SE201815C1

SE201815C1 -

Info

Publication number: SE201815C1
Authority: SE
Publication date: 1965-01-01

Description

KLASS INTERNATIONELLSVENSK C23 if48 d1:7/ PATENT- OCH REGISTRERINGSVERKET Ans. 3217/1959 inkom den 3/4 1959 utlagd den 10/5 196 METALLGESELLSCHAFT AG, FRANKFURT A.M., FORBUNDSREPUBLIKEN TYSKLAND Forfarande for att underlatta kallbearbetning TJppfinnare: H Keller och A Mayr Prioritet begard 'ran den 5 april 1958 (FOrbundsrepublikert Tysktand) Foreliggande uppfinning wiser ett forfarande for kallbearbetning med hj alp av zinkfosfat innehallande overdrag fOr arbetsstycken, som endast aro avsedda att genom kallbearbetningen underga en ringa till mattlig deformation och som efter kallbearbetningen ej skola uppvisa nagra ytterligare bearbetningen stOrande roster av fosfatskiktet pa ytan. CLASS INTERNATIONAL SWEDISH C23 if48 d1: 7 / PATENT AND REGISTRATION AGENCY Ans. 3217/1959 was received on 3/4 1959 issued on 10/5 196 METALLGESELLSCHAFT AG, FRANKFURT AM, FEDERAL REPUBLIC OF GERMANY Procedure to facilitate cold processing TJppfinnare: H Keller and A Mayr Priority requested on 5 April 1958 (Federal Republic) a process for cold working with the aid of zinc phosphate containing coatings for workpieces which are only intended to undergo a slight to moderate deformation through the cold working and which after the cold working should not show any further machining large grids of the phosphate layer on the surface.

For underlattande av kallbearbetning har det visat sig myeket lampligt att anbringa fosfatskikt pa arbetsstyckets yta. Man har salunda pafort fosfatskikt saval for att underlatta dragning av -L.-radar, ror och profiler, som for att underlatta kallflytningspressning och dj updragning. To facilitate cold working, it has proved very convenient to apply phosphate layers to the surface of the workpiece. Phosphate layer saval is thus available to facilitate the drawing of -L. radar, tubes and profiles, as well as to facilitate cold flow pressing and dj drawing.

Fosfateringen av ett arbetsstyekes yta har hittills sett goda resultat vid stora deformationsgrader. Vid medelstora till sma kalldeformationer har man emellertid mott svErigheter som det efter kallbearbetningens slut pa arbetsstyckenas yta kvarstannande ieke onskvarda rester av fosfatskiktets, som inverkade storande pa den efterfoljande blankglodgningen eller elektroplateringen. The phosphating of a workpiece surface has so far seen good results at high degrees of deformation. In the case of medium to small cold deformations, however, difficulties have been encountered which, after the end of the cold working on the surface of the workpieces, do not remain uninsured residues of the phosphate layer, which had a disturbing effect on the subsequent gloss annealing or electroplating.

Hittills liar det ej varit mojligt att pafora ett fosfatskikt, som i tillracklig grad underlattar kallbearbetningen isynnerhet for medelstora och stora deformationsgrader och som trots detta aven yid mindre deformationsgrader forbrukas i sa stor utstrackning, att storningar av det beskrivna slaget joke upptrada. Hitherto it has not been possible to apply a phosphate layer which sufficiently facilitates the cold working, especially for medium-sized and large degrees of deformation and which, despite this, even smaller degrees of deformation are consumed to such an extent that disturbances of the type described joke occur.

Forfarandet enligt foreliggande uppfinning kannetecknas darav, att arbetsstyckena behandlas med fosfateringslosningar som innehalla oxidationsmedel och zinkfosfat samt minst ett kondenserat fosfat, i synnerhet pyro-, tripoly- eller hexametafosfat, i mangder av 0,01-0,8 g/ 1, raknat som alkalimetallsaltet av den ifragavarande kondenserade fosforsyran. The process of the present invention is characterized in that the workpieces are treated with phosphating solutions containing oxidizing agent and zinc phosphate and at least one condensed phosphate, in particular pyro-, tripoly- or hexametaphosphate, in amounts of 0.01-0.8 g / l, shaved as the alkali metal salt of the condensed phosphoric acid in question.

Forfarandet kannetecknas vidare darav, att man for komplettering av fosfateringslosningarna tillshtter 0,1-2,g kondenserat fosfat per m2 behandlad yta. The process can be further characterized in that 0.1-2 g of condensed phosphate per m2 of treated surface are added to supplement the phosphating solutions.

Enligt uppfinningen pafores fosfatskiktei med hj alp av en nitritaccelerator liksom aven minst ett kondenserat fosfat innehallande losning, som kompletteras med sa stor mingd nitrit, att vid kompletteringen forhallandet nitrit : kondenserat fosfat utgor 2: 1 till 1: 6 foretradesvis 1: 2 till 1: 4. According to the invention, the phosphate layer is aphorised with the aid of a nitrite accelerator as well as at least one condensed phosphate containing solution, which is supplemented with such a large amount of nitrite that in the addition the nitrite: condensed phosphate ratio is 2: 1 to 1: 6, preferably 1: 2 to 1: 4.

Forfarandet enligt uppfinningen kan exempelvis med fordel anvandas vid kallbearbetfling av rör, isynnerhet svetsade rOr och profilror. Svetsade ror eller profilror underga efter svetsningen endast en forhallandevis ringa tvarsnittsminskning, som framfiirallt tjanar till att homogenisera svetsen. Harvid komrner det an pa aft med ringa avdragsgrad uppna en skarp profilering av profilkanterna, utan att en storre tvarsnittsminskning an erforderlig. Deformationsgraderna motsvara emellertid sdllan mer an -% minslming av vaggtjockleken, och en sadan deformation kan genomforas i ett a tva stick. The method according to the invention can, for example, be used to advantage in cold working of pipes, in particular welded pipes and profile pipes. After welding, welded tubes or profile tubes undergo only a relatively small cross-sectional reduction, which primarily serves to homogenize the weld. In this case, it is possible with a small degree of deduction to achieve a sharp profiling of the profile edges, without a larger cross-sectional reduction being required. However, the degrees of deformation correspond to a greater reduction in the thickness of the cradle, and such a deformation can be carried out in one or two sticks.

Vid anyandning av de kanda fosfateringsforfarandena, t. ex. med hjalp av oxidationsmedel hmehallande zinkfosfatlosningar, kvarbli vasentliga mangder av fosfatskiktet efter deformationsforloppen pa ytan. Om emellertid ett fOr kallbearbetning avsett fOremal fos- Dupl. kl. 7 b: 4/50; 487/08 2201 8 faterats med fosfateringslosningar, som dessutom innehalla ett kondenserat fosfat i den angivna mangden, forekomma efter bearbetningen praktisld taget inga rester av fosfatskiktet pa ytan, atminstone icke stOrre mangder an att en stOrningsfri blankglodgning och aven en elektroplatering med framgang kan genomforas. When inhaling the known phosphating procedures, e.g. with the aid of oxidizing agents containing zinc phosphate solutions, substantial amounts of the phosphate layer remain after the deformation processes on the surface. If, however, a for cold processing intended fOremal fos- Dupl. at 7 b: 4/50; 487/08 2201 8 coated with phosphating solutions, which also contain a condensed phosphate in the specified amount, after processing practically no residues of the phosphate layer occur on the surface, at least not larger amounts than a fault-free gloss annealing and also an electroplating with success can be performed.

En sarskild fordel med pafOrandet av fosfatskikt med anvandning av de enligt uppfinningen fOreslagna fosfateringslosningarna ar, att man med hjalp av dessa 15sningar aven kan phfOra homogena fosfatskikt awn pa blankglodgat material, °eh att aven svetsar bli jamnt overdragna med fosfatskiktet. A particular advantage of the application of phosphate layers using the phosphating solutions proposed according to the invention is that with the aid of these solutions homogeneous phosphate layers can also be formed on glossy annealed material, and that welds can also be evenly coated with the phosphate layer.

I jamforelse med de kanda fosfateringsf5rfarandena är sldktbildningen med hjalp av fosfateringslosningar, som innehaila kondenserade fosfat, dessutom gynnsam, emedan kemikaliefOrbrukningen och slambildningen aro mindre. Ftir paforandet av fosfatskiktet forbrukas c:a 30-50 % mindre kemikalier i jamforelse med de fosfateringsforfaranden, som vanligtvis anvandas for underlattande av kallbearbetningen. In comparison with the known phosphating processes, the sludge formation with the aid of phosphating solutions, which contain condensed phosphate, is also favorable, because the chemical consumption and sludge formation are less. For the application of the phosphate layer, about 30-50% less chemicals are consumed in comparison with the phosphating processes, which are usually used to facilitate the cold processing.

Forfarandet enligt uppfinningen kan framforallt tillampas vid kallbearbetning av svetsade profiler, t. ex. for framstallning av dorroch fonsterprofiler. For pafarande av fosfatskild pa sadana profiler aro de hittills anvanda fosfateringsforfarandena foga lampade, emedan de kvarlanma vasentliga hterstoder ph ytan, under det att det enligt uppfinningen f0- reslagna fosfateringsforfarandet med anvandning av fosfateringslosningar, som innehalla kondenserade fosfat, visat sig utomordentligt val lampat. The method according to the invention can be applied above all to cold machining of welded profiles, e.g. for the production of dorroch window profiles. For the application of phosphate shields to such profiles, the phosphating processes used hitherto have been lamped, while the remaining essential residues remain on the surface, while the phosphating process proposed according to the invention using phosphating solutions containing phosphate-containing phosphates is selected.

Exempel 1. Av bandstal pa en rorsvetsmaskin framstallda ror med 46 mm ytterdiameter och 2 mm godstjocklek underkastades en rekristalliserande glocigning under skyddsgas vid 720° C och aktiverades darefter en kort stund i c :a 15-procentig, varm svavelsyra. Efter grundlig kallvattenspolning i 5-10 minuter fosfaterades riiren. For fosfateringen anvandes en losning Hied foljande sammansattfling: 5,0 g/1 zink 3,9 g/1 P20 8,0 g/1 NO3 0,2 g/1 NaNO2 0,2 g/1 natriumhexametafosfat ROren hollos neddoppade 5-10 minuter i badet, som hölls vid en temperatur av 55° C. Efter fosfateringen spolades Toren i kallt vat-ten, infettades vid rumstemperatur i en vattenhaltig, tvalhaltig smorjrnedelslOsning och torkades. Vid den foljande dragningen pa ror dragbank reducerades roren i fOrsta sticket till 40 mm ytterdiameter och 1,8 mm vagg- tjocklek samt i andra sticket utan mellanbehandling till 36 mm ytterdiameter och 1,5 mm vaggtjocklek, dvs. motsvarande en total tvarsnittsminskning av 40 %. Example 1. Tubes made of strip steel on a pipe welding machine with 46 mm outer diameter and 2 mm wall thickness were subjected to a recrystallizing glocigning under shielding gas at 720 ° C and then activated for a short time in about 15% hot sulfuric acid. After a thorough cold water rinse for 5-10 minutes, the rice was phosphated. For the phosphating solution a solution was used. The following composition was: 5.0 g / l zinc 3.9 g / l P 2 O 8.0 g / l NO 3 0.2 g / l NaNO 2 0.2 g / l sodium hexametaphosphate ROren hollos dipped 5-10 minutes in the bath, which was kept at a temperature of 55 ° C. After the phosphating, the tor was rinsed in cold water, greased at room temperature in an aqueous, oily lubricant solution and dried. During the following pulling on the drawbar tubes, the tubes in the first slot were reduced to 40 mm outer diameter and 1.8 mm cradle thickness and in the second slot without intermediate treatment to 36 mm outer diameter and 1.5 mm cradle thickness, ie. corresponding to a total cross-sectional reduction of 40%.

I ett annat fall bearbetades pa samma satt fosfaterade ror med 32 mm ytterdiameter och 1,6 mm vaggtjocklek i det fOrsta sticket till 29 mm ytterdiameter och 1,3 mm vaggtjoeklek, och i det andra sticket utan mellanbehandling till 25 mm ytterdiameter och 1,0 mm vaggtjocklek, dvs. motsvarande en total tvarsnittsminskning av 51,4 %. In another case, phosphated tubes with 32 mm outer diameter and 1.6 mm cradle thickness were processed in the same way in the first groove to 29 mm outer diameter and 1.3 mm cradle thickness, and in the second groove without intermediate treatment to 25 mm outer diameter and 1.0 mm cradle thickness, ie. corresponding to a total cross-sectional decrease of 51.4%.

Jamfort harmed fosfaterades motsvarande repr pa vanligt satt i en fosfateringslosning med den ovannamnda sammansattningen men utan kondenserat fosfat samt kallbearbetades ph det beskrivna sattet. Medan vid den enligt uppfinningen fOreslagna behandlingen ett homogent oeh tatt fosfatskikt erholls saval ph rOrytan som ph svetsen, var fosfatskiktbildningen vid fosfateringen med ett bad, som ej inneholl kondenserat fosfat, ojaran Over hela ytan och framforallt ph svetsen. De med losningar utan kondenserade fosfat fosfaterade roren gingo fOljaktligen oroligt genom dragbanken och hade period-vis benagenhet att skramla, medan de enligt uppfinningen fosfaterade roren kunde dragas storningsfritt. Efter tva stick i dragmaskinen hade ytan av de ror, som fosfaterats i losningar utan kondenserade fosfat, morka flaekar och var pa storande satt Overtaekt med rester av fosfatskiktet, varfor man icke heller efter blankglodgningen av roren kunde erhalla en fullgod yta, pa vilken en elektroplatering hade varit mojlig. De enligt uppfinningen fosfaterade roren visade dare-mot efter tva stick en ljus, metalliknande yta, som icke heller vid efterfoljande glodgning vallade nagra som helst svarigheter for de fortsatta foradlingsoperationerna. Framf8rallt kunde en elektroplatering genomforas utan storning. Compared with this, the corresponding rep was usually phosphated in a phosphating solution with the above-mentioned composition but without condensed phosphate and was cold-worked in the manner described. While in the treatment proposed according to the invention a homogeneous and absorbed phosphate layer is obtained both the surface and the weld, the phosphate formation was during the phosphating with a bath which did not contain condensed phosphate, the ojaran over the whole surface and above all the pH weld. The tubes phosphated with solutions without condensed phosphate consequently passed anxiously through the drawbar and periodically had a tendency to rattle, while the tubes phosphated according to the invention could be drawn without disturbance. After two stitches in the tractor, the surface of the tubes, which had been phosphated in solutions without condensed phosphate, had dark flakes and was largely covered with remnants of the phosphate layer, so that even after the glossy annealing of the tubes it was not possible to obtain a good surface on which an electroplating had been possible. The tubes phosphated according to the invention, on the other hand, showed, after two sticks, a light, metal-like surface, which, even on subsequent annealing, did not cause any liability for the further refining operations. Above all, an electroplating could be carried out without interference.

Den i exempel 1 angivna fosfateringslosningen kart hallas verksam genom komplettering med hjalp av en losning med foljande sammansattning: 202,0 g/1 zink 330,0 g/1 P20 199,0 g/1 NO3 Losningen kompletteras dessutom med nitrit och kondenserat fosfat, fOretradesvis i farhallandet 1: 1, varvid den tillsatta mangden beraknas med hansyn till nitrithaltens uppratthallande. The phosphating solution indicated in Example 1 is kept active by supplementing with the aid of a solution with the following composition: 202.0 g / l zinc 330.0 g / l P20 199.0 g / l NO3 The solution is additionally supplemented with nitrite and condensed phosphate. Preferably in the ratio 1: 1, the added amount being calculated with a view to maintaining the nitrite content.

For fosfateringen kan man aven anvanda losningar med andra oxidationsmedel, och da. 291 83 framforallt zinkfosfatlosningar eller 18sningar, som atminstone innehalla zinkfosfat., Som ytterligare oxidationsmedel ha klorat i bland-fling med nitrat, nitrit enbart, visat sig gynnsamma. Lbsningarnas halter av kondenserade fosfat utgora awn i dessa fall 0,01-0,8 g/1. Liisningarna kunna forutom zinkfosfat aven innehalla andra tillsatser, t. ex. kalciumsalter, framf &alit kalciumfo slat, mangansalter, framforallt manganfosfat, jarnsalter, framforallt jarnfosfat. For the phosphating, one can also use solutions with other oxidizing agents, and then. 291 83 especially zinc phosphate solutions or solutions which at least contain zinc phosphate. The contents of the condensed phosphate liquids in these cases are 0.01-0.8 g / l. In addition to zinc phosphate, the leaches may also contain other additives, e.g. calcium salts, especially calcium phosphate, manganese salts, especially manganese phosphate, iron salts, especially iron phosphate.

Exempel 2. For ansattning och komplettering anvandes ett vattenhaltigt koncentrat med foljande sammansattning: 113,5 g/1 Zn 348,0 g/1 P20 126,5 g/1 C3 47,0 g/1 Na20 Ett med denna losning framstallt bad hade foljande sammansattning: 3,1 g/1 Zn 9,4 g/1 P20 3,4 g/1 C3 1,3 g/1 Na20 Till detta grundbad sattes 0,12 g/1 pentanatriumtripolyfosfat, i ett annat fall 0,1 g/1 natriumhexametafosfat, och i dessa bad, ilksom aven i ett bad utan tillsats, fosfaterades st.ilror 8 minuter vid 70° C medelst neddoppning. P samma satt som angetts I exempel 1 intAlades roren darefter och drogos. Efter dragningen visade de r6r, som behandlats i baden enligt uppfinningen, en vasentligt ljusare, nastan blank yta, under det att j5.mforelseroren fortfarande uppvisade vasentliga Aterstoder av fosfatskikt och smorjmedel. Baden kompletterades med det ovan angivna koncentratet till konstant zink- och fosfathalt. Vid kompletteringen tillsattes kondenserat fosfat i sadan mangd, att till badet, raknat per m2 behandlad yta, sattes 0,5 g natriumhexametafosfat resp. 1 g pentanatriumtripolyfosfat. Example 2. An aqueous concentrate with the following composition was used for preparation and supplementation: 113.5 g / l Zn 348.0 g / l P 2 O 126.5 g / l C 3 47.0 g / l Na 2 O A bath prepared with this solution had the following composition: 3.1 g / l Zn 9.4 g / l P20 3.4 g / l C3 1.3 g / l Na2 O To this basic bath was added 0.12 g / l pentasodium tripolyphosphate, in another case 0.1 g / l sodium hexametaphosphate, and in these baths, as well as in a bath without additive, the phosphor was stirred for 8 minutes at 70 ° C by immersion. In the same manner as in Example 1, the tubes were then inhaled and drawn. After drawing, the tubes treated in the baths of the invention showed a substantially lighter, almost glossy surface, while the tubular tubes still showed substantial residues of phosphate layers and lubricants. The baths were supplemented with the above concentrate to a constant zinc and phosphate content. In addition, condensed phosphate was added in such an amount that 0.5 g of sodium hexametaphosphate resp. 1 g of pentasodium tripolyphosphate.

Claims

Patent claim:

1. Process for cold working with the aid of zinc phosphate containing Coatings for workpieces, which are only intended to undergo a slight deformation after cold working and soon after the cold working should not show any further processing of large residues of the phosphate layer on the surface, treated with phosphating solutions containing oxidizing agents and zinc phosphate and at least one condensed phosphate, in particular pyro-, tripolyoiler hexametaphosphate, in amounts of 0.01-0.8 g / l, shaved as the alkali metal salt of the condensed phosphoric acid in question.

2. A process according to claim 1, characterized in that 0.12.5 g of condensed phosphate per surface treated is added to supplement the phosphating solutions.

3. Process according to claim 2, characterized in that the phosphate layer is Ophorised with the aid of a nitrite accelerator as well as at least one condensed phosphate containing solution, which is supplemented with such a large amount of nitrite that in addition the nitrite: condensed phosphate ratio is 2: 1 to 1: 6 10- in a row 1: 2 to 1:

4., Request publications: Patents frcin France 1,138,208; United Kingdom 530 006, 604 325; USA 2,758,919, 2,826,517.