DE2033899A1 - Process for the surface treatment of a material made of iron or iron alloy - Google Patents

Description

PATENTAISiWAUTE DR. INQ. OTTO STURNER. DR. FRIEDRICH EMAYER

. Ina. O. Stürner-Dr. F, Mayer-753Pforzhelm, Juliua-Naeher-Str, 13 ~ l

76aPforaheim June 30, 1970

Jullue-Naeher-Str. 13 UneerZelohen Dr.M /]? I ·

L J-

Your Zelohon

Pa t β η ta η m e I dung

Applicant; Messrs. Toyota Jidosha Kogyo Kabuehiki Kaisha and Kabushiki Kaisha Toyota Ghuo-. Kenkyusho, -Toyota-shi, and Nagoya-shi, Aichi-ken, (Japan)

Designation: Process for the surface treatment of a material made of iron or iron alloys

The invention relates to a method for surface treatment of components or tools made of iron or iron alloys that are exposed to constant wear or impact.

It is known that boron is generally used to increase the hardness of Steels used. It is commonly used for finished components or tools, such as welding dies Surface hardness or wear resistance due to diffusion of boron to increase in the surfaces. The disadvantage of dies.ee conventional method is that the so treated products under mechanical impact easy to break due to the lack of toughness. Iron alloys with a low content are also known of zirconium.

! The invention is based on the task «, a process of At the beginning of the above-mentioned kind of training so that the treated

Ö098S4 / 1.S2.8

Surfaces of iron and iron alloys are both tear-resistant and wear-resistant

This object is achieved according to the invention in that the surfaces of. Iron and iron alloys are impregnated with zirconium in addition to boron, * in order to increase the diffusion depth of the boron »

According to a Yerfahrensvariante sur surface treatment of iron or iron alloys of these materials' is formed by immersion in a mixture to the pulverized boron or boron compounds and powder-W verisiertem zirconium or zirconium compounds and under the influence of a heat treatment. . DiffusionseMciats, in particular. Boron and Zirfeo- Ώ.ΪΈΤ- "Tfehält. For this see. Boron compounds / such as B ,, u ₃ S'eBj, Borais wan boric acid and. Zirconium _{compounds such as Fe-Zr 8} ZrO ₂ and ZrJL, _p where 1 is halogen. "

Conveniently, & s © expected §emically an addition! Is added ^ ά®τ at least one of the.02yö @ _ö larbönatej, Phosphat®, Cyanate umio ä © r Alkali- = and. Alkaline earth metals ι Ton @ röe | Silisimacarbide. and the like consists, it is the task of these additives to ^ 'increase the rate of diffusion iroa boron and zirconium', to bring about the formation of a protective diffusion layer and also to ensure good machinability o -

Also kanii ^ fiea §eaise! I eia BiM © sitt © l vl® kat mit öler olm © giisatgg> t © ff © © fdgisgofeea warden _o . Aas äiessa © © eilseli g @ ^ Iläet © Säst © w ± 2? Ä on the OöQSiiläöhe des

fabric

achieve full diffusion when the paste and the surface of the material by means of a high-frequency induction heating is heated.

Furthermore, according to the invention, the surface treatment can be carried out by heating the materials in a grass cover containing both gaseous boron and gaseous zirconium compounds. It is advisable to use a non-oxidizing carrier gas such as hydrogen, nitrogen, helium or argon in order to be able to introduce these compounds in the gaseous state into the heat treatment furnace. BF, ι BCl ,, BI ~, BBr ,, B ₂ Hg and the like are used as gaseous boron compounds, and ZrFj, ZrCL ·, ZrBr ,, ZrI are used as gaseous zirconium compounds. and the like are used.

In another embodiment of the invention, the surface treatment can be carried out by immersing the material in a high-temperature molten bath made from a mixture of boron and zirconium compounds. Although the melting point of both boron at 23OO ° C and of zirconium with 1,900 ⁰ C above the melting point of iron with 153O ° C, the compound mixtures melt of these metals at about 900 ⁰ C. Therefore, the impregnation with boron and zirconium with Immersion of materials made of iron and iron alloys in a bath of the melt mixture of these compounds can be achieved over a period of several hours. In this case it is advisable to correctly choose the melting point of the bath and the diffusion rates of boron and zirconium by adding an additive to the melt mixture which has been selected from at least one of the alkali oxides and salts and alkaline earth metals.

009884/1625

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Surface wear, due to flex · reinforced® 'through « 'annotation of boron as follows: ?? ImpsSgaieruu ^ 'Bit- IiE--. konimn.

The steps described below for «■ to play. obtained Brgeteisse ». GSÄassi icy Figures demonstrated * or "by hand"? © a B placed." . . .

Eb äseigen: (* ■ with ntal

Fig. -1 * a. Photomicrograph etesr Qmereeteitteo - "■■

■ ";'of a test piece, äas according to Example I = I-. ■ ■, ■" deals with vmräe,. ■■ ■ '■. ■.

Jig. 2 * one. Microphotography, iea Qnersetolttes ■ of a test piece * naoh example ΪΙ «1 ,

Pig · 3 a diagram of a * Biff-ßsioastlefe ia Ab «'- dependence on the temperature according to Example 11 =

IFig «. 4 a-Diagraaaa- des'Pros'.entaateils "des

. . ned .zirconium depending on v@ai.QS "temperature aaeh. Example. 11-1 _d

lig · 5 *. a microphotograph of the cross-section .a test piece nasli Example II-2 / "-

fig »6 a diagram at the diffmsieiastief.e in

dependency on the B & duration of handling aacli. '. Example Hl-I ₁ '.''

Fig. 7 a Biagraiiia 'äer Mika? O «7iökorshärt © -Ia . ■ Dependency τοη ier Sif

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tetr ^ g the ATbscteotkfeempessite 02G ⁰ G

and the starting temperature 200 ⁰ C ₀ lic tung. was with a BIoiiaiiiscliIoirasLotiliBe qe £ üio yorgescfarielienen iluSe ^ caeliliifen »Obnolil elüi I5si .with the 'conventional 7r-drive w EinsatzhSrten, ililrieiarsitemci fachencltenii. Seteaucii loicht 'C% orfIäeheziii? LDOG and the forrichtrag as a result of EiDana ^ i EU break go * ;, iaaitj, ti <sfreu Tosi dor? according to the procedure according to lifhaaclolten Vorrisfo '^ ag na βία rj 2500 Arbeitseinsütiscn Iiclae cracks

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Me surface cLieo! «\ 25 ei χ 49 α piece of legi <v? Toit steal for M"? Oi * .li2r.cnbautni3e ( S0r22) was with Liuer: a. 2 ibiq öi ^ iicE layer 3 ¹ Q a- «u 40 Sewi ^ htspr ^ Lecten ame 1 ^ 0 7-Da ea _a 525 feinhöltii 'su 40 f ^ Wic ^ t ^ proreat ^ a ^r ^ \ c r ^% cij , a ^ "7t: η cd.» Sieve fineness and much more. * P

ca.- 560 'Siebfeiiit-cit "^ \ le r.ro ItI ^ IjJliirc' Gemisch lestrirliuP» P ™ r CaafT'i th ^ ^ | j _C 5 2OC = · 4CO ⁰ P 2 to ^{-4 hours ii 1} cl animal " ϊ ^τ , ißl ^ ftoier gptroeöot unö. as.-schlieBeaä 1? felr ^ ndWi ^ mg Is ei »^ r nocbfeefiEoaiJ-Hci coil with eimee Iii'tieaiaiöhmessei · worn Ji wm erfedtnt Vext .. £ ttr the ppo ^ firecwc ^ s was> 0 K? ic Bad ffe the Aa .gangslel« t% as IC ^f ? l, e Me Bi ffasioa ^^ csio ¹ DEATH. 332? ι? Zirkoaiüiä i>et2'vs. 25Af vjtil the Obeir-FläcIjoBliäi-fairy of the piece

00988.4 / 1825

Table 1

number 1

Upper
area Upper
fl "ehe Yer »
am
manure Particle
size
(Siebfeinho) G-ev / icht material depth
²⁰ Z * depth B ₄ C
Zr 325
100 60
20th
20th depth
d. diffusions
schi hurries
</ *) 220 Zr 0 _fl 04 material O ₉ 07 depth
d.Diffueione-
layer Hr 0 2 ¹ Ver
am
manure Particle
regards
(Siebfeinti ") weight B ₄ G
ZrO ₂
Na ₂ CO ₃ 325
360 60
20th
20th 200 0.87 0.03

ITr. 3

material Upper
area Upper
area Ver
am
manure Particle
size
(Sietofeinh.) ■ * weight Depth .
d. Diffusion
layer
O) depth
20 / fr depth
20 / t- B ₄ O
Ee-Zr
Ha ₂ OO ₅ 325
200 60
20th
20th Zr 250 0.61 material 0.04 depth
d. Diffusion
layer Ir. ■ 4- ' Zr Ver
am
manure Particle
size
(.Siebfelah.) 6-ev / icht B ₄ O
ZrOl ₄
Na ₂ OO ₃ 325
200 ■ 60
20th 250 . 1.88 0.10

0098 84 / 162S

Example II-1 (fas-

Test pieces made of unalloyed steel for 14 hm χ 20 ms for Masehinenbauteil © (JISgSIQö) were placed in a furnace which was charged with -Ifeaserptoff including BGl, and SrGl ₇ ! The specimens Mirfi'sa 1 Stisata T at temperatures of 800 ° C »9GÖ ° are guided by BGi ^ with an icon-""damming temperature foa ~ 73 ° C and by ZrGl," with a temperature foa 150 <= »200 ^{0 G} e imö 1000 ° Ö © shitat «fig» 2 3 © igt the photomicrograph of a cross section of the specimen. the one hour t »ei 900 ° ö b © foa & d <§lt x-xsarä®, Me analysis showed that cisS sisti äsx ä © 5? ! ate e @ s ?. The surface of the diffusion layer IqB and is Iaa @ sa of the Mf'fusioasaohicht mainly formed f'© _n B liatt © «. Ms Ug ₀ 3 _P in which the -Beslalmiig suiseliea Biffmsionstisf © land Betrluiäg-s--

is clear ersiciitliehj, tos ea _o 55/2 bei © iner vom 900 ⁰ O ersislt tiuräe _ä bei ν iner Beaa2iälis * getGiHj5e3iSit ^ ?? yq '& 1000 0 feoimte wegsa. der Bildung 7on klQiaiea]? @ e & £ tQ $ M§ siafsi®Äeaet @ lleffiä © Diffueionsschielit, © E3i®lt "t7 © 5? (ä @ ao .tJi © srss Iig _o 4 · erfiii" irlliGli .- "feeueist öi ® lozLtgeafliioseiJseaganaljs® - der öherfläüho ier liffiiglongseliieMs the zirconium "content ciisr Mxfesioasselalooks ait constant © aäsr treatment temperature- increased" from fig ο 4 "1st © Tbösafalls @ how the effect is <3% , ie keeping the temperature constant "at 2QO ^ o tma? the H @ aga S © s ^; gaseous ZrGl ^ s äas Is hydrogen subliEisirte _s · about.® than at 150 ° G.. -. - ■

i. t - -T ir Si _ 2 ß- vj'Ji; i * j otiootüeis an ©

had been passed, heated at a temperature of 90O ^{0 C.} The sample was then for 6 hours in a furnace with a gas filling consisting of hydrogen, the vo, held by RHER at a temperature of 200 ⁰ G ZrCl. had been passed, heated again at 100 ° C. Thereafter, the specimen was slowly cooled. Fig. 5 shows a microphotograph of the cross section of this test piece. The diffusion depth was approx. Fl'iche and $ 0.05 zirconium were contained in a surface depth of 20 U.

Example II-3 (gas process)

In the Imprägnlerbehandlung a forging from steel When wurde- (JIS: SED4) for four hours at 950 ° C Ln furnace exposed to a hydrogen gas atmosphere, both the BCL and ZrC1. contained. This gas bag was produced by hydrogen by kept at -73 C BCl, and kept at 200 ⁰ C ZrGl. directed. The forging ^{die was then quenched from 1050 0} C heat, followed by two tempering at 60O ⁰ C,

Because the forged with the help of this forging die Ketal Heat Resistant Steel (JISiSUHI) 1st, enters so much wear and tear on the die that its end of service life after 2500 to 3000 work assignments is. A die, which according to the inventive method has been treated, but has a service life of 5,000 to 6,000 work assignments, which is double that Corresponds to the service life of a conventional die. The formation of heat cracks was low and the Accuracy of die-made products satisfactory.

00 98 8 4/1625

BeJBpiejLJEII-1 "(jflÜBsij gkeits-Yerfahren l

18 mm χ 40 mm specimens of unalloyed structural steel (JIS s 84 5G), tool steel (JlSgSKS ₁ , JISsSHH, JISsSfCD61) and malleable cast iron (JISsKOHO) were immersed for 1 to 8 hours in a ^{molten bath heated to 95O 0} C, which had a weight of 50 parts from Boraxs, au 30 weight · = percentage of ZrO ₉ ρ to 10 Gewichtsprosenten from _Β Δ C and to 10 percent by weight of HACL consisted »Figo shows the relationship swischen immersion time, d _o h =, treatment time and the Diffusionetiefe in these specimens ,, measured with the help of microscopic sub-booking "The qualitative spectral analysis confirmed" that all diffuelon layers contained both boron and zirconium ",

Belsplel_III-2_ ()

An ¥ armsehmiede stamping die made of Xiasrmarbeits die steel (JISsSKD61) was immersed for 5 hours at 95O ° C in a molten bath with the same composition as in Example III-1. The stamping was then quenched from 1050 ° G heat, followed by twice Tempering at 600 C. The service life of the

. The die was 9915 jobs, about three times as much as the average of 3800 work inserts for the service life of conventional embossing dies »

Example III ~ 5 (happiness method l

A Warmschmiedegesenk from hot-work steel (JISsSO4) was 5 hours in the bath of a Schmelzgemicchee with the same composition as dipped at 900 ⁰ C in Example III -1. Then the die from 1050 ⁰ C heat was quenched and once at 62O ⁰ G and once at 600 ⁰ C. The life of the die was 14820 jobs, about 5 »5 times 009884/1625

as long as the average service life of conventional dies with 2700 work assignments. This die did not show any cracks during its entire service life

Example IV-1 ( Electrolytic "Process);

A 18 mm χ 50 mm coupon of mild steel (JISJS450) was dissolved in a molten .with 85 Nominal chtsprozenten borax and 15 percent by weight zirco "niumoxyd immersed and, as a cathode used» 2 hours at a temperature of 900 ⁰ C under the action of a current density of 12 A per square decimeter electrolysed. Curve 2 in Fig. 7 shows the relationship between the diffusion depth and the micro Vickers hardness of this test piece. Curve 1 in Fig. 7 shows the same relationship as above for a test piece treated by the conventional method, namely, by immersion in a bath of molten borax containing no zirconia and electrolysis under the same conditions as mentioned above. The surface hardness of the diffusion layer in the test piece treated according to the method of the invention was 1520 compared to 1120 for the test piece treated according to the conventional method. 8 and 9 show photomicrographs of the cross-sections through the diffusion layers of test pieces which were treated according to the conventional method and the method according to the invention, respectively. The impregnation depth was 100 ^ for the test piece produced by the method according to the invention compared to 50 ^ / 1 for the test piece produced by the conventional method. Curves 3, 4 and 5 in FIG. 10 each illustrate the influence of the percentage

009884/1625

L ^ b an ZiEkoniumosqrd on di © Yiskesiität d © s on the impregnation depth in the test pieces and on the hardness of the "diffusion top layer" It is clearly evident; that in all cases the maximum value © Tb @ i -5 to 15 $ "content zirconia nrerden reaches ₀ Sin-ßshalt to Zirkoniumozyö of more than $ 30 is not advantageous because _5. the solubility τοη zirconium oxide In the bath with a .portion "won / -approx. 30 $ the saturation point © See ₀ S ¹ Ig ₀ 11 illustrates the relationship between a hard® ü®i? Biffuslonsschicht dör after the

Surface and the Äalassteiipiratiir
it is shown that the occasion © aperatMr does not. Has an influence on the hardness. Bah @ r ^ esrlagsst see the hardness ae after the esiiaetaa§sg © ®ä © es Tt ^ fahrea treated tool not ,, w @ na äas Werkseug wäteenä of use due to the Temperateraastiega AaIaSt © mperaturen, "as, 3 clsraiaf hiiidoiitetj that look nseh the erfiadungs · = γ '; - · ;; - "- ferfahren behandolt © l'J © RLSS © iag® for a long ^f re" brtiiioh eigaen "

It is also said ₉ that ice is aa @ h according to the invention. ■ Farfahresi hardened frolestüok has an extraordinary toughness _f since no signs of flaking are observed _g although a kl isi Serb arose when a 5 kg gaw blow from a height of 1500 am onto the surface fi @ l during an impact test ₀

Table 2 contains the results of spectral analysis on the hardened case eiass Naeh the Invention = "process according .behandelten Probestüofess plays the violin and ₈ that the Sinsatzschioht © Inesi Hoh © a proportion of boron-containing zirconium IIad The orhaadeas ¥ @ ia represents other elements. is on the crucible aue rostfrei®!
which during the Elekteolys © as Mod © <äl <3nt © _t

ORIGINAL INSPECTED

Table 2

element ■ Β 2r Cr Hi Approx Ha Mg Analyzes
value · * - ++ +++ + (Wf) + (f) + (Wf) + (Wf)

In addition, were not treated and after the inventive devices Procedure "treated specimens" at a temperature of 95O ° C for one hour of the external atmosphere also acetate. In the first case one observed the education and the flaking off of an oxide layer on the surface of the test pieces, but in the second case no oxide layer was observed, although a slight one Oxidation discoloration was visible. In this way

Vlass the proof has been furnished ', Dafi ^r desirable according to the method erflnäuhgegeniäßen treated specimen Antioxydatieneeigenschaften comparable to those \ ^r on steel of roptfreiem, beeitct.

Example I V- £ ( electrolytic process)

A Warmochmiedegesenk made of hot work die steel was dipped into an existing S5 to percentages by weight of borax and from 15 Gewichtsprosenten zirconia (srop) Sehmelsbadgemiseh electrolytically and impregnated for two hours under the action of a current density of 10 A per square decimeter at 105 ⁰ C. Then the die from 1050 ⁰ C Hitae was quenched and tempered twice at 55O ⁰ C, followed by cooling in. Cl done. The life of this die was 7089 jobs, which is three times the life of a conventional die with £ 650 jobs. In addition, there were neither heat cracks nor one

9884/1625

Reduction of the surface hardness of the die, although the surface temperatures of the die reached ^{700 to 800 0 G in continuous operation during closed-die forging.}

Example IV-3 (Electrolytic Process)

Three clamping pins made of unalloyed tool steel (JISiSKJ) for grinding the inner circles of gears were immersed in a molten bath made of $ 80 parts by weight of borax and $ 20 parts by weight of zirconium oxide and electrolytically impregnated for 2 hours at 880 ° C. under a current density of approx. 15 A per square decimeter. subsequently, these pins were quenched from 840 ⁰ C heat annealed at 16O ° C and then cooled in oil. these cones had exactly six times the life of cones, which were produced in a conventional die, and their accuracy was greater.

Example IV-4 (Electrolytic Process)

A hot forging die made of hot-work die steel (JIS: SED61) was electrolytically impregnated in a molten bath of 90 parts by weight of borax and 10 parts by weight of zirconium oxide for 2 hours at 900 ^° C. under a current density of 15 A per square decimeter. The die was quenched in a vacuum from 1050 ° C heat and annealed twice at 55O ⁰ C and 'finally cooled in gas. The service life of this die was 13,340 jobs, roughly double the previous service life of 6,800 jobs.

In Examples IV-1 to IV-5, the method of the present invention was to materials made of carbon steel used in accordance with and to materials made of alloyed steel, however, the erfindungsgemäSe Imprägnierbe-

009884/1625

trading also in cast iron and sintered products ! Ferroalloy applicable. With the aid of the treatment according to the invention, an insert layer can be created of extreme hardness, a diffusion layer with a desired level of toughness, and a Produce an oxidation-resistant surface layer. Figures 12 and 13 show photomicrographs of cross sections impregnated zones in test pieces treated by the method according to the invention from each ordinary cast iron (JISjFG25) and spheroidal graphite cast iron (JIS: FGD4O), In both cases, the Surface hardness of the impregnated zone values for the Micro Vickers hardness, which was between 1100 and 1200. Pig. 14 shows a photomicrograph of the cross section through the impregnated zone of a test piece, a ferro-alloy product of powder metallurgy, with a carbon content of $ 1. This showed the surface hardness of the impregnated zone a value of 1150 micro Vickers hardness.

009334/162

Claims (10)

2033839 claims 1. A method for the surface treatment of a material made of Elsen or iron alloys including heating the material, characterized in that it is brought into contact with a mixture of boron or boron compounds and zirconium or zirconium compounds in such a way that a diffusion layer is formed in the surface of this material contains both boron and zirconium in particular. ■ ...- ■■■. · 2. The method according to claim 1, characterized in that the mixture consists of a boron or boron compounds and Zirconium or zirconium compounds existing powder mixture and the material in this powder mixture is packed. 3. The method according to claim 2, characterized in that that an additive is added to the powder mixture, which consists of at least one of the group of oysts, carbonates, phosphates and cyanates of alkali and alkaline earth metals, Is composed of alumina and silicon carbide selected substance. 4. The method according to claim 2, characterized in that that a binder such as A "tylsilicate this Powder mixture is added and a paste made from this Mixture is applied to the surface of the material. 009884/1625 5. The method according to claim 1, characterized in that that the mixture of gaseous boron and zirconium compounds consists. 6. The method according to claim 1, characterized in that that the mixture is a weld pool consisting of boron and zirconium compounds, and the material is immersed in this molten bath. 7. The method according to claim 6, characterized in that that an additive is added to the molten bath, consisting of at least one of the group of oxides, carbonates, phosphates and gyanates of the alkali and alkaline earth metals, Alumina and silicon carbide is made up of a selected substance. 8. The method according to claim 6, characterized in that that the material is immersed in this molten bath as a cathode opposite an anode and electrolytically is impregnated. 9. The method according to claim 8, characterized in that that an additive is added to the weld pool, consisting of at least one from the group of oxides, carbonates, Phosphates and gyanates of alkali and alkaline earth metals, Is composed of alumina and silicon carbide selected substance. 10. Process for the surface treatment of a material made of iron or iron alloys, characterized in that there is a heating stage of the Material includes, while the material with boron or boron compounds is brought into contact to form a boron-containing diffusion layer of the material surface and a subsequent stage of Heating of the material, during which the material in contact with zirconium or zirconium compounds is brought to this layer with zirconium too penetrating L.Q 0 9 8 8 4/1 p. 2 p BATH ORIGINAL