DE1669942A1 - Metal-polymer compositions and articles made therefrom - Google Patents

Description

Dipl-Ing. F.Weickmann, Dr. Ing. Ü.Weickmann, Dipl.-Ing. H.Weickmann D1PL.-PHYS. Dr. K. Fincke patent attorneys

ΙΐΙ · ίΥ 8 MÜNCHEN 27, MÖHLSTRASSE 22, PHONE NUMBER «3921/22 'DD > J & HC

Oasis 11, 275-J?

ΐΗϋί 1> OW ÜJtiiiä-xIÜAL UUtIPiLiY, 929 üast Main ritreet, Midland, lü cni ^ aii / Y. bX. *.,

Metal polymer compositions and articles thereof

Me Jirfinduiiij; concerns metal-polymer compositions uxid ü-egens cäxiüe, especially moldings from a composition, those made up of a larger proportion of metallic particles una a smaller portion of an adhesive, tliermoplndtli-jc: /> en Ordered polymer, as well as a manufacturing process same.

Lightweight metallic objects are suitable for many Purposes of use where both strength and low G-ewicnt are required - ^ in usual practice for the production of metal objects consists of the pre-pressing of metal powders and sintering with formation coherent, eiOrmter masses. In the production of compacted moldings made of light metal powders, such as

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_{However, o} nesium, aluminum and beryllium arise. For example, (1) such lietall are generally not sinterable, (2) additional compression and heat treatment are required in order to obtain structures of satisfactory i'estigicei c, {')) the net all point to the x'eilcn The surface is exuded before pressing and sintering doors, and (4) these metals have a tendency to y-recirculate the interior of the iiatrics and temples during the shaping process. Attempts have already been made to utilize the slight formation of harmful oxide films by methods such as sintering the liberation in an inert or reducing atmosphere, which in addition Cost uuu juiiv; endings together with unwanted i'estigkeitsaii / enscnaften of -froauktes obtained have jedocn ei..f- v / a ^^ e dennte Anweiidung such methods verhinüf-rt.

These disadvantages are eliminated according to the invention by compositions of (a) 65 to ^] -) b vol.; J finely divided metal particles and (b) 35 to 5 vol. lViuteiligen adhesive thermoplastic polymer! fed ;, present thoroughly mixed and aie by application of pressure and härme be formed into coherent i'orialingen. ~~ "

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r of the J-ESEI earning "volume" is the volume liier understood, v / elcues seen from the mass or weight of the metal particles of the miti used tnei'moplasti material durcn division is ernalteii by the respective! density.

-euäii one embodiment of the jirl 'binding, the above-mentioned 3 components (a) and (b) are mixed with one another, (2) the obtained mixture in the desired shape, (3) the molding increased'j-'temperatures uixG ' .Printing exposed to sun melting of polymerizate and metal particles, and (4) the molding obtained is cooled. In this process, the mixture is heated and compressed in a single step, which makes the application relatively constant, e.g. 15 ° to 20 ° C, in the mold, so that it is not necessary to apply excessively high pressure to shape the proaUiCt , it has been found that molded products with good strength and tensile properties are obtained when they are at the liaximal temperature , heated to the mold and metal-polymer mixture Four den, ejected. Once ejected, the moldings can be cooled without a carrier without losing their shape.

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According to another embodiment of the invention (1) component (a) mixed with component (b) as described above, (2) brought the mixture into a mold, (3) pressurized the mixture,

(4) Removed the object obtained from the 3? Orm and

(5) the molded article is subjected to elevated temperatures Fusion of the plastic material with the surface subjected to metal particles.

In a preferred embodiment, about 90 to about 70 vol. # of the metal particles with about 10 to about 30 vol. $ Of a fine powder of an adhesive thermoplastic Polymer, such as a copolymer of ethylene with an ethylenically unsaturated one Carboxylic acid, mixed. In the mixture, the polymer powder particles are very small compared to the metal particles, and the polymer powder substantially covers the surface of each metal particle. the obtained mixture is at temperatures of about 150 ° G brought into any desired shape. The molded article is then cooled.

The invention is particularly advantageous for use of metal particles that have oxide on their surface

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have layers "It is known that metal particles which have no oxide coatings" can be pressed together and sintered. However, it is difficult to maintain a strong bond between the lights. It is known to be very difficult _r sintered articles to form even when oxydüberzogene metal particles are used t. Attempts have been made to expose oxide-coated metal particles to a carbon monoxide or hydrogen atmosphere to reduce the oxide on the metal, but not all of the coated particles are easily reduced. Since an adhesive, thermoplastic polymer is used according to the invention to "bond the metal particles together, either pure metal or oxide-coated particles can be used to manufacture the sintered objects. The metal particles which can be used in the invention include, for example, magnesium, magnesium alloys such as magnesium-aluminum , Magnesium-zinc and magnesite-tin alloys, aluminum, aluminum alloys such as aluminum-silicon and aluminum-copper alloys, iron, copper, blue, titanium and beryllium, metal particles advantageously have a size of 0.84 to 0.04 mm * preferably from 0.3 Me 0.07 ram *

The adhesive thermoplastics can be used as polymers in the invention. Preferred examples thereof are normal, graft or block copolymers of a larger n ■ Antei l-ethylene and about 3 to about 20 wt. Fo, based on the copolymer, of an acidic comonomers, which to oC, ß-ethylenically unsaturated mono- and Polycarboxylic acids and acid anhydrides having 3 to 8 carbon atoms per molecule and the partial esters of these polycarboxylic acids in which the alcohol group has 1 to 20 carbon atoms. Such acidic ominonomers include, for example, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaeonic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monomethyl fumarate and monoethyl fumarate.

The polymer particles should be small enough to the Surface of each metal particle in the polymer-metal mixture essentially to cover. Preferably the polymer particles should be less than 0.07 mm and preferably less than 0.04 mm.

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The polymer metal composition according to the invention can be used to produce variously shaped. Objects
produce, for example by bringing the composition into a compression molding press with the desired shape and exposing it to temperatures of 135 to about 260 ⁰ O and a pressure of at least 1.4 kg / cm. The mold is cooled and the molded composition ejected. The special properties of the polymer used not only result in good adhesion with connection of all metal particles, but also result in good adhesion
Sizing effect for the molding when it is ejected from the mold. The lubricant properties of the
Polymeriaats therefore enable the molded article to be ejected from the mold without breaking or cracking the egg product.

Uu the iOrmgegenetände according to the invention include, for example, toothed wheels, chain wheels, washers, weight washers, and tubes and hollow rings from which
such useful articles are subsequently made.

In the following examples, the metal polymer compacts formed at elevated temperature were adjusted to proportional

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tional limit, tensile strength and percentage contraction investigated, the experiments were carried out by placing a metal polymer molding between the plates of a hydraulic press was brought. The press is equipped with a pressure measuring device and an extensometer, which measured the vertical distance the top plate moved as the load increased » When the load is increased, the format of the compact proportionally decreased (contraction). When the However, loading has reached a point where a given loading results in greater contraction of the compact than with lower pressures. The pressure or the load at this point is called the proportional limit. With the continuous increase in Another point was reached where the compact cracked. The pressure at this point is called the tensile strength designated. The percentage contraction is obtained by dividing the length of the compressed compact at Tear point through the original length, i.e. the length of the compact before applying pressure, and multiplying the quotient by 100 is determined.

The following examples illustrate the invention without to restrict them.

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example 1

95.00 g of aluminum beads with a diameter of 0.149 to 0.044 mm were together with 5.0 g (12.4 vol.>I>) of a finely divided aerylic acid copolymer (8% by weight; brought sealable container. The mixture of metal and polymer was thoroughly mixed by shaking the container for about one minute. In the intestine, the mixture was placed in a mold with a cylindrical S'orm recess 19 mm in diameter and 30 mm in height and compressed therein. During the Verdichtung'wurde l'emperature to 107 ° C and the pressure increased to 70 kg / mm, and this ÜJemperaturgrad mid pressure were aufrechteriialten about 1 minute "The compact was then ejected nus of the mold and again 1 hour 177 ⁰ U heated and then cooled to! Room temperature.

The compact was examined and found to have the following properties the end;

Proporitonal limit (kg / cm) 147

Tensile strength (kg / cm ² ) 259

Contraction, '/ <* 7

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Example 2

The procedure. of Example 1 is lent in ve sent repeated except that the polymer-Metallzusaramensetzung was while she was in the i'ori, heated to 195 ⁰ G, and at the same time / mni subjected to a pressure of 35 kg. The pellet was still in the l ^? orm cooled to 93 ^Q ö and then ejected and cooled to room temperature.

The compact obtained had the following properties:

'Proportional limit 189 kg / cm

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Tensile strength ^: "' 210 kg / cm

Contraction 3>

Be i s ρ i e 1 3

The procedure of Example 1 was followed. essentially like repeated, but 90 g of aluminum pellets and 10 g . (23 VoI · $ '«)" of the mixed graft polymer instead of the in Example 1 applied amounts used. The received The compact had the following properties:.

ο proportional limit 105 ^

Tensile strength 245 kg / cm ²

Contraction ; 17 5 «

BATH

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Example 4

The procedure of Example 2 was essentially repeated, however, 90 g of aluminum pellets and 10 g (23 Vol "'; o) of the graft copolymer instead of the in Example 1 used amounts used The obtained The compact had the following properties:

Proportional limit 84 kg / cm

Tensile strength 224 kg / cm

Contraction 16%

example

The "procedure of Example 1 was essentially repeated however, 85 g of aluminum pellets and 15 g (30 vol.fo) of the graft copolymer were used instead of the in Example 1 used amounts used. The received The compact had the following properties:

Proportional limit 140 kg / cm

Tensile strength 228 kg / em

Contraction $ 21>.

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Claims (1)

- '- "■ ■■■■: -... _ 12 - PA Ϊ EM " T A E S. PR Ü GHE 1. Shaped article made of a metal polymer together, et surig, dadurcli marked that he was 65 to y5 vol / o fine metal particles and 35 to 5 vol.> S finer xeilcheii of an A-iisclipolyjnerisatsat of ethylene and Contains utnylenically unsaturated carboxylic acid. ι ... ■ J-egeixötand according to claim T, characterized in that the metal particles consist of aluminum and the copolymer consists of ethylene and acrylic acid. " 3. 'A method for producing a shaped metal polymer article, characterized in that (1) together (a) 65 to 95 Vol. ^ Fine metal ■ particles and (b) 35 to 5 Vol ~ L. ^L ß> fine particles of a copolymer of ethylene mixed with an ethylenically unsaturated carboxylic acid, "(2) the mixture obtained is brought into a desired shape, (3) exposed to the molding of elevated temperature and pressure to fuse the particles of polymer and metal with one another , and (4) the obtained fused product is cooled. © AD ORIQINAL 109829/1724 4. The method according to claim 3, characterized in that the gc code is rejected, that the metal particles. made of aluminum and the .mischpolymerisat consist of ethylene and acrylic acid. 5. The method according to claim 3, characterized in that the metallic particles have a size of greater than
0.84 mm and the Mis clip ο lymeri sat particles a drab of
be less than 0.074 mm » 6. The method according to claim 3, characterized in that after the mixture has been shaped, the molding
only pressure and then an increased temperature
is exposed. 7. molding composition consisting of 65 Ms. 95th> fine Hetallteilchen volume and 35 »t is 5 vol.> ⁰ finer i'eilchen a riischoolycierisats of ethylene with an ethylenically unsaturated carboxylic acid-. 8 »Molding compound according to claim 7, characterized in that that the tall particles are made of aluminum and the copolymer consists of ethylene and acrylic acid. 9. Molding composition according to claim Q _3, characterized in that it contains 90 to 70 vol.> Aluminum and 10 to 30 vol.; < Hiβcupοlymerisat, __ 108829/1724