DE1938595A1 - Coating for composite items and process for its manufacture - Google Patents

Description

DB-ING. DIPL.-IMQ. M. 8 "ΟΙρ -..- PHYS. IR» DIPL.-PHVS.

HOGER-STELLRECHT-GRiESSBACH-HAECKER

PATENT LAWYERS IN STUTTGART

A 37 472 Td. \ -

July 18, 1969

Texas Instruments Incorporated, Dallas / Texas 13500 North Central Expressway

Coating for composite articles and process for their manufacture.

The invention relates to protective layers, in particular on assembled parts of equipment and apparatus,

There is a definite need for the coating of equipment and machine parts that consist of several with one another soldered or welded sections are assembled so that. the entire part including the Connection points protected against harmful external influences

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009830/1026

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1969

that could destroy the part ". Examples of harmful external influences against which to Protect The present invention aims to prevent oxidation and erosion or pitting. . .

Because it is often desirable to use the favorable basic properties of a material, but this is not possible if -it is not protected against the environmental influences to which it must be exposed, find the coatings according to the invention a very important application in many areas. With the arrangements of the blade or wing sections in jet engines E.g. the blades or wings are often soldered into a retaining ring so that a composite Part that often falls victim to erosion and corrosion when exposed to the engine Exposed to sand, ice, dust, etc. To such a machine part To make erosion and corrosion resistant, it is not only necessary that the blades and the Retaining ring be provided with a suitable protective coating, Rather, the areas of the soldering must also be and welds are protected in this way.

In the past, such problems were caused by application dissolved by coatings of e.g. titanium carbide, which is applied to the The substrate, e.g., the metal, has been applied by exposing the metal surface to a gas stream of titanium tetrachloride and a hydrocarbon such as methane. became. The gaseous reactants were in the presence of the Brought together a metal base that was usually kept at a temperature between 900 and 1200 ° C, they reacted with one another to form titanium carbide, which was firmly deposited on the metal surface. The hydrogen chloride and others in the reaction

0Q9830 / 1026

A 37 472 b - 3 - .

1969- 193 8SS B

formed gaseous products were from the room in which this reaction was carried out, deducted. This method has already been described in detail earlier (USA patent 2 962 388), as well as a device with the help of which hard and dense coatings of this type can be applied (US Pat. No. 2,884,894).

One of the problems that frequently arises when a metal is coated with titanium carbide at temperatures between 900 and 1200 ° C. is the loss of the tempering toughness in this metal. It is generally known that metals, in particular steel or certain titanium alloys, are hardened by first bringing them to a temperature of 1000 ^° C. or higher, whereupon they are quickly quenched. After the quenching, the metal is then tempered at a temperature of approximately 500 to 600 ° C. so that the metal becomes less brittle and, in turn, tougher. If a hardened and tempered metal is heated again to a temperature between 900 and 1200 ° C, for example to apply a coating made of a hard material such as titanium carbide, the hardness and tempering toughness of the metal are lost again. However, if the metal is quenched again after the coating has been applied in order to harden it, the coating can be damaged because the metal piece changes its dimensions when it is cut off. This change in dimensions can lead to cracks in the coating or cause the formation of a rough surface and ultimately also cause the coating to separate from the metal surface. This not only calls into question the integrity of the coating, but rather the metal as a carrier material no longer has sufficient strength, so that the coating is made thicker

0 9 8 3 0/1026 originally inspected

A 37 472 b - 4 -

July 18, 1969

l> -35 ■ ■: ■: '.

must be so that it is resistant to the forces to which he can be exposed.

Another problem that arises particularly when applying coatings to assembled apparatus parts is the difficulty of achieving adequate adhesion between the coating and the looseness, weld, or other material that provides cohesion between the connected parts. This difficulty is exacerbated when coating processes are used which rely on penetration of the coating and the base material by diffusion, since these processes easily lead to a coating which has a different composition in different areas on the substrate. This problem is particularly acute at the points where the sections are connected to one another, be it by soldering, by a weld or by some other material that brings about the cohesion between the connected parts. Furthermore, a problem often arises in the coating process, caused by different diffusion speeds, when materials with a very different composition, such as a solder that connects parts made of stainless steel to one another, are involved in the construction of the apparatus part the constituents of a coating diffuse into a soldering surface, completely different from the diffusion speed of these constituents, into a surface of stainless steel .. Such unequal diffusion ratios lead to uneven coatings, which under severe working conditions can give rise to pitting and punctiform corrosion. . ■

: 'Q _: Q 9 8 3 0/10 2 8 original inspected

^{A 37 472 b} ■■. ■■ - -5 -

June 18, 1969

The invention was based on the object of providing a protective layer for using a composite mass together— ' to create set objects that can be applied without the aforementioned disadvantages and one according to the invention Protective layer is characterized in that the protective layer consists of a carbon-nitrogen-metal or. -Metalloid compound, in particular from a carbonitride of a metal or metalloid in a homogeneous, solid Solution on the surface of the sections and on that of the composite material and the latter penetrates in areas near the surface, the metal or metalloid a transition metal of groups IVb, Vb, VIb of the periodic System or silicon or boron. Based on a procedure in which. the heated object Is exposed to a gas stream containing the reactants to form the protective layer, according to the invention for Production of the protective layer also proposed that the object is heated so much, - that the composite material softens, and that a gas stream is used which contains carbon, nitrogen and the metal or metalloid in one contains such a state that these elements are reactive.

The chemical deposition from the vapor space according to the method according to the invention results in a completely uniform coating on an assembled apparatus part including the areas in which the sections are connected to one another ₉ regardless of the chemical composition of the respective sections and the material used to combine them, the coating the metal carbonitride results in a firmly adhering, hard erosion and corrosion-resistant surface, which enhances the performance

INSPSCTEÖ

A 37 472 b'-6 - '19385S5

18 july 1969 i.

b-35.

Ability, and the service life of the Äpparat part on which it was applied, significantly improved. The coating according to the invention can also be applied to assembled metal parts at relatively low temperatures, so that. the tempering toughness of the metals or alloys, of which the parts of the entire arrangement are made, is not lost. It should be pointed out, however, that higher separation temperatures can also be used if the parts of the arrangement are appropriately thermally insensitive different softening points can be used. It follows that a suitable coating temperature can be selected, this temperature depending on the composite to be used and on the decomposition temperature of the reactants used to achieve the coating.

In a preferred embodiment of the invention, the entire arrangement is generated before it is used with the the gas flow used in the deposition is brought into contact with it, heated at least to a temperature which corresponds to the softening point corresponds to the specific connecting material used to unite the sections.

As already mentioned above, the inventive method can ' They can be used to coat practically any assembled piece of equipment in which the individual Parts are united with the help of bucket composite material, which can be softened and then hardened again to

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§09830 / 1021

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July 18, 1969

b-35. ■

to maintain the necessary dimensional stability of the parts. For example, the process can easily be set up for this to "coat parts that are soldered together, the applied temperature being above the softening temperature." the alloy or metal used as solder according to the specific situation. Further "welded parts" can also be coated; and in a preferred embodiment of the invention is the .compound mass is an alloy, a solder or a pure one Metal, such as this, for example, "is the pail in a weld seam.

As already mentioned, the method according to the invention is in its most general form using a current carried out by gaseous reactants, which is a carbon source, which is a special hydrocarbon or a combination of hydrocarbons, contains a specific metal and nitrogen. In a preferred Embodiment of the method according to the invention the gas stream passing over the heated composite article contains a total of molecular hydrogen, a carbon-containing compound or a mixture of such compounds, which are within a certain Easily decompose in the temperature range, a compound containing at least one metal, which also decomposed under the influence of heat, molecular nitrogen and / or a heat decomposable nitrogen compound * In another embodiment, the nitrogen is supplied in the form of a single compound which contains both nitrogen and carbon and which are combined in one thermally decomposed in a certain temperature range.

A 37 472 b ■ '- 8 - ·' 1 938590 July 18, 1969 ■■■■■■ · ■■■■ "·. ■

Metal-containing ones suitable for the process according to the invention reactive compounds include metal halides or metal halides. A preferred group of halides is characterized by the general formula MeX, in which η is the valence of the metal or metalloid, Me and X is a halogen, e.g., fluorine, chlorine, bromine, iodine, where Me silicon, boron or a transition metal from subgroups IV, V and VI of the Periodic Table of Chemicals Elements can be. In general, the tetrahalides the transition metals, such as titanium tetrachloride or bromide, preferably used. In some cases, however also the; dihalides and trihalides may be useful, especially if the coating is at higher temperatures be made or the amount of hydrogen chloride formed should remain limited. .

Among the suitable carbonaceous compounds for the The reaction mixture includes cyclic and acyclic hydrocarbons with up to 18 carbon atoms in the molecule: which decompose easily at higher temperatures * Examples are paraffins, such as. about methane, ethane, propane, Butane, pentane, decane, pentadecane, octadecane, as well as aromatic compounds such as benzene and its halogen substitution products, such as chlorobenzene, dichlorobenzene, di-chromobenzene etc. Natural gas is a particularly preferred source of carbon because it contains a greater number of hydrocarbons. contains and is readily available.

The gas stream of the reactive compounds contains at another preferred embodiment of the invention glass Process hydrogen, nitrogen, a hydrocarbon or a mixture of hydrocarbons and

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100830/1026

A 37 472 b
July 18, 1969
b-35

a halide of a metal from the group specified above. Preferred is the use of natural gas as the hydrocarbon and titanium tetrachloride as the metal halides, though of course also other easily accessible hydrocarbons, such as propane can be used well as metal halide together with titanium tetrachloride.

Other carbonaceous compounds that are used can in order for the coating reaction the carbon and the nitrogen and also the hydrogen are available which is required as a reducing agent for the metal halide are i.a.i

Hydrazine and a carbonaceous compound (i)

^Ri ; n - < ^Ri . , ' (H)

R ₁ - N = N - R ₁ '(III)

R ₁ - N = N - NH - R ₁ '~ * ■ (IV)

H - N '

. ■ - ZR ₀ , and .... (V) ·

In these formulas, R ₁ denotes a hydrogen atom, a cyclic or acyclic hydrocarbon radical having 1 to 18 carbon atoms, such as Z ₀ B. an alkyl, cycloalkyl, aryl or aralkyl group including the amino substitution products thereof ρ provided that at least one of R ^ Groups

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9890/1028 ' ° * ^mtHAL

A 37-472 b- · - 10

July 18, 1969 ■

b-35 ■■ - ■■ ■ "■■■;, ■ -... ■" .... . ■■. ■ ·.

■ 19385S5

in the same way: ■ Molecule "is a hydrocarbon solid. E ^ represents a cyclic or acyclic aliphatic Hydrocarbon radical with 1 to .18 carbon atoms inclusive the aromatic and amino substitution products thereof *

The easily activated carbon compounds that can be used together with hydrazine are hydrocarbons with. up to 18 carbon atoms in the molecule, such as methane, athari, propane, butanes, pentanes, decanes, octadecanes and mixtures thereof, as well as aromatic compounds, h 'such as benzene and halogen substitution products thereof. In addition, nitrogen-containing hydrocarbons such as alkyl amines, pyridine and the compounds characterized by the general formulas (II) to (VI) above can be used.

! Typical examples for the compounds (II) to (YI) are: 1,2-dimethylhydrazine, 1,1-dimethylhydrazine, 1,2-dioctylhydrazine, 1, T diphenylhydrazine, 1,2-diphenylhydrazine, 1-ethyl-2-phenylhydrazin, i-Phenyl-2-o-tolyhydrazine, 4 ", Λ .'- Biami'nohy- ^ ' drazobenzene, 1,2-] 3i-1-naphthylhydrazine, 1,1'-diazoaminobenzene, 1,1'-biazoaminonaphthalene, diazomethane., Diazoheptane, diazodecane, Diazopentadecane, hydraaimethane, hydrazitane, hydxazi- ^ decan and the like more.

Accordingly, in another preferred embodiment of the method of the invention, in which a heated composite article is coated with a metal-carbon-nitrogen compound _? a stream of vaporous reactive compounds is used, which consists of two components j first a metal or metalloid halide and second a compound, the nitrogen

- -: - ^: - ■■ '-' ■ / ^: - -. ' - - - ''. ■■■■■■ "'■ ■ ■ - ■' ■ '-. T-1: - ■■'" ■■

IHSPHCTEO

A 37 472 b - 11 -

July 18, 1969

b-55. · ■ - ■ - '.. ■■

■ .. 193859C

contains substance and carbon. The halide is preferably characterized by the general formula MeX, in which with X is a halogen and with η the valence of the metal or Metalloids Me. The compound containing carbon and nitrogen is preferably a those mentioned in group (II) to (VI) above reactive Links.

In a particularly preferred embodiment of the invention In the process, the metal halide is a metal chloride and especially a titanium chloride. A functional one Combination as a gas stream contains titanium tetrachloride and 1,1-bimethylhydrazine or, as an alternative, hydrazine and one Hydrocarbon, together with hydrogen and / or nitrogen as carrier gas.

As already mentioned above, an alloy, a solder or a metal is preferably used to combine the sections to form the apparatus part; in addition, the entire arrangement is first heated to a temperature at which the alloy or metal softens and at which the reactive compounds which are used to coat the arrangement decompose. Under these conditions, a metal halide and a carbon-nitrogen compound from the above-mentioned groups (I) to (VI) are preferably used as components of the gas stream used for the coating for the process according to the invention. As in the previous embodiments, a metal chloride, e.g. titanium chloride, is preferred as the metal halide, and a mixture of nitrogen as the carrier gas for the gas stream used for the coating, titarite tetrachloride and 1,1-dimethylhydrazine or, instead of the latter compound,

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009830/1026 ^0RiemAL

A 37 472 b - 12 -

July 18, 1969. · ''

* ~ ³⁵ . 1938590

Hydrazine and a hydrocarbon are used. Provided that, as in the above-described embodiments of the method according to the invention, a metal chloride and nitrogen- and carbon-containing compounds from groups (I) to (VI) are used, the sections of the entire arrangement are preferably connected to one another with a solder which contains about 53 "to about 55 wt% silver, about 39 to about 41 wt% copper, about 4 to about 6 wt% zinc, and about 0.5 'to about 1.5 wt% ^a / o mekel . In this embodiment of the method according to the invention, it is further advisable to choose the decomposition and coating temperature in the range between approximately 400 and approximately 1200.degree.

Additional reactive compounds that are both carbon as well as nitrogen, and those for the inventive Processes that can be used include aminoalkines, pyridines and alky! Amines, for example ethylenediamine, Triaminoethylene, pyridine, trimethylamine, triethylamine and the like .. ■

Accordingly, the gaseous reaction stream can be hydrogen, a halide of a metal or metalloid from the group listed above and a nitrogen-containing one Contain hydrocarbons, preferably ethylenediamine, pyridine or trimethylamine. Acts under these conditions the metal halide is preferably titanium tetrachloride. In a particularly preferred embodiment of the method according to the invention, a layer of titanium carbonitride is used deposited in solid solution from the vapor space on the object, the parts of which to form the finished assembly are soldered together by initially

- 13 -

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- 15 -

A 37 472 b - 15 -

Jul 18, 1969 -

b-35 ''

1938585

In this way it is ensured that the composite material is converted into a softened or molten state before the reactive compound selected for the formation of the coating is decomposed into the desired metal-carbonitride coating. Particularly useful compounds are tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium and tetrakis (diphenylamine) titanium. The solder used is again preferably one which contains about "to about 55% by weight of silver, about 39 to about 41% by weight of copper, about 4 to about 6% by weight of zinc and about 0.5 to about 1.5% by weight contains. $ nickel, wherein the temperature at which the reaction is carried out is in the range between about 700 ° C and approximately 1200 ⁰ C., the subject matter most commonly used are turbine blades made of stainless steel for a jet engine, soldered in the retaining rings. The thickness of the txtan carbonxtride coating is preferably from about 0.013 to about 0.038 mm.

For a better understanding of the invention, a few typical examples of the method according to the invention now follow should explain in more detail.

example

A jet engine turbine blade sector was soldered together from a blade made of AM 355 stainless steel and a retaining strap made of AM 309 stainless steel using a silver-copper solder of the following composition: silver 54 1 wt. $, Copper 40 - 1 wt. j £, zinc 5 ί 0.5 wt. # and nickel 1 - 0.25 wt. This solder corresponds to the aerospace industry specification AMS 4772 A and ASTM specification ASTM - 260. The melting point of this solder is

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009830/1026

A 37 472 b. . - 16 -.

July 18, 1969

b-35 .-- ■ '- ·

at about 718 C and the softening temperature is about 856 ° C.

Then a reactive vapor gas bromine was made from hydrogen, Generates nitrogen, titanium tetrachloride and natural gas; the natural gas had the following composition:

component proportion of
(Weight percent) methane 87-91 Ethane ' 6.18 propane 2.76 n-butane 0.88 Isobutane - 0.30 Isopentane 0.17 Pentane 0.21 nitrogen 1.19- Carbon dioxide 0.18 helium .0.04 Hydrogen sulfide 2 ppm Ethy! Mercaptan 10 mg / m

The engine turbine sector and tether were then placed in a reactor which was evacuated to remove the air '. Then you filled the reactor with Hydrogen and heated the assembly to 900 ° C. After the assembly had reached this temperature, the Gas stream with the reactive constituents passed over it for 3 hours at the following rates: Hydrogen 150 l / min., Nitrogen 23 l / min., Titanium tetrachloride 2.5 ml / min., Natural gas 21 l / min. «Then. ^ - '.;

_ 1 * 7 _

Q0S830 / 1026

ORIGINAL INSPECTED

A 37 472 b. . - 17 -

July 18, 1969

b-35 ''

193859G

. ■ / urde the arrangement from the turbine sector and the retaining strap removed from the reactor and cooled. It was found that a very large hard, solid solution of titanium carbonitride had precipitated. A close look and micrographs of one Cross-section through the assembly, including the loosening point, confirmed that the coating was on all parts of the assembly including the soldered material adhered well and firmly. Erosion and corrosion tests showed that the Coating the embossed material and the soldered Very effective protection.

It is of great importance that the method according to the invention is very flexible so that it can be carried out in commercially available systems. The arrangement to be coated is preferably placed in a reaction chamber with a suitable holder and heated to a temperature at which the reactive material in vapor form which is to be used decomposes when it comes into contact with the arrangement. Thus, the temperature to which the substrate must be heated depends on the particular reactive compounds used; it is generally in the temperature range between about 400 C and approximately 1200 ⁰ C. A temperature of about 400 ° C can for example be applied when the vapor reaction system composed of the following components: titanium tetrachloride, Äthylentriamin, hydrogen and nitrogen; a temperature of about 900 ° C or higher is used in a system of titanium tetrachloride, natural gas, hydrogen and nitrogen. After the object has been brought to the required temperature, the gas stream, which contains the intended reactive compound or the corresponding compounds, is allowed to flow directly over the surface of the substrate, so that the metal carbonitride is deposited on the substrate. The atomic ratios between the metal, the reactive nitrogen

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July 18, 1969. ■ '■■ -

b-35 ■

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substance and the reactive carbon in the steam-gas stream are generally not critical and can be varied both by the type and the proportions of the individual components in the reaction gas stream,

The metal carbonitride coatings produced according to the invention Processes generated contain the selected metal or metalloid, the carbon and the nitrogen in a phase with a uniform crystal lattice. The hardness of the common transition metal carbide structures will generally on the strong binding forces and the very difficult change of position of the non-metal atoms in the crystal lattice The material titanium carbide is characterized by metallic, ion and covalent atomic bonds the end. The metallic bond is generally, however only of little influence, as can be seen from the small number of movable charge carriers. The ion binding fraction is, however, of greater importance; it is stated to be about 1.3 electrons that of the 2 ρ state of the carbon atom in the 3 d state of the titanatoin transfer. The presence of covalent bond components between the next and next but one neighbors is on the physical properties such as hardness, brittleness and strength of the material are of the greatest influence. ·

The metal carbonitrides present in solid solution have Crystal structures very similar to those of transition metal carbides are; however, they differ from these materials in that they are made to measure can, so that they combine the desired properties in a particularly favorable manner. This will be chosen such a mode of operation that the bonds form in the desired type and number. The possibility, to make the bindings to measure, and thus the own

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0098 30/1026

A 37 472 b - 19 -

July 18, 1969 . .

to influence the shafts of the carbonitrides accordingly, is due to the use of the valence electron, which nitrogen has more in comparison to carbon Creation of bonds in the crystal lattice caused.

As already mentioned, with the help of the invention Process different types of materials are coated; these include ferrous metals, titanium, ceramic materials and refractory metals such as tungsten, molybdenum, niobium and tantalum.

From the embodiments of the invention described above Process shows that the nitrogen, the carbon and the appropriate metal or metalloid can be supplied by the most diverse connections; For example, connections are available that unite all these three elements in one molecule; However, connections that do not include all of these elements are sufficient included so that they either go together with the missing element itself or with a compound that has this missing element Element contains, can be applied. It is only necessary that these elements in a reactive form are present if they work with the surface of the material to be coated under the respective coating conditions Objects come into contact. Furthermore, it is not necessary, as in the example above it appears that the carbon source is a pure compound is to get good coatings.

The constituents containing carbon, nitrogen and the metal or metalloid can be any suitable Technology can be brought into a reactive form. As above

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009830/1026

A 37 472 b - 20 -

July 18, 1969

19385SG

Mentioned can be the gas-steam flow, which has the three components contains, - are passed over the objects brought to a higher temperature, so that they are on the hot surface 'Reach their reactive or activated state. However, it reads within the scope of the present invention that any other suitable technique can be used, with which the three components in the gas-steam flow, the is passed over the surfaces to be coated, can be converted into an active state.

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009830/1026

ORIGINAL INSPECTED

Claims (9)

Patent claims An object made up of several parts and covered with a protective layer and its parts are at least partially connected to one another by means of a compound causing a compound, characterized in that, that the protective layer consists of a carbon-nitrogen-metal or metalloid compound, in particular from a carbonitride of a metal or metalloid in homogeneous, solid solution on the surface of the pieces and insists on that of the composite mass and penetrates the latter in areas close to the surface, wherein the metal or metalloid is a transition metal of groups IVb, Vb, VIb of the periodic system or silicon or boron. 2. The article according to claim 1, characterized in that the composite mass is an alloy in a manner known per se, a soldering compound or e ^ n /? vie ^; all is and the protective layer consists of titanium carbonitride. 3. Article according to claim 2, in particular consisting of Stainless steel turbine blades soldered into retaining rings for jet engines, characterized in that the composite is a solder of approximately 53 to 55 percent by weight silver, 39 to 41 percent by weight copper, 4 to 6 percent by weight zinc and 1/2 to 1.5 view. ^ is nickel. 4. Article according to claim 3, characterized in that the titanium carbonitride layer is approximately 12. 10 to 39. 10 ~ ³ mm thick is. - 22 00 ^ 830/1026 IN A 37 472 b - 22 - 5. The method for producing an article according to one or more of the preceding claims, wherein the heated The object is exposed to a gas stream containing reactants for forming the protective layer, thereby characterized in that the article is heated so much that the composite material softens, and that a gas stream is used which contains carbon, nitrogen and the metal or metalloid in such a state that these Elements are reactive. 6. The method according to claim 5, characterized in that k the article above the softening point of the composite is heated before the gas flow acts on it. 7. The method according to claim 5 or 6, characterized in that that the gas stream contains a hydrogen-containing organic compound which is at the temperature of the object decomposes and yields carbon, nitrogen and the metal or metalloid in the reactive state. 8. The method according to claim 5 or 6, characterized by the Use of a hydrogen, at least one hydrocarbon and a halide of the selected metal or gas stream containing metalloids. f 9. The method according to claim 8, characterized by the use of chlorobenzene as the hydrocarbon and of Titanium tetrachloride as a metal halide. 10. The method according to claim 8, characterized in that natural gas is used as the hydrocarbon and titanium tetrachloride is used as the metal halide. - 23 - 009830/1026 ORIGINAL INSPECTED A 37 472 b - 23 - July 18, 1969 * -35 .-: ■ :. -. - · 193 85 9 11. "The method according to claim 8, characterized in that Titanium tetrachloride is used as a metal halide, propane, chlorobenzene or natural gas as a hydrocarbon : will. 12. The method according to claim 6, characterized in that the gas stream is hydrogen, a halide of the metal or metalloids and a nitrogen-containing hydrocarbon. 13 «Method according to claim 12, characterized in that .that titanium tetrachloride as the halide and diamine ethylene, pyridine and / or trimethylamine as the hydrocarbon will. 14. The method according to one or more of claims 5 to 13, characterized in that the composite mass is an alloy, solder or other metal is used. 15. The method according to claim 6, characterized in that the gas flow contains titanium tetrachloride, natural gas, hydrogen and nitrogen and, as a composite material, a soldering material is used. 16. The method according to claim 5, characterized in that the object zväschen to a temperature approximately 700 ° C and 1200 ° C is heated. 17. The method according to claim 7, characterized in that the organic compound is distributed in a carrier gas is for which nitrogen and / or hydrogen are used. - 24 - 009830/1026 A 37 472 Td - 24 - June 18, 1969 ' 18. The method according to claim 7, characterized in that the organic compound has the general formula Me wherein Me is the metal or metalloid and R is hydrogen and / or a hydrocarbon radical 1 to 18 carbon atoms and the organic compound has at least one such hydrocarbon radical contains. 19. The method according to claim 18, - characterized in that the object is heated to a temperature below the decomposition temperature of the organic compound lies. 20. The method according to claim 18, characterized by the use from TetrakisKdiraethylaminoHitan, Tetrakis- (diethylamino) -titan and / or tetrakis (diphenylamine) titanium as an organic compound. 21. The method according to claim 5, characterized in that the gas flow acts on the object in the absence of molecular hydrogen "and a metal or metalloid halide of the general formula Me (x) and contains at least one of the following compounds: Hydrazine and a carbonaceous compound (I) ^{Rl R} i \. (ID ^R l ^R l R ₁ -N = NR ₁ , «« Ο R ₁ -N = N-NH-R * ^IV ) - 25th 009830/1026 ORIGINAL {Ν $ Ρξ0Τ50 A 37 472 b - 25 - July 18, 1969 b-35, 193S595 H-N JU. other
^ H ² where η is the valence of the metal or metalloid, χ is a halogen, R _{1 is} hydrogen and / or a cyclic or aayklian hydrocarbon radical with 1 to 18 d ο · Γ en
Carbon atoms or amino-substituted derivatives and Ro is also one of these radicals or their aromatic or amino-substituted derivatives and at least one Rj is formed by such a radical. 22. The method according to claim 21, characterized in that a metal chloride, in particular a titanium chloride, is used as the metal halide. 23. "The method according to claim 22, characterized in that the gaseous reactants used are essentially titanium tetrachloride and 1,1-dimethylhydrazine. 24. The method according to claim 22, characterized in that the gaseous reactants are essentially titanium tetrachloride, Hydrazine and at least one hydrocarbon can be used. 25. The method according to claim 23 or 24, characterized in that nitrogen is used as the carrier gas for the reactants is used. 26. The method according to one or more of claims 20 to 25 »characterized in that when using a Solder as a composite material, the object is heated to a temperature between approximately 400 ° C and 1200 ° C will. 009830/10116 ORIGINAL INSPECTED