DE1483347A1 - Process for the electrodeposition of metals - Google Patents

Description

PATENT ADVOCATE

HELMUT GORTZ

¹ Frankfurt a. Main ² °

Schneckenlior'sfr. J /. Ui. _o | jO44 Gxy / Gw UNIO) I CATIBIDB C OHPORA'PIGif, 2? O Park Avsnua, Vie «? York, N ₆ Y ₀ 1oo17 / USA

the end. a? .e. '"..- rolytinoivs» »AbachaiJexi of

Mr. L'rfindana; did .. 'ifft a process in the electrolyte laugh abachaids? ο: · ι iisvtlXon, iri'j'cK: .3 special from hltaebot »t; äßä: l5en Mitall ,, their? _t <;. 'v * .i ^s r'.ui <jm ui'.r? Vr. '. Biuii-j.iisßiTio inabea ^ n-isre concerns the invention a ^v i: -rfa'rtren »ura / Λ> i» i.Jftri ron zircon, Hafnimi, VanadiuD, Hiobium _t "

, Siol; rt'En and WolfxtiK in Pona from densely, fine-grained, nichiohton «liach the inventive method can a>; - ^; \ a «s diasen Matellen, ihi'cn I.fJiile.?.*utVTen and their connections

Plr> .ti <dTttn ^ en wnd objects hear all who eich 'J glaitte vavl ßhiichrslVMßa surface fcche auoaoichneno

'in where. liv; i; r ;;) n Jalxaolmtoa vix-ΰ a, ^. 4'oöer Toil dar mentioned metals uw. r '":: * ?: ·.' Lv ^ ifiiw.r-en elsSctrolytieoh Xn Forsa von Ubersügen ab « .ifshli;. ·."'"'! Ns iifcsi; ra? .Don these: * Hetallc and Leglernngea on documents Ttrj - :; '« / α v- Ä-M! C> iif) ds) Tt £ '? E.vf'ila'i: n' τ «ϊϊτβη ⁽ 3β * _β There are already procedures ai> !. 'olr.:-r<;-'Λγ>:}.!<Β'χΛ Aliaahtij.dcK by Mirkon »ffiöbiua _e fantalg chromium,; ολ, ί u:.> R ₍ voli'rua vat! HAi'uitiia vo ^ geiichlagono For zircon, niobium and Tiiitfi. ¹ ir. · '; «a Rbövc λρ.οΙι don biiiii> * i * i; jeri procedure not,» öglioh seveaen, (light *,;' · '! ΐζνί £ οι-ζι1,', <!, E \ iearamf !; ahJl) i iaiitie lohlchtau hf3.cauatallen ₀ to Hiist.eji F.illez srhieJ.t raun this dieae metals in granular Fora, the j ^h:!.! i '; ^c:: * auniK-a'iifioechnolvsnii, anrjamifflen;? eimlat or sonatvie processed v.urden. UoI these Vorfaiu ^ n the metals Ia Fora τοη dense, tI * Γ η! jern od *> in Fora deposited by dendrites, which are removed from the nuts «,

V, u uinC η.]. '' (Irdiii ^ ü achoii Vüi-fahra »aur electrolytiaohen Abaoheidunf ■ by C ;. t;»; and Wallias: in Foisj zuaantnonltän ^ eoler layers known at Chic ·: ta ', rn. i hiev alloriingii lmner a w & aari ^ en electrolyte «»

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"u8 be the Chi'oia after depositing bai hahan feaporafriren, fjeteapert" woboi the Ab3o'neidun are £ s oteta hard odor brittle and often lUosQ "" thaAtene Baher _o rapid by about softer The b? & uia.t "n Process for the deposition of tungsten are Ria Ausgan, -> 3utoffe seuarstoffhaltigo connections, as.B ₀ 'A'olfraeate ver «

Iiifolgedeg! 3sn iet the ab / jeochioiiane Wolfra "not ductile" he vsi'l. &. v. make these procedures very lan ^ siuB and can only be used with

n Tija-eratui *; n ünrchp & leads voxdcn _r where the Wolfrae wlrd through the Aufaniv ^ 'voa Fohlmstoff sprörlo ₀

? fctc3? ita ^: olrtunj U 193 ^ · '? VIa / 4 "c int a process ΐϊ-crdeu," Γ-ιτοΙι velchee the mentioned ifechtoile in the electrolytic deposition; Ron hitaobouiändi ^ en metals are sold _o Rao ^ diseeis? srftäliren vantenaot aan a system with a Katfcode _e one anode and ai-uw sciifsaliiflunui ^ ou Klaktrolyten _t there are no nsniionw ^ rten Mßa ^ en ron Chldenc contains and in wea-anU-lohon aua one (Iruadochselae consists "the" ionigrit-ana a fluoride of ffaliiin _t Hubidiu »and / or Cäeiua and in addition sin ^ aitor ^ o fluoride contains another sleaentea, of the electrical voltage oreihe higher ateht than dea abxu · = · separating © KetalI ₀ Me Hclraelse farner contains at least one fluoride of the absiischaiditnäa ι metal a ^ at choice ^ eoignet «rr

the fluoride in d * .r Seidels »and a (psei ^ nete temperature, the in which Hegel swisciea 575 and 900 ° G lies, and finally at An wendnng: a suitable street density, succeeds ea, density, hanging "Divide down on the cohesive of the metal" According to this procedure Can't only dense, fine-grained, suaaajsen-hanging ab " Divorces dos Metle »to make a good yield» You can do that Do you also use the process for refining the metals? Against" This procedure is based on the previous / experienced ones from »that no pulverulent precipitates or dendrites can arise» hai to

BATH ORIGINAL 909811/0883

It has now been found that such a Processes within the Scheel * de · electrolytes large temperature difference « exist "thereby" grounding thermal currents, which move the small particles contained in the corridor stop and prevent them from abaetsan on the bottom of the sef & asee "" Hence some of these particles present in the melt get lost Cathode and form on the metallic precipitated humps, Roughness and other irregularities

Bleee small particles in the melt consist mainly of fine ▼ Granted metals or metal compounds · They are heavier than the Scheel * · so d * B them in a quiet swath sloh gewtthnlffloh settle on the ground «Me thermal currents hold this small particles in airculating movement within the bath "

In the case of the turn electroplating process, the baths in the cone are cleaned by filtration. However _, when using boiled salads as electrolytes, filtering is very difficult and requires pumps and filters occurs particularly in the electrolytic deposition of heat-resistant metals, where larger temperature differences within the Sobaelse are often encountered »

The meaning of the invention is "in the new process, by which ·· these disadvantages are largely avoided · Another subject matter the invention solder a process but electrolytic deposition of Metals from a Sohmelae to a · cathode, with roughness and Unruly smudges & peculiarities on the surface of the deposit · avoided world-wide are · The procedure is used in particular in the case of ■ oheiduns of hitacbeetändlgen metals, their alloys and compounds at temperatures of 600 ° C and above ο

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Dae erfindunrrsgomäfle Seduce is characterized ₉ by heating the zone above and tin the Berühruiufeflaohe "wipe the gas and the electrolyte in the" 9y "system to a temperature the fewest · dio fJchnelateaperatür the electrolyte reached this" ground thermal Strümun /? On largely avoided within the melt "

The "River 1 is an inch"? for electrolytic deposition from 59- ßcYmolzoncn salts., It has a thermal insulation 10 and is equipped with old wood enclosures 11 for the electrolyte and heat clusters 12 _O and over the contact surface between the gas and the sleeve a further resistance shell 13 arranged

The Piß * 2 selgt #raphiech Teaperaturprofile »in a typical cell according to Figo 1» The figure ä shows the temperatures * that are observed * when the oasaone is not heated ο This curve is typical for the temperature differences in the usual cells _o The curve The temperatures in cells according to the invention in which the saezone is heated »

In normal cells with molten salts, heat losses occur mainly "on the upper surface of the melt. These heat losses are 100 or more times higher than the heat losses from the insulated conductor" Melt from 779 to 800 ^° C. on the surface of the melt is 72 kw / m. In smaller cells with a diameter of 15-2o om, differences in temperature can only be observed within the top 15 cm of the bath. In the larger cells with a diameter of, for example, 90 om, the temperature differences extend to a depth of about 50 om. In such systems, the temperature area is maintained by thermal agitation with a heat loss of about 72 kw / m from the surface.

BATH ORIGINAL -5-

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The objectives dor invention "reaches earth _t when the zone lh the fötichbaröchaf the Reriihnm ^ t BflSche" wipe gas and melt as high cvliit / is it that thermal currents within the Schmelse weit.rjwhoud vöA'üdoUun. Wertioüo Ia allgoaisin & n, enough ee, this zone on the o-.hsieltii.cJ.ipex'ötui '«ine electrolytes asu erhitaeno Ale Schatelno temperature v / ird diojenigo Tempera door called, at which eich the he nt on floods Tuilc.hen boira Slowly cool down the melts ", Lias" Tfiapsratur hiin ^ -t of the respective composition of the LJchnei.ae el < and therefore integers for metals, Lej * iexiinfifaa or their / herbindungen "

Dia iVLii'KOiijrlusjto in the oboron parts of the · i'chiaelao arise in «r ^ '- er;, in.ie through ntr & hlunß and by conduction through the upper wall« l> arch da »orfindun £ 8 £ emäQ« process if ea »dieao succeeds as far as hsrabausatxeni that iva rosontlichen a temperature is reached and tharnisoho currents do not occur» int es dun foer.en Tuilohen within the Schaelse atö ^ lioh, β j .sh r / i testicles ϋ.οχ '' hurry to depose.

In the case of "olektrolytischen Platioren τοη hitsobeotändisen Metals di ·"ii'JTie troll over and uu the contact area with gas and smelting high o:? hitat that the Teupernturuntereohlede svrischon aen oburai mhA the lower parts the aisle is not very air. 1o ° C, Toruw; av * isQ not nohr ale 2 ⁰ C, betragono In many cases iat 9 ') 3O'; ar appropriate, dleeo zone so high that a srirkliohen thermisoh ?!} (Ileich / 3, « wioht x wiechon the Ga «and the Schaelae exists»

The method for the zone is not critical; one can apply wr -.- jchi ^ d ί Ίβ Ui'.tol hiorfiir · One can x «B« in addition to the resistance ·· heizu vjsn to dio 3shmßlxsone ^ 'resistance, among other things the Gaasone herua FORMATION "ne provision may also Witrmeschirae above the Gassone, üb su avoided and a thenlsohes balance Λ-jlraoht za 3Thalten _o more Wanieverluete

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much as it has already been said, the inventor of jsijem ancestors can be found everywhere Use where electrolytic deposition can be obtained should, and where the temperature differences within the electrolyte so / proβ are "that thormia-like currents occur" ^ aa procedure 1st It is particularly suitable for use in the above-mentioned cases Torgeschla ^ ensn process sun deposition τοη heat-resistant metals « This older procedure "embodies a theory of theory in the production of very corrosion-resistant items for industrial and railitfcrische

After this process, a lichraelae is used as the electrolyte, which only contains fluoride. Other anions, such as chlorides, bromides or oxides, are only found in the molten material as only slight "impurities". Larger quantities of these substances are obtained the absoheidun ^ en in Fora a l'ulvere or from!) endriten _o Here, of course, your TTerstellun? the knowledge of the fluorides in the water, the air tightness and the tea temperature are correlated to one another from dense, ausanunenhaa. ^ ending deposits. in the melt uiid of the kind of absuaohoidenden Met & lleo ab ^, By simple experiments from case au l'all this " Οτηντ, οη" can easily be determined ""

The electrolytic melt bath consists of at least one “fluorite! of the metal to be deposited and from the '! Rundschaelzeo The orundachnelzeo consists of at least one fluoride of potassium, rubidium or cesium and of at least one fluoride in another element that is higher in the electrical voltage series than the metal to be deposited. The composition of the Schmelsbades for the formation of dense, "usamraen-dependent" precipitation depends not only on the temperature and the current density, but also on the type of coating that covers _a ! Sum Abaoh, iden of zirconium, siobium, tantalum, volfram and molybdenum, the trundechmelt should consist of between 10 and 90 ow "; i, preferably between 30 and 73 wt.; *, at least one fluoride of potassium, rubidium and cesium. The rest of the

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BATH ORIGINAL

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nohnelze comprises at least one fluoride of another element, the areihe in the electric Spannun ^ stands higher than the metals deposited as Grundsctaelze used aan Torsugsweise a eutectic mixture of the fluorides of lithium, Watriua and Kallua, the 29,25 Qew "£ LItBiUBfIuOrId ₁ 11 , 7o contains OEW ₀ ^ Natriumfluorld and 59.05 Ge "·", "Kaliuafluerid and melts at about 454 ⁰ C" Further suitable compositions are described below in examples "

The concentration of fluoride in the metal to be deposited is honed on the composition of the basic shell, on the temperature, on the current density and the type of metal to be deposited «For example, the fluorides of zirconium, Mobiua or Tantalum in the round melt in concentrations between wall 3 «3ew« 7 &, preferably between 5 and 15 '? «* ·?> · contain its when separating of tungsten, the melt should be between 1 and 33 Ce »«? », preferably between 3 and 10 ow «#, contain metallic tungsten« leg deposition of molybdenum the melt should be between 1 and 20 ow «^, preferably between 3 and 10 ow.?*, containing metallic molybdenum When separating vanadium, chromium or flafniua from dea eutaktisohen Tonically dsr fluorides of lithium, Katrlua and Kaliua are said to be the fluorides of the metal to be deposited in the case of Chroa and Hafnlua in amounts of β% by weight C, generally in the case of vanadium in an amount of 1o wt. # His present

The metal fluorides used can be simple or complex. When using a complex fluoride, the cation must be higher in the electrical voltage relation than the metal to be deposited | the anion must not contain any oxygen. Typical metal fluorides that can be used are the single and double fluorides, such as potassium hexafluorocarbonate, kallua hexafluovanadate ₍ potassium peptafluoronlobate, kaiiuaheptafluorotantalate, potassium hexafluorochromate, potassium hexafluorohydrohydrate, the solubility of some metals

^ ORIGINAL -β-

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If it is rather small, it can be converted to a lower level by uctuating the metal. For example, when depositing metal or molybdenum, it is advantageous to use metallic tungsten or molybdenum in the form of metal, and then form Introducing T / olframhexafluoride or molybdenum hexafluoride "These are insoluble per se and can be introduced into the melt through a graphite tube". The metallic tungsten or molybdenum then reduces the insoluble, gaseous hexafluoride to a soluble fluoride _f from which the tungsten or molybdenum is then electrolytically deposited ο

The metals zirconium and hafnium are removed from their four-fold state, Tantalum from its 5-valent state and chromium from its 3-valent state Separated state · They are not used with the other metals in the state of the highest valence, but needs connections of the 3-valent vanadium and molybdenum and 4 "-valent niobium and Wolframs · In this older case, corresponding connections of the metals can be made outside the aisle and then suggested But you can also use the metal ion in the lane accordingly redusleren »When using tungsten hexefluoride, the tungsten BU of a connection lower vertigkelt, as a precautionary measure by touching of the gaseous tungsten hexafluoride with metallic tungsten in the Schmelse achieved »A further reduction takes place through electrolysis instead of·

Electrolytic deposition should not be inert oxidizing atmosphere, e »B · of argon, neon, helium or in a vacuum be carried out · The inert (Jas can be rendrnok or Another pressure can be used at which it is essentially inert opposite the üchmelee and the metal. The container for dl Schmel can consist of any material, da · dl · Schmelse or das deposited metal is not damaged and from the Sohmelse during d ·· Operation ·· is not attacked »

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The te «; jeraturea and stroadiohten b« in the separation depend on the .ιβι? to do? the enamel »and from the type of absusche id end abo In general, the upper (bridle for the current density from aut cioy ftmaentx'a; lon des Fluorides dee to be deposited! ίΞ-fcallefle Dio T <üap * rratur dasj Kl«> ktrolytan It must of course always be above h »lb dos:» chraa ^ i; p ^ ikt9S lA> s ^ oao Kan ltfum S ₀ Bo zirconium absoheiden

'jcabhodi see current density of 5 - 4o au / ca, preferably? ■> «3o» ft / ya _f and with ei only Teaipea ativr tou 675 - Öoo C "rorzuga" \? oi «e at 75ο ° ί? β tantalum came from ^ eBeclied at a current density of ^ - 100 kA / ou _e Torau ^ awoise 4o «A / on and at one

Temperature from 7oo - 8 * 3o C ₁ Torau / »aweiae be :. 8oo C ₀ niobium can ύ

at a current density of 5 "100" A / cm _f 50 IiA / cn ", and at a temperature of 675 ° C, preferred

Up to 77 '0' Hafnium can become t.bg9fichiäde'i at a current density of? o nk / on ' and a temperature of 75o C. Yanadiuu can

uarden b »i olner Shrondicht τοπ ^ o αλ / om and one vo .-. i 77o Ce Chroa can wegchijdon nerdeu at a Hfcroadlcht. «. Of 25 * = 60 mA / sb and a temperature of 8oo

can t, O) ßouchiedt; n nerd <m at a ^ r Btromdieho of 2 ~ 2oo mA / 'ju ι voc -'. o ^ eweie © 1o - 1oo «Α / ca, and a temperature of 600 - 900 C ₁ -for * u * swsii ~ e 7oo -> 0 ^r ) OC ₀ Tungsten can be deposited vox the at oinor LUromdiohtö vou j - 2oo mA / om, preventive Io «loo ΒΑ / ο» _t and at a »; r temperature of 52 ^l > »900 ° C, precaution at 72: 3" B ¹ Jo ⁰ O ₀ That bind of course only balupielavoiae information that does not include the ^ oi'eniitaud of the invention »ο11βη ₀

Electrically conductive! Hope and alloys can be used as

used for the cathoie "earth" The only thing to be said is that the basic material does not react strongly, and that it is not at or below the operational level. Vtai can exemplarily: s important re-

preserved on 'interlaffen made of rustproof steel, oraphite, and copper · In some cases it can be "open measure, since" Orund

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material Torscubehandeln, Zo3 "anodiaoho The suitable selection ό / Λβ Grundieatoriuln and its pretreatment depend on different Uiftstiindon _u This includes the type of the degrading metal, the" form dia zn platiorandan object οs and the permissible tolerances "'Vonri des a ^ ooc ii "dane metal τοπ dor backing away to" ground, Kf) is swecloaüßig aolche documents to die, you again use canoe. "

The quaIIo for lau aliaufichoitfindo metal is either the melt or the anodo odor boideoo The type of anodtj depends on whether it or the cutting edge is the source for the metal lato used "on here" for the anode, so it should be soluble and whole or at least off. Part of dom ebauccheldcmden of metal * 3ie, the Fora of Mtiibon, Platton, Bchoitoon, from i "hnitt 's or other objects have" Using a tsllchcn / Öriaigea Anodonaat ^ riftl, it may by a 3ieb,:; _Ο Β _Ο from Hickol, attseaaenjehalten terdene Vorwendet nan the anode as Nielli, oo can the voltage between the cathode and anode below the Zerootaua ^ uepannunff der * 3chael »e

If the suhmelne dsu Klohtrolyte is used as the quo113 for the decomposing metal, then an insoluble or soluble anode or a hydrogen electrode can be used, depending on the material to be deposited. An insoluble anode made of graphite or carbon can be used if such compounds are disintegrated in which the ketal1 is present in the highest valency, i.e. _a in the case of compounds of zirconia, raffia, tantalum, chromium _o If an insoluble anode is used, the voltage must be at least as high as the zereetiun ^ iipoteatial dor Schaelseo All the metals mentioned can be independent lg of the valency in which they are present, if a hydrogen electrode was used or an anode was used, which contains an active metal and was lithium, sodium, potassium, magnesium, calcium and / or aluminum. In these cases the voltage does not need to be as high as the decomposition potential of the chemical substance, including the resistance of the chemical, is sufficient

BADORiGfNAL «

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Electrolytes and the low polarization of the electrode see below overcome «used« to an anode on an active metal, so the fusion becomes duroh the pluoride of the active metals, that aich forms on the anode, and by deposition of the heavy metal gradually diluted at the cathode for continuous work but let ea it is best to let the swathe run around and out of it Remove the active metals from the fluoride outside the cell and the pluoride de · abeusoheidenden Metall · susueetsen »In general is a tfasseretoffelectrode for electronic decomposition Advise that no active metals are needed, and because the anode product, i.e. hydrogen fluoride, escapes from the melt in bubbles, as it is less corrosive than the gaseous one Pluor, which arises on the insoluble anode · Therefore enables the TTassetoff electrode the use of cheaper and more rented er holds building materials for containers, soher walls, pipes and others Components of the

Sa the concentration of the fluorides of the absolute metals · during of operations · decreases, oo must there. · Bath refreshed with MetallfluorId so that the concentration of the ··· fluoride · in the 3chmelee continuously within the required Orenaen 1st · So must one β · Β «in the electrolytic deposition of zirconium, tantalum or hob the concentration of the metal fluoride in the aisle «wipe 5 and 3o flew «? I hold.

The Absoheidungen obtained by the process of the invention have «• ine density of at least 98 i> of the theoretical density of the metal you can usually meohanisch deform without breaking su, and · substantially free of non-eetaliiaohen impurities It seems As to whether there is no upper limit for the thickness of the Abechelduars obtained by the process of the invention, the diohte suaaamenhangfiende schiohten with a bucket dloke of more than 13 mm and made by the dleoem process "

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H & ch dfii * lirfindun,? Can documents of any desired form be electroplated from the above-mentioned metals? ViCKQU dor guton Streukraifc J.ut the demonstrator particularly suitable to un metals on koiiplisiari; f; formed pads or on internal surfaces

After the «ancestor of the üritidua / ;; kümien does. Objects of any arbitrary shape were made. The way in which the formed body is separated from the Tintargo depends on AeT 7, USA "raensetsmii? the base UUD Hirer For "off of the Fora of the object and of whether the base will rerwendet again soil" You can solve zobo a flat washer "from Niohol in Sftlpettrerure or aechanisch entferatm by withdrawing ϋρ & ηοη or drilling _o Kine underlay · cua graphite can bosondero easily raeohtmißci; removed _o

A "document uu" niokol ^ Holybdän-Chroa ^ Iieglerun? can easily by simply A.bzitjhe: i be separated from DSSU fib ^ eochiedenen Met ll ₀

Kaoh the 7erfatiren the invention may niebt only pure metals but also vareohietUne Legiorungön or Verbindur ^ s of these metals are deposited · Hiersu kttnn win dor peeled the fluorides of the ent "speaking material" zuset £ s _r needed üb the "ewüneohte alloy obtained or compound shown below, or by rerwendete one secondary anodes from the gewünsohten material Thus, let S ₀ B ₉ tightly ·, Hueaamenhäivrenäe layers deposited clay Zirkoniumdibcrid when "rlektrolysiert a melt dio from the Oiundschmelze with Io - 9o OEW ^ potassium fluoride. , Rubidium fluoride and / or cesium fluoride, the remainder being the fluoride of another. Element consists, DME in the electric Spannunßsreihe ot closer "ht as zirconium and boron" should ac The Scheel further 5 ~ 3o weight "^ include one Zirkoniumfluorids, calculated as simple fluoride j and slept lent to them 5-11 1 * Bortriflvorid tnthalton , and was in the form of a fluoroborateo

BATHROOM 0RIG5NAL -13.

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Suitable liiundechrcelsen for the deposition of zirconium- »diboril are the eiitektisohen mixtures of the fluorides τοη Lithium _e Katraust and Kaliun odor the fluorides of potassium and lithium odo? The fluoride of potassium and hairiua "Bas gaseous ßortrifluorid can be introduced into" a path which reveals potassium "flv.3r.ld; ι da »flortri? luorid and dau F & liunfluorid set oich d v.iR ir.norhalb dor Sohnelso with the formation of potassium fluoroborate '» ι _r so C.txB daa boron trifluoride in the imelae actually

alη FluorooxRt is present. You can also directly add the appropriate amounts of potassium fluoride, hydrofluoroborate and potassium fluoroconate (K ₂ '^ ^? <)'Liso'iuiio Finally, you can also use other suitable compounds in order to use the boron trifluoride

That depositing Zirkondiboriä is at temperatures of 7oo "9oo ° C, asuiae at 775" 873 ⁰ C, performed and "was with cathodic

2 2

StxouiUchten from 3 ~ 35o bA / cb, precautionary 15ο = 2oo λΑ / ο _o 1) 1

The anode used in this case contains a larger amount of pre-suction of zirconium

Example I.

A new electrolysis cell with a copper rod was used as a cathode trorusndat »The tube consisted of a eutectic mixture of lithium / fluoride, sodium fluoride and potassium fluoride and contained 15 tantalum fluoride. The electrolysis was carried out at a shell temperature of 775 U '»^ Ld a cathodic strondicht» of 30 mA / cw duroh ^ e leads, Di-)' /, rush «ar nut isolated and covered with a V / ärmesohira | * u-Wfirae uurde the Gaaaon «above isr aisle no eye»

leads; ₀ li ^ ßHunriSn «announced that within the 3ohaelse awisehen the u id lower. Share leapatic differences of more than 50 ° C

i _# i) le formed on the cathode Platlerung consisted of Tantr.l, nlno Diohte of 16.6 e / oa (had the theoretisoho Dlohte of Tnr.tal)} a Hurt "of 95 DPH, and was aueaaaenhanßend" A · ge -

909-11 / 0883

ifr

Close inspection, however, showed that the surface was rough and

One wiederholto as "ancestors under otherwise identical conditions" dt dor Auanahue that especially the Qausone hertun and around the BerührunftSSBono uiirl dor between Gaο Schmelso susätaliehe Hei * Yorrichtun <* en attached * Ereno During electrolysis haizto nan the üaaaone so high that Within the melt, in an essentially uniform temperature, there was "if3s" un.Ten pointed out that only within the top 2 = 5 o'clock the Schiticlzo Terapsnztaruiit goodbye ("radon beetandeno The platings obtained were smooth, had no bumps, and were superior to those made without heating ₀

Example II

In sine? HlolctrolyiKiivnalle only use a copper cathode! The bath consisted of a eutectic mixture of lithium fluoride, latriuafluoxid and potassium fluoride and contained 1o weight _o ? '»Ifiobiuafluorido The elecrolysiJ vnjrde at a temperature of 775 ° C and a temperature of the rest of the time I $ earbeitot _g F> e the same t Temperatxiinintarwchiedo feat. ^ Eotellt »The coherent deposit on the cathode consisted of Jfiobiufflo. Its surface was rough and

If, on the other hand, the Gassone and the touch were heated according to Example I. Fläohe "between the gas and the smelter, so were the resulting Plating was smooth and did not contain any dents; those without Heisun / T of the gas zone manufactured superior

Example III

The procedure was as in Example I, the Schmelie 15 containing tungsten fluoride ₀ The electrolysis was carried out at a

BATH ORIGINAL 909811/0883 -15- ♦

Aisle temperature τοη 775 C and a cathodic Stroediohte

of 3o hA / c "*" For the rest, as naoh Example I was working and the observed Teaperaturdifferenzcn within the corridor were 4ieeelben _e The Fl "tierun & bestund ans Vfolfraa and was co» rappelled flamaenhünsondo liine'Vteitaue visit that the surface rough and unregclfiaßig was «

If you worked JetRt, as described in Example I under Heiaun ^ der Gaaaonc and the contact xone awiochen Schneise and Qä «, so were

the entotondenen Pltttif, rv \ ngfln / ^ latt, did not have any rows and were

superior to those manufactured without heating the Gaaaone _P ™

909 811/0883

Claims (1)

Claims Tried & u «olelctrolyteiohen separation of iietullen, theirs Alloys and compounds on a cathode in an electro » lytiechea cell old oiner Scheele "" and one oaesone, thereby gelcennasiotnetf that one the JSone over and around the ßsrührungsflache dos Gate; » since the shell i: ui at least the cabinet temperature des Kl <? k '»xolyten Method according to Claim 1, which is marked by the fact that the Zone above and around the l'crühxnm'rsfläche * of the iiaiiee with the lichmclce heats up to such a temperature that within the S No tooperature below between the upper and lower part of the rhyme Bchlodo over to C etntet «hene Method according to Claim 1 or 2, characterized in that one counts the Cieazon «and the tichaelüe at im wooentliehen the same Temperature IiSIt ₀ Are you looking for a de? Claims 1 «· 3 _t characterized in that one zura Abfrchoiden τοη? ₍ irkoniue, Kafniue, Vanadium, Hiobiuiftp Tantal, Chrom, Moljrbdön, Wulfroa, their Gemieche, Leffierun ^ n or Ver « bonds have an electrolysis temperature of less than 575 ° C Process according to claim 4, characterized in that all electrolytes are made of a melt which does not contain any significant amounts of chlorides, brouidons and oxides, essentially of a sundeclimelue of at least one fluoride of potassium, rubidium and / or cesium and at least one fluoride Element which is higher in the electrical power supply series than the separating metal, bcateht, and v _; miffe <; one a fluoride of the metal to be deposited "r ^ hftlt" BATH ORIGINAL 9098 11/088 3