This invention relates to a process of heat treating compacted iron-based powder compositions. More particularly, the invention relates to a process, in which iron compositions are mixed with thermoplastic resins, compacted and heated. The process is particularly useful for making magnetic core components having good soft magnetic properties and high strength.

US-Patent 5 268 140 discloses a method for pro¬ ducing a high-strength iron-based component by powder- metallurgical techniques. According to this method a powder composition of iron-based particles, which are coated or admixed with a thermoplastic material in the presence of an organic solvent, is compacted in a die at a temperature above the glass-transition temperature of the thermoplastic material and the obtained component is separately heated at a temperature that is at least as high as the compacting temperature up to about 800°F (427°C) . The resulting component has increased strength and can be used as a structural component or as a ag- netic core component. Furthermore, this patent discloses that, according to the most preferred embodiment, the thermoplastic material is present as a coating on the surfaces of the individual iron particles. In variations of this embodiment the iron particles can be double- coated such as where, in addition to an outer layer of the thermoplastic material, the particles nave a first inner coating of an insulative material such as iron phosphate.

In brief, the present invention concerns a process, according to which powder compositions of iron-based particles are admixed with a thermoplastic material. The obtained mixture is compacted at a temperatue below the glass-transition temperature or melting point of the

SUBSTITUTE SHEET

thermoplastic material and the compacted product is heated in order to cure the thermoplastic resin. Subse¬ quently the obtained compacted component is optionally annealed to a temperature above the curing temperature. Specifically, the invention concerns a process for powder-metallurgical preparation of products having high strength and improved soft-magnetic properties compris¬ ing the following steps a) treating particles of an atomised or sponge iron powder with phosphoric acid at a temperature and for a time sufficient to form an iron phosphate layer material, b) drying the obtained powder, c) mixing the dry powder with a dry powder of a thermoplastic resin selected from the group con¬ sisting of polyphenylene ethers and polyetherimides and oligomers of amide type, and with a low- .= melting lubricant to form a substantially homoge¬ neous particle mixture, d) compacting the obtained powder mixture in a die at a temperature below the glass-transition temperature or melting point of the thermoplastic resin e) heating the compacted product to the curing temperature of the thermoplastic resin, and f) optionally annealing the obtained component to a temperature above the curing temperature of the thermoplastic resin.

In step a) of the process, particles of an atomised or sponge iron powder are preferably treated with an aqueous phosphoric acid solution to form an iron phos¬ phate layer at the surface of the iron particles. The phosphoric acid treatment is carried out at room tem¬ perature and for a period of about 0.5 to about 2 hours. The water is then evaporated at a temperature of about 90°C to about 100°C in order to form a dry powder. Ac-

SU3STDTUTESHEET

cording to another embodiment of the invention the iron powder is treated with phosphoric acid dissolved in an organic solvent.

The phosphorous layer should be as thin as possible and at the same time coating the separate particle as completely as possible. Thus the amount of phosphorus is higher for powders with a larger specific surface area. As sponge powders have a higher specific surface area than atomised powders the amount of P should generally be higher for sponge powders than for atomised powders. In the first case the P amount may vary between about 0.02 and 0.06, preferably between 0.03 and 0.05 whereas in latter case the P amount might vary between 0.005 and 0.04, preferably between 0.008 and 0.03% by weight of the powder.

The thermoplastic materials used in the process of the invention may be polymers having a weight average molecular weight in the range of about 10 000 to 50 000 and a level of crystallinity that allows them to be dis- solved in an organic solvent. More specifically, the polymers are polyphenylene ethers, polyetherimides or any other of the polymers mentioned in US patent 5 268 140 which is hereby incorporated by reference. A commercially available polyetherimide is sold under the trade name of ULTEM® resin. The most preferred ULTEM® resin is ULTEM® 1000 grade. Another thermoplastic mate¬ rial which can be used according to the invention is an oligomer of amide type having a weight molecular weight less than 30 000. Oligomers of this type are disclosed in PCT/SE95/00636 which is also incorporated by refer¬ ence. Specific examples of oligomers are orgasols such as Orgasol 3501 and Orgasol 2001 available from Elf Atochem, France. These types of polymers are less amor¬ phous,i.e. more crystalline than the polymers according to US patent 5268140 and are not distinguished by glass-transitions temperatures but by melting points.

SUBSTBTUTESHEET

The particle size of the thermoplastic material is not critical. It is however preferred that the particle size is below about lOOμm. The amount of the thermoplas¬ tic material may vary between 0.1 and 1% by weight of the iron powder, preferably between 0.2 and 0.6% by weight.

In contrast to the process disclosed in the US patent 5 268 140, it is mandatory to use a lubricant in the process according to the present invention. Various lubricants can be used for mixing with the iron and thermoplastic particles. The lubricant, which preferably is of the low-melting type, may be se¬ lected from the group consisting of metal stearates, waxes, parafins, natural or synthetic fat derivates and oligomers of the amide type discussed above. Examples of commercially available lubricants which can be used in the process according to the invention are Kenolube® available from Hδganas AB Sweden, H-wax® available from Hoechst AG, Germany and Promold® available from Morton International of Cincinatti, Ihio. In this context it should be mentioned that the oligomers of amide type could be used either as thermoplastic resin or as lubri¬ cant or both. Thus, according to one embodiement of the invention, the insulated iron powder is mixed only with the oligomer in question, compacted at a temperature be¬ low the melting point of the oligomer, heated for curing the oligomer and optionally annealed.

The lubricants are used in amounts of 0.1 to 1%, preferably 0.2 to 0.8% by weight of the iron powder. The powder composition of iron, thermoplastic resin and lubricant can be formed into molded components by an appropriate molding technique with a conventional die without any additional heating equipment as in the pro¬ cess according to the US patent. However, the mixture of iron powder, thermoplastic material and lubricant can also be preheated to a temperature below the glass-tran-

SU ^Q GTflTUTE SHEET

sition temperature or melting point of the thermoplastic resin before it is fed into the die which is also pre¬ heated to a temperature below the glass-transition tem¬ perature/melting point. According to a preferred embodi- ment, the powder composition can be formed into molded components by a cold compaction process, i.e. the com¬ pacting step is carried out at ambient temperature. The compacting step is carried out at a pressure between about 400 and 1800 MPa. In the final, optional heat treatment or annealing step, the compacted and cured mixture is subjected to a temperature well above the curing temperature of the thermoplastic material. For the preferred thermoplastic materials according to the present invention, this in- volves heating to a temperature between about 100 and

600°C. Preferably the temperature varies between 200 and 500°C and most preferably between 300 and 400°C. The heat treatment is preferably carried out in one separate step. The main difference between the present process and the previously known process is that the process accord¬ ing to the present invention involves a compacting step which is carried out at at temperature below the glass- transition temperature or melting point of the thermo- plastic resin. From this follows that the present pro¬ cess is less energy consuming and accordingly less ex¬ pensive at the same time as, quite unexpectedly, essen¬ tially the same soft-magnetic properties can be ob¬ tained. Additionally, the use of lubricant in the powder mixture eliminates the need to lubricate the die which is necessary in the process according to the US patent. Another advantage over the known process is that the present process can be carried out without the use of any environmentally detrimental organic solvents and in a conventional die.

SUB ^S TITUTESHEET

The specific thermoplastic materials used according to the present invention eliminate the need of using alternating temperatures and pressures for obtaining the best results as is the case according to German Patent 34 39 397. This feature makes the present invention far more attractive from an industrial point of view than the process according to the German patent.

As regards the soft-magnetic properties it has been found that, at high frequency, the permeability versus frequency curves are essentially the same for products prepared according to the present invention as for the products prepared according to the known process. Also the strength of the materials is similar.

The invention is further illustrated by the follow- ing examples.

Example 1

A mixture based on SCM100.28 (an iron powder avail¬ able from HOganas AB, Sweden) was treated with aqueous phosphoric acid and dried in order to provide a phospho¬ rous coating on the iron particles. A total of 1% or¬ ganic material composed of 0.5% Ultem®, particle size <70μm and 0.5% Promold lubricant was dry-mixed to achieve a sample of a homogeneous material. A mixture was based on ABM 100.32 (an iron powder available from Hδganas AB, Sweden) which has been treated with phosphoric acid and dried in order to provide a phosphorous coating on the iron particles. A total of 0.7% organic material composed of 0.6% Orgasol and 0.1% Zn-stearate lubricant was dry-mixed to achieve a sample of a homogeneous material.

An iron powder TC, prepared according to the US patent 5 268 140 and marketed by Hoeganas Corporation, Riverton N.J. as TC powder, was used as a reference sam- pie. This sample was based on an iron powder with a phosphorous coating. An additional coating of Ultem®

SUBSTITUTE SHEET

1000 had been provided on the phosphate-insulated iron particles. (1% of the Ultem polymer was dissolved in an organic solvent and mixed with the phosphate-insulated iron particles. The solvent was then evaporated.) All the samples were compacted at 600 MPa. The products according to this invention, i.e. the products containing Ultem® and Promold® and Orgasol® and zinc stearate, respectively, were compacted at ambient tem¬ perature in a conventional press. The twin-coated or double-coated powder according to the known process was pre-heated to a temperature of 150°C, and compacted in a die heated to 218°C, which is just above the glass- transition temperature of Ultem® 1000. All three samples were subsequently annealed at a temperature of 300°C. The magnetic properties are essentially the same for the cold-compacted product comprising Ultem® and Promold® according to the present invention as for the warm-compacted known product based on the double- or twin-coated product. The product based on Orgasol® and zinc stearate has a somewhat different profile with higher permeability at low frequencies and lower permeability at higher frequencies as shown by the permeabiliy versus frequency curves of Figure 1.

Example 2.

The mixture is based on ABM 100.32 (an iron powder available from Hϋganas AB, Sweden) , which has been treated with phosphoric acid and dried in order to pro¬ vide a phosphorous coating on the iron particles. A to- tal of 1% organic material composed of 0.5% Ultem® and 0.5% Orgasol® lubicant was dry mixed to achieve a samp¬ le of a homogeneous material.

A mixture treated with phosphoric acid as above and based on ABM 100.32 with 0.5% Ultem® and 0.5% Kenolube® lubricant was dry mixed to achieve a sample of a homo¬ geneous material.

SUBSTITUTESHEET

A mixture treated with phosphoric acid as above and based on ABM 100.32 with 0.6% Orgasol® as both lubri¬ cant and thermoplastic resin was dry mixed to achieve a sample of a homogeneous material.

The samples were compared after compacting at 600 MPa and ambient temperature followed by heat treatment at 300°C for 60 minuted in air. The strength is compared in Table 1.

Table 1

Material Density Green strength

300°C 60 minutes air 600 MPa 600 MPa

ABM 100.32+0.5% ϋltem(D.M.) + 8.83 g/cm ³ 80 N/mm ² 0.5% Kenolube

ABM 100.32+0.5% ϋltem(D.M.) + 6.89 g/cm ³ 108 N/mm ² 0.5% Orgasol

ABM100.32+0.6% Orgasol 7.15 g/cm ³ 107 N/mm ²

The samples were compared after compacting at 800 MPa and ambient temperature followed by heat treatment at 300°C for 60 minutes in air. The permability versus frequency is disclosed in Fig. 2.

Exemple 3

The mixture was based on ABM 100.32 (an iron powder available from Hϋganas AB, Sweden) which has been treated with phosphoric acid and dried in order to pro¬ vide a phosphorous coating on the iron particles) . A to¬ tal of 1% organic material composed of 0.5% Ultem and 0.5% Orgasol lubricant was dry mixed to achieve a sample of a homogeneous material. A mix based on ABM 100.32 with 0.6% Orgasol as both lubricant and thermoplastic was dry mixed to achieve a sample of a homogeneous material.

The effect of warm compaction at approximately 600 MPa compared to ambient temperature compaction at 800 MPa is shown in Fig 3 and 4. The temperature for warm-

SUBSTITUTE SHEET

compaction is powder temperature 110°C-115°C and the cooling temperature 130°C for both samples. This is be¬ low the glass-transition temperature (Tg) for Ultem. In the case of Orgasol, the temperature is below the melting point (Tm) .

SUBSTITUTESHEET