisulfonske kiseline i njihove soli. In this context, the term "long-chain" is understood to mean larger C4i (chains). Long-chain alkyl radicals are preferably unbranched, but it is also possible to use branched alkyl mono-, -di- and -polysulfonic acids and their salts.

Soli upotrebijene u pogodnom oličenju ovog pronalaska su alkalnometalne soli, zemnoalkalnometalne soli, NH4<+>soli, NR4<+>soli (gde je R = alkil) i njihove smeše. Salts used in a suitable embodiment of this invention are alkali metal salts, alkaline earth metal salts, NH 4<+> salts, NR 4<+> salts (where R = alkyl) and mixtures thereof.

U jednom pogodnom oličenju ovog pronalaska, ovaj aditiv sadrži (obuhvata) kao najmanje jednu njegovu komponentu, jedinjenje CH3 (CH2) nS03H ili njegove soli, gde je n ^ 10 i n £ 18. U praksi, ova jedinjenja često imaju naročito povišenu stabilnost i povoljna su sa tog aspekta. In one suitable embodiment of this invention, this additive contains (comprises) as at least one of its components, the compound CH3 (CH2) nS03H or its salts, where n ^ 10 and n £ 18. In practice, these compounds often have a particularly increased stability and are advantageous from that aspect.

Pogodnije, ovaj aditiv sadrži (obuhvata), kao najmanje jednu komponentu, jedinjenje CH3 (CH2)nS03H ili njegove soli, gde je n ^ 12 i n £ 17; čak pogodnije, ovaj aditiv sadrži (obuhvata), kao najmanje jednu komponentu, jedinjenje CH3 (CH2)nS03H ili njegove soli, gde je n ^ 14 i n £ 16. More conveniently, this additive contains (comprises), as at least one component, the compound CH3 (CH2)nS03H or its salts, where n ^ 12 and n £ 17; even more conveniently, this additive contains (comprises), as at least one component, the compound CH3 (CH2)nS03H or its salts, where n ^ 14 and n £ 16.

Ovaj pronalazak se takođe odnosi na primenu pronalazačkog aditiva kao agensa za poliranje (glačanje) u hromnim elektrolitima. U jednom pogodnom oličenju ovog pronalaska, koncentracija aditiva je između ^ 0,05 g/l i £ 20 g/l, pogodnije £ 0,1 g/l i £ 10 g/l, i najpogodnije ^ 1 g/l i ^ 3 g/l. This invention also relates to the use of the inventive additive as a polishing (ironing) agent in chromium electrolytes. In one suitable embodiment of the present invention, the concentration of the additive is between ^ 0.05 g/l and £ 20 g/l, more suitably £ 0.1 g/l and £ 10 g/l, and most suitably £ 1 g/l and £ 3 g/l.

Ovaj pronalazak se takođe odnosi na upotrebu (primenu) pronalazačkog aditiva kao aditiva u polimernim nagrizajućim sredstvima (močilima). Ovi pronalazači su našli, da se neočekivano, pronalazački aditiv može koristiti ne samo u hromnim elektrolitima već takođe u prethodnom tretmanu polimernih metaliziranja. U ovim nagrizajućim sredstvima (močilima), ovaj aditiv ima efekt kvašenja i smanjuje površinski napon ovih nagrizajućih sredstava (močila) koja sadrže hromnu kiselinu. Pozitivni uticaj na formiranje magle hromne kiseline i unošenje (povlačenje za sobom) je uporedljiv sa efektima koji su gore opisani za hromne elektrolite. This invention also relates to the use (application) of the inventive additive as an additive in polymeric etching agents (wets). These inventors have found, unexpectedly, that the inventive additive can be used not only in chromium electrolytes but also in the pretreatment of polymer metallizations. In these mordants, this additive has a wetting effect and reduces the surface tension of these mordants containing chromic acid. The positive effect on chromic acid mist formation and entrainment is comparable to the effects described above for chromic electrolytes.

Ovaj pronalazak se takođe odnosi na upotrebu (primenu) aditiva koji sadrži (obuhvata), kao najmanje jednu komponentu, jedinjenje CH3 (CH2) nS03H ili njegove soli, gde je n M0 i n ^ 18, pogodnije n M2 i n ^ 17, čak pogodnije n M4 i n ^ 16, ili njihove smeše kao aditiv u polimernim nagrizajućim sredstvima (močilima) . This invention also relates to the use (application) of an additive that contains (comprises), as at least one component, the compound CH3 (CH2) nS03H or its salts, where n M0 and n ^ 18, more suitable n M2 and n ^ 17, even more suitable n M4 and n ^ 16, or their mixtures as an additive in polymeric corrosive agents (mortars).

Gore pomenute komponente koje se trebaju primeniti prema ovom pronalasku i one koje su zahtevane i opisane u radnim primerima nisu predmet bilo kakvih naročitih izuzetnih uslova u pogledu njihove veličine, trodimenzionalne konfiguracije, selekcije materijala i tehničke konstrukcije (dizajna), tako da se selekcioni kriterijumi koji su poznati u ovoj oblasti mogu primeniti bez restrikcije. The above-mentioned components to be applied according to the present invention and those that are required and described in the working examples are not subject to any particular exceptional conditions regarding their size, three-dimensional configuration, material selection and technical construction (design), so that the selection criteria that are known in this field can be applied without restriction.

Dalji detalji, osobine i prednosti predmeta (sadržaja) ovog pronalaska su evidentni iz podzahteva i iz opisa pronalazačkog primera koji sledi, u kojem je - na čisto ilustrativan i neograničavajući način - detaljno opisana jedna primena (upotreba) pronalazačkog aditiva. Further details, properties and advantages of the subject matter (content) of this invention are evident from the subclaims and from the description of the inventive example that follows, in which - in a purely illustrative and non-limiting way - one application (use) of the inventive additive is described in detail.

Primer I: Example I:

U kupatilu koje sadrži 400 g/l hromne kiseline, 5 g/l fosforne kiseline, 3 g/l kalijum-nitrata, 3 g/l fluorida retkih zemalja (npr., cerijuma, lantana) i, kao pronalazački aditiv, 2 g/l natrijum-pentadekansulfonata, pri temperaturi od 20-25°C i gustini struje od 20 A/dm<2>izvršeno je prevlačenje (hromiranje) sa crnim hromom. In a bath containing 400 g/l of chromic acid, 5 g/l of phosphoric acid, 3 g/l of potassium nitrate, 3 g/l of rare earth fluorides (e.g., cerium, lanthanum) and, as an inventive additive, 2 g/l of sodium pentadecane sulfonate, at a temperature of 20-25°C and a current density of 20 A/dm<2>, coating (chroming) was carried out with black chrome.

Dodatkom ovog pronalazačkog aditiva bilo je moguće da se smanji površinski napon do vrednosti od 29,8 mN/m. By adding this inventive additive, it was possible to reduce the surface tension to a value of 29.8 mN/m.

U sledećim (priključenim) istraživanjima je nađeno da je deponovan (prevučen) hromni sloj imao vrlo uniformni izgled. Naročito je poboljšana disperzibilnost elektrolita. Testiranje nekoliko limova je dalo disperziju hromnog sloja koja je poboljšana u prošeku od 1,0-1,5 cm prema odgovarajućim testovima u Hull-ovoj ćeliji. In the following (attached) investigations, it was found that the deposited (coated) chrome layer had a very uniform appearance. The dispersibility of the electrolyte is particularly improved. Testing of several sheets gave a chromium layer dispersion that was improved by an average of 1.0-1.5 cm according to the corresponding Hull cell tests.

MATERIJALI I METODE MERENJA MATERIALS AND MEASUREMENT METHODS

Površinski napon je meren sa K8 tenzimetrom (instrumentom za merenje napona pare) iz firme Kruss u Hamburgu. Ovaj aparat radi prema Du Noiiv-vom postupku sa prstenom. Meri se sila tečne lamele koja se pomoću prstena povlači na gore. Tečnost se podiže sve dok postoji kontakt ovog prstena sa površinom. Pomoću torzione vage se meri sila potrebna da se podiže platinski prsten. Ova je utoliko veća Sto se dalje vuče prsten iz ove tečnosti. Na tački primenjene najveće sile, kada se prekida lamela, postoji ravnoteža sila iz koje se može izračunati površinski napon ove tečnosti. Geometrija prstena se uzima u obzir (račun) pomoću specifične kalibracije instrumenta izvršene od strane proizvođača. Surface tension was measured with a K8 tensiometer (instrument for measuring vapor tension) from Kruss in Hamburg. This apparatus works according to Du Noiiv's ring procedure. The force of the liquid lamella, which is pulled upwards by means of a ring, is measured. The liquid rises as long as there is contact of this ring with the surface. A torsion balance is used to measure the force required to lift the platinum ring. This one is all the bigger the further the ring is pulled out of this liquid. At the point of the greatest applied force, when the lamella breaks, there is a balance of forces from which the surface tension of this liquid can be calculated. The geometry of the ring is taken into account (calculation) by means of a specific calibration of the instrument performed by the manufacturer.

Gustina struje se određuje merenjem jačina struje sa ampermetrom i upućivanjem na poznatu geometriju površine komponenata koje treba prevući hromom (hromirati). The current density is determined by measuring the current strength with an ammeter and referring to the known geometry of the surface of the components that should be coated with chrome (chrome).

Disperzibilnost elektrolita se određuje izračunavanjem (procenjivanjem) limova posle testova sa elektrolitom u Hull-ovoj ćeliji. Disperzija hromnog sloja se određuje merenjem ekspanzije (širenja) prevučene površine na limu nakon što je ovaj prošao operaciju (radnju) testa. Merenje se vrši lenjirom. Uopšte se prevlači nekoliko limova i mere pod istim uslovima da se dobiju pouzdane srednje vrednosti. The dispersibility of the electrolyte is determined by calculating (estimating) the sheets after tests with the electrolyte in a Hull cell. The dispersion of the chromium layer is determined by measuring the expansion (expansion) of the coated surface on the sheet after it has undergone the operation (action) of the test. Measurement is done with a ruler. Generally, several sheets are coated and measured under the same conditions to obtain reliable mean values.

Claims (6)

1. Aditiv za vodene rastvore hromne kiseline, naznačen time, što je bez fluornih površinski aktivnih materija i što je biološki razgradijiv, što je CH3(CH2)nS03H ili njena so, gde je n 12 do 17, pri čemu je pomenuta površinski aktivna materija jedina površinski aktivna materija i koji ima u rastvoru hromne kiseline koji sadrži pomenuti aditiv površinski napon od £ 35 mN/m i koji ima u aplikaciji u elektrolitičkom prevlačenju hromom (hromiranju), određenu pri 45°C i 6000 Ah protoka naelektrisanja, u rastvoru hromne kiseline koji sadrži pomenuti aditiv stabilnost od ^ 4 h.1. Additive for aqueous solutions of chromic acid, characterized by the fact that it is free of fluorine surfactants and that it is biodegradable, which is CH3(CH2)nS03H or its salt, where n is 12 to 17, wherein the mentioned surfactant is the only surface-active substance and which has in the chromic acid solution containing the mentioned additive a surface tension of £ 35 mN/m and which has in the application in electrolytic plating by chromium (chroming), determined at 45°C and 6000 Ah charge flow, in a chromic acid solution containing the aforementioned additive stability of ^ 4 h. 2. Aditiv prema zahtevu 1, naznačen time, što je n jednako 14 do 16.2. Additive according to claim 1, characterized in that n is equal to 14 to 16. 3. Aditiv prema zahtevu 1 ili 2, naznačen time, što rastvor hromne kiseline koji sadrži pomenuti aditiv i koji se upotrebljava u elektrolitičkom prevlačenju hroma (hromiranju), ovaj rastvor hromne kiseline ima gustinu struje od 35 A/dm<2>do 60 A/dm<2>.3. Additive according to claim 1 or 2, characterized in that the chromic acid solution containing said additive and used in electrolytic chromium plating (chroming), this chromic acid solution has a current density of 35 A/dm<2> to 60 A/dm<2>. 4. Primena aditiva prema bilo kojem od zahteva 1-3 kao sredstva za poliranje (glačanje) u hromnim elektrolitima.4. Application of additives according to any of claims 1-3 as means for polishing (ironing) in chromium electrolytes. 5. Primena prema zahtevu 4, pri čemu je koncentracija aditiva između 0,05 g/l i 20 g/l.5. Application according to claim 4, wherein the concentration of the additive is between 0.05 g/l and 20 g/l. 6. Primena aditiva prema bilo kojem od zahteva 1-3 kao aditiva u polimernim nagrizajućim sredstvima (močilima) kao predtretmanima za polimerna metaliziranja.6. Application of additives according to any of the requirements 1-3 as additives in polymeric etching agents (wets) as pretreatments for polymeric metallization.
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011102052A1 (en) 2011-05-19 2012-11-22 Anke Gmbh & Co. Kg Wetting agent for electrolytic application and its use
US9771661B2 (en) * 2012-02-06 2017-09-26 Honeywell International Inc. Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates
TWI456093B (en) * 2012-06-26 2014-10-11 Dexnano Chemicals Co Ltd Method for black chromium oxide and black chromium oxide electroplating layer thereof
ES2766775T3 (en) * 2013-09-05 2020-06-15 Macdermid Enthone Inc Aqueous electrolyte composition that has reduced air emission
US10087540B2 (en) 2015-02-17 2018-10-02 Honeywell International Inc. Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same
CN105177640A (en) * 2015-08-04 2015-12-23 重庆立道表面技术有限公司 Efficient high-performance and high-hardness chromium plating process
CN110565124A (en) * 2019-08-05 2019-12-13 宣城金诺模塑科技有限公司 Chromium plating solution for automobile ornaments and electroplating method thereof

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1012463B (en) * 1954-10-05 1957-07-18 Friedrich Kessler 5, 0 to 50, 0 m roll tape mass with automatic rolling device
DE1034945B (en) * 1956-05-15 1958-07-24 Riedel & Co Smoothing agent and bath for electrolytic chrome plating from an aqueous hexavalent chromic acid solution
US3041257A (en) * 1960-08-25 1962-06-26 Westinghouse Electric Corp Chromium electroplating
US3745097A (en) * 1969-05-26 1973-07-10 M & T Chemicals Inc Electrodeposition of an iridescent chromium coating
CN87100440B (en) * 1987-01-27 1988-05-11 中国人民解放军装甲兵工程学院 Methods of Brush Plating Copper on Non-Conductive Materials
DE3723198A1 (en) * 1987-07-14 1989-02-16 Bayer Ag FOAM-RESISTANT ADDITIVE IN ACID SOURS AND GALVANIC BATHS
US4997686A (en) * 1987-12-23 1991-03-05 Surface Technology, Inc. Composite electroless plating-solutions, processes, and articles thereof
US5453175A (en) * 1989-11-06 1995-09-26 Elf Atochem N. A., Inc. Protection of lead-containing anodes during chromium electroplating
ATE150100T1 (en) * 1989-11-06 1997-03-15 Atotech Usa Inc PROTECTION OF LEAD-CONTAINING ANODES DURING ELECTRICAL COATING WITH CHROME
WO1994004722A1 (en) * 1992-08-14 1994-03-03 Blasberg Oberflächentechnik GmbH Anode for use in electrolytic chrome-plating
DE4328883C2 (en) * 1993-08-27 1996-08-14 Bayer Ag Process for the preparation of molded polyamide parts for the subsequent electroless metallization
DE4436391A1 (en) * 1994-10-12 1996-04-18 Bayer Ag Process for direct galvanic through-plating of two-layer printed circuit boards and multilayers
EP0860519A1 (en) * 1997-02-12 1998-08-26 LUIGI STOPPANI S.p.A. Chromium plating from baths catalyzed with alkanedisulfonic-alkanesulfonic compounds with inhibitors such as aminoalkanesulfonic acids and heterocyclic bases
DE19828545C1 (en) * 1998-06-26 1999-08-12 Cromotec Oberflaechentechnik G Galvanic bath for forming a hard chromium layer on machine parts
DE10033433A1 (en) * 2000-07-10 2002-01-24 Basf Ag Process for electrolytic galvanizing from electrolytes containing alkanesulfonic acid
DE10124631C1 (en) * 2001-05-18 2002-11-21 Atotech Deutschland Gmbh Direct electrolytic metallization of insulating substrate surface, used in circuit board production, e.g. for metallizing fine holes, uses pretreatment with water-soluble polymer and acid solutions of permanganate and thiophen compound
DE10255853A1 (en) * 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Manufacture of structured hard chrome layers
JP2005240180A (en) * 2004-01-30 2005-09-08 Riken Corp Sliding member having composite chromium plating film and method for manufacturing the same
DE102004019370B3 (en) * 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Production of optionally coated structurized hard chrome layer, used e.g. for decoration, protection or functional coating on printing roller or stamping, embossing or deep drawing tool uses aliphatic sulfonic acid in acid plating bath
DE102004026489B3 (en) * 2004-05-27 2005-09-29 Enthone Inc., West Haven Process for the metallization of plastic surfaces

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