EP0719349A1

EP0719349A1 - Process for preparing a powder mixture and its use

Info

Publication number: EP0719349A1
Application number: EP94926797A
Authority: EP
Inventors: Norbert Dautzenberg; Karl-Heinz Lindner; Klaus Vossen
Original assignee: Mannesmann AG
Current assignee: QMP Metal Powders GmbH
Priority date: 1993-09-16
Filing date: 1994-09-09
Publication date: 1996-07-03
Anticipated expiration: 2014-09-09
Also published as: US5628046A; CA2165087A1; CA2165087C; JP3572078B2; WO1995008006A1; JPH09502766A; EP0719349B1; ATE165628T1; ES2115257T3

Abstract

PCT No. PCT/DE94/01087 Sec. 371 Date Oct. 31, 1995 Sec. 102(e) Date Oct. 31, 1995 PCT Filed Sep. 9, 1994 PCT Pub. No. WO95/08006 PCT Pub. Date Mar. 23, 1995A process for fabrication of sintered articles from a molybdenum-containing steel alloy by atomization, pressing, and sintering. The melt used for atomization has a molybdenum content determined as a function of the sintering temperature which lies in a range of 1050 DEG -1350 DEG C. The carbon content of the powder mixture is no more than 0.05% by weight and the reduction annealing takes place in a temperature range of 850 DEG -950 DEG C.

Description

Process for producing a powder mixture and its use

The invention relates to a method for producing a powder mixture according to the preamble of claim 1 and the use of such a powder mixture for the production of sintered parts with high toughness and density.

The production of mechanical components from iron materials by means of sintering technology has compared to a production by cutting

Forming (e.g. turning, drilling, milling) the great advantage that the actual shaping in a single operation practically without the

Waste material can occur and is therefore faster and less expensive for series parts. The parts will

for example on a hydraulic metal powder press in a mold using a pressure of, for example, 7 t / cm ²

Green compacts are pressed and then in an oven at about 1120-1150 ° C

(Normal sintering) or also sintered at about 1250-1280 ° C (high-temperature sintering) in order to achieve sufficient static and dynamic strength. Due to the manufacturing process, sintered parts are always smaller

Density than that of the corresponding solid material (theoretical Density) because they are penetrated by pores. In the case of ferrous materials, the actual density of the sintered parts is usually around 60-92% of the theoretical density, depending on the pressure applied and the shape of the part. This inevitably results in one

Impairment of the mechanical properties, which leads to the fact that sintered parts have so far hardly been used with particularly high mechanical stress, especially since larger dimensions to compensate for this disadvantage cannot generally be accepted because of the associated increase in volume and weight. In addition, the pores contained in the sintered part can act as internal notches, which leads to a drastic reduction, in particular of dynamic ones

Strength properties can lead.

In order to reduce the pore volume of sintered parts, it is known to use the iron-based powder with a higher phosphorus content. This leads to a significant shrinkage during the sintering process and thus to an increase in density. The shrinkage of the sintered part is taken into account in the geometric design of the press mold by appropriate oversize and can thus be largely compensated for. However, the addition of phosphorus, which can be done either by appropriate alloying to the melt used in powder atomization or by admixing phosphorus compounds to the iron-based powder, has the disadvantage that it is only used to a certain extent

Density increase can be used because higher phosphorus contents tend to cause embrittlement of the sintered part and thus the sensitivity to the notch effect is further increased.

Another way of achieving a higher density, that is to say a reduction in the pore volume, is to be seen in the so-called double-sintering technique, in which the pressed body is added after a first sintering

usually about 700 - 900 ° C one more pressing and one final final sintering. Because of the double pressing and sintering, this is a very

costly process.

An iron-based powder is known from WO 91/19562, which is said to ensure a comparatively high impact strength. It prescribes 0.3 - 0.7% by weight phosphorus and 0.3 - 3.5% by weight molybdenum as alloying elements. Any other alloying elements present are limited to a maximum of 2% by weight. The molybdenum content is preferably 0.5-2.5% by weight and that of phosphorus

0.4 - 0.5% by weight (addition in the form of Fe ₃ P in particular). An upper limit of 0.07% by weight is recommended for carbon. This iron-based powder is suitable for normal sintering temperatures (below 1450 ° C). The test results shown in this document show that optimum proportions exist for both phosphorus and molybdenum, in which the impact strength is particularly high. So it rises

Impact resistance with a powder with 0.5% by weight phosphorus

The molybdenum content rises steeply from 0 to 1.0% by weight, reaches a maximum in the range of 1 to 2% by weight and even drops below 3.5% by weight of molybdenum to below the initial values.

Furthermore, DE 29 43 601 C2 discloses a prealloyed steel powder for producing high-strength sintered parts which contains 0.35 to 1.50% Mn, 0.2 to 5.0% Cr, 0.1 to 7.0% Mo, 0 , 01 to 1.0 V, maximum 0.10% Si, maximum 0.01% AI, maximum 0.05% C, maximum 0.004% N, maximum 0.25% oxygen, balance iron and other manufacturing-related impurities. The low C content is required to get a good one

To enable the steel powder to be pressed, which is produced by water atomization of a corresponding melt and subsequent reduction annealing at 1000 ° C. Before being pressed into green compacts, this steel powder is lubricated with lubricants (e.g. 1% zinc stearate) in the usual way. added and additionally mixed with graphite powder in order to be able to set the desired C content in the sintered part. The amount of graphite powder added is regularly several tenths of a percent (eg 0.8%), since the sintered parts are hardened in oil after sintering

to obtain sufficient strength values. The ready to press

Metal powder mixture must therefore have a sufficiently high C content for tempering steel, taking into account the burn-off losses to be expected during sintering. The sintering process inevitably creates a structure due to the C content, which depends on

The cooling rate consists of martensite or martensite and bainite or bainite and pearlite. In order to achieve a density that is close to the theoretical density of steel, it is provided that the sintered parts undergo a forging process before the heat treatment

undergo.

In the case of gears that are subject to high mechanical stress, in addition to the highest possible tooth root bending fatigue strength, a high one is particularly important

Tooth flank load capacity required. Therefore, such gears are usually hardened. For a material with a relatively high

However, phosphorus content leads to an inadmissible embrittlement of the component.

The object of the invention is therefore to provide a method of the generic type which produces a ready-to-press steel powder mixture from which sintered parts can be produced with high density, which with good

Surface hardenability, in particular good dynamic

Have strength properties and can therefore be used without using the complex double sintering technology or a forging process for mechanically particularly heavy-duty components, in particular as gears for automotive transmissions and the like

stressed components. As a side task, the use of Powder mixture according to the invention for the production of such components can be specified.

This object is achieved with regard to the method by the features of patent claim 1. Advantageous embodiments of this method are specified in subclaims 2 to 7. The use of the powder mixture produced according to the invention for the production of

Sintered parts are characterized by the features of claim 8 and can be further developed in an advantageous manner by the features of subclaims 9 to 14.

It was completely surprising that it could be found that e.g. by gas atomization, gas / liquid atomization or preferably by

Water atomization of a steel melt containing molybdenum and subsequent

Reduction and soft annealing at 850 - 950 ° C steel powder after mixing with common lubricants in powder metallurgy

(eg zinc stearate) can be processed into components that only have an extremely small pore volume, ie a density close to the theoretically highest possible density of the material (eg 95 to 98%). All that is required is a simple pressing using customary pressures in the range 6.0-8.0 t / cm ² , preferably 6.5-7.5 t / cm ² . The sintering temperatures can range from 1050 -

1350 C, with higher temperatures being preferred. This means about up to 1150 ° C when using belt furnaces and about for walking beam furnaces

1250 - 1300 ° C (high temperature sintering). High-temperature sintering can further increase the achievable density compared to normal sintering.

The powder mixture according to the invention is characterized in that it is practically phosphorus-free, that is to say it contains phosphorus only as an impurity (P <0.02% by weight). The minimum required molybdenum content The molten steel that is to be used for the powder production depends on the intended sintering temperature during the later production of the sintered parts. In any case, a content of 4.0% by weight is already sufficient. For economic reasons, an upper limit of 5% by weight, preferably even only 4.5% by weight, should not be exceeded. At a sintering temperature of 1120 ° C 3.8% by weight of molybdenum and at 1280 ° C even 2.7% by weight are sufficient. Due to the melting tolerances to be taken into account, it is advisable to increase these lower limit values by, for example, 0.5% by weight to 4.3% by weight or 3.2% by weight. The minimum required molybdenum can be determined as a function of the sintering temperature T _s as follows:

The molten steel to be atomized not only has to be practically phosphorus-free, but also must not have any appreciable carbon content (C <0.01% by weight) so that the powder remains sufficiently soft and easy to press. To increase the strength, in individual cases, although this should even be avoided if possible, graphite can be added to the powder, which, however, may at most lead to a carbon content of 0.06% by weight in the powder mixture. Limiting the carbon content to max. 0.04% by weight and in particular to a max.

0.02% by weight. The powder can also contain the usual contaminants of a molten steel. In addition to molybdenum, other metallic alloy additives are not required, but usually do not interfere if they do not assume too large values. Overall, these additional alloy elements should not exceed a total of 1.0% by weight, preferably 0.5% by weight. To increase the strength of the Alloy can be expedient in particular the addition of chromium (preferably without further additional alloy elements) within the limits mentioned.

When processing the powder mixture according to the invention, it is advantageous to carry out the sintering process in a reducing atmosphere, in particular in an atmosphere containing at least 10% by volume, preferably 20-40% by volume, of hydrogen. So that will

achieved, for example, that the elimination of nitrides is avoided or reduced to a minimum. For example, it is advisable to use forming gas, ie a mixture of H ₂ and N ₂ . Higher

H ₂ contents tend to improve the density that can be achieved during sintering, which, due to the setting of the powder mixture according to the invention, takes place exclusively in the alpha phase and therefore strongly promotes density sintering (without the formation of a liquid phase). The cooling after sintering does not require any special measures. The sintered parts have a purely ferritic structure made of FeMo mixed crystals.

The sintered parts can then be subjected to a calibration, which leads to a deformation in the surface area

(Leveling the roughness) and thus to a better one

Surface quality and dimensional accuracy. Thereafter, case hardening can be carried out in a known manner, which is particularly recommended for gears and similarly stressed parts, since it leads to a substantial increase in the surface hardness and to the introduction of

Residual compressive stresses. In the case of gearwheels, it is advisable to subject the toothing area to soft scraping before case hardening. After hardening the gears, the usual grinding of bores and flat surfaces can be carried out.

The sintered parts produced in this way have a close to theoretical maximum density, it being particularly noteworthy that the remaining pores are small, self-contained and round and therefore do not have any significant notch effect. This results in excellent dynamic strength values as well as high surface hardness after case hardening, which are of crucial importance for wear resistance and tooth flank load capacity, for example.

The invention is explained in more detail with the aid of the following exemplary embodiment. Figures 1 and 2 show, in different magnifications, micrographs of sintered parts made from the material according to the invention.

From a molten steel with (% by weight)

<0.01% C

<0.02% P

3.2% Mon

The rest of the iron and usual impurities (<0.5%) were produced by spraying water into a fine, spicy steel powder. After a reduction annealing for approx. 70 min at approx.

900 ° C was the powder, which has a residual oxygen content of less than

0.15% by weight and after sieving had a grain size of less than 0.2 mm

0.8% by weight of micro wax mixed as a lubricant. On a hydraulic

Metal powder presses were produced from this material using a pressure of 7 t / cm ² test specimens according to ISO 2740, the

then at a temperature of 1280 ° C for approx. 30 min in one

Oven sintered under forming gas (80% N ₂ , 20% H ₂ ). At a

Subset of the test specimens was then case hardened at 920 - 950 ° C in an oven with a C potential of 0.8%, which led to a hardening depth of approx. 0.4 mm. The

Examination of the test specimens showed the following values: Sintered density 7.60 + 0.04 g / cm ³

(96 - 97% of theoretical density)

Flexural fatigue strength with 2 × 10 ⁶ load changes

after case hardening approx. 450 MPa

approx. 180 MPa without case hardening

Elongation at break sintered A ₅ > 25%

The extremely low porosity results from the micrographs of FIGS. 1 and 2, the advantageous round design of the pores being clearly evident from FIG. 2.

Claims

1. Process for producing a ready-to-press powder mixture

Steel powder, which is produced by atomization, in particular water atomization, a carbon- and phosphorus-free molybdenum steel melt with usual impurities and subsequent reduction and

Soft annealing is generated, and then mixed with conventional lubricants and, if necessary, to set a

Carbon content is mixed with small amounts of graphite powder to produce sintered parts with high toughness and density,

characterized,

that a melt is used for the atomization, the

Motybane content depending on the intended sintering temperature T _s lying in the range of approximately 1050-1350 ° C. is and at least

is that the carbon content of the powder mixture is limited to a maximum of 0.06% by weight and that the reduction annealing in

Temperature range 850 - 950 ° C takes place.

Method according to claim 1,

characterized,

that the content of other metallic alloy elements in the

Steel melt to a total of max 1.0% by weight, preferably

0.5% by weight.

3. The method according to claim 2,

characterized,

that chromium, in particular chromium, without any other alloying elements, is added to the melt.

4. The method according to any one of claims 1 to 3,

characterized,

that the molybdenum content for a sintering temperature of 1280 ° C is at least 3.2% by weight.

5. The method according to any one of claims 1 to 3,

characterized,

that the molybdenum content for a sintering temperature of 1120 ° C is at least 4.3% by weight.

6. The method according to any one of claims 1 to 5,

characterized,

that the molybdenum content is limited to a maximum of 5.0% by weight, preferably to a maximum of 4.5% by weight.

7. The method according to any one of claims 1 to 6,

characterized,

that the carbon content (graphite powder) to max. 0.04% by weight, in particular limited to 0.02% by weight.

8. Use of one generated according to one of claims 1 to 7

Powder mixture for the production of sintered parts with high toughness and density, with the proviso that the parts are pressed as green compacts by simple pressing technology with a pressing pressure of 6.0-8.0 t / cm ² and then at a temperature in the range of 1050-1350 ° C under a hydrogen containing at least 10% by volume Atmosphere, in particular an N ₂ H ₂ atmosphere are sintered and have a ferritic structure.

9. Use according to claim 8,

characterized,

that the H ₂ content is 20-40% by volume

10. Use according to claim 9,

characterized,

that the pressure is 6.5 - 7.5 t / cm ² ,

11. Use according to one of claims 8 to 9,

characterized,

that the sintering temperature is 1250 - 1300 ° C.

12. Use according to one of claims 8 to 11,

characterized,

that the sintered parts are then subjected to calibration.

13. Use according to one of claims 6-12,

characterized,

that the sintered and optionally calibrated parts, in particular manufactured as gear wheels, are subjected to case hardening.

14. Use according to claim 13,

characterized,

that the sintered and calibrated gears before

Case hardening in the tooth area.