EP1740343A2

EP1740343A2 - Non-corrosive auxiliary agents, based on alkali fluoroaluminates and containing co-precipitated metallates, for soldering aluminium

Info

Publication number: EP1740343A2
Application number: EP05715974A
Authority: EP
Inventors: Ulrich Seseke-Koyro; Andreas Becker
Original assignee: Solvay Fluor GmbH
Current assignee: Solvay Fluor GmbH
Priority date: 2004-03-20
Filing date: 2005-03-11
Publication date: 2007-01-10
Also published as: BRPI0508978A; DE102004028093A1; RU2006137081A; JP2007529322A; MXPA06010750A; US20070277908A1; WO2005092563A3; WO2005092563A2; KR20060132004A

Abstract

The invention relates to non-corrosive auxiliary agents based on alkali fluoroaluminates, for soldering aluminium and for refining aluminium alloys, to their production and to their use. According to the invention, said non-corrosive auxiliary agents contain metallates. To form the metallates, metal compounds of elements in the 2<nd> to 5<th> main groups of the periodic table or of elements in the sub-groups are used in the form of salts or oxides as co-reactants. In particular e.g., the halides, nitrates, carbonates, sulphates, phosphates, borates, hexafluorosilicates or oxides of said compounds are used. According to the invention, the metal compounds are introduced into the reaction mixture comprising of hydrofluoric acid, and/or alumina hydrate and/or an alkali compound. The time of the addition of the metal compound can be varied in accordance with the desired degree of functionalisation of the surface.

Description

Non-corrosive auxiliary materials for aluminum soldering Description

The invention relates to non-corrosive auxiliaries based on alkali fluoroaluminates for aluminum soldering and / or for refining aluminum alloys, the production of the auxiliaries and their use as a flux for soldering components made of aluminum and aluminum alloys or as an additive for introducing metals into aluminum alloys.

Assemblies of parts made of aluminum or aluminum alloys can be manufactured by soldering these parts. Usually, a flux based on fluoroaluminate is used for this, which frees the surface of the components to be soldered to one another from oxidic buildup.

Fluxes based on potassium fluoroaluminate are particularly suitable for soldering aluminum or low-magnesium aluminum alloys. Such a method is disclosed in British Patent GB 1,438,955. The preparation of corresponding fluxes is described, for example, by Willenberg, US Pat. No. 4,428,920 and Meshri, US Pat. No. 5,318,764 and Kawase, US Pat. No. 4,579,605. Magnesium-containing aluminum alloys can be soldered with good results using a flux composition containing cesium. The addition of certain metal silicates in certain quantities can make the solder metal unnecessary.

When soldering, the procedure is such that the flux and a solder metal are applied to the components to be connected. The flux can be applied, for example, in the form of a slurry, as an aqueous suspension, as a paste or powder. The components are assembled in the desired position and heated. First the flux melts and cleans the surface, then the solder melts. The parts are then allowed to cool. The object of the invention is to provide non-corrosive auxiliaries which can be used as fluxes or for refining alloys, and to provide a process for the preparation of these novel non-corrosive auxiliaries based on alkali metal fluoroaluminates. The new auxiliaries are said to improve solder flow and improve the surface, for example.

The non-corrosive auxiliaries according to the invention are characterized by a content of co-precipitated or admixed metallates.

These auxiliaries based on alkali metal fluoroaluminates are produced by known manufacturing processes, in which the reactants hydrogen fluoride, aluminum hydroxide (alumina hydrate) and alkali compound, preferably alkali hydroxide and at least one metal compound, preferably in the form of their salts, e.g. Halides, nitrates, carbonates, sulfates, phosphates, borates or hexafluorosilicates and / or their oxides are brought into contact with one another.

The auxiliaries according to the invention are preferably used as a flux for soldering components made of aluminum and / or aluminum alloys, the composition of the surfaces of the components to be soldered functionalizing at the same time due to their composition. The auxiliaries according to the invention are also suitable as an additive in aluminum production or as an additive for introducing metals into aluminum for the purpose of alloy refinement.

The base compound alkali fluoroaluminate is usually prepared by reacting alumina hydrate with hydrofluoric acid to fluoroaluminic acid in a first process step. This fluoroaluminic acid reacts in a precipitation step with an aqueous alkali compound, whereupon the desired alkali salts of the complex fluorides of aluminum are precipitated.

The auxiliaries according to the invention based on alkali fluoroaluminates are prepared by reacting alumina hydrate (aluminum oxide thhydrate) with hydrogen fluoride in the presence of an alkali compound, in one embodiment according to the invention metal compounds of the 2nd to 5th main group of the periodic table of the elements, in particular compounds of strontium, indium, tin, antimony or bismuth, preferably in the form of their salts, in particular their halides, nitrates, carbonates or their oxides, are added to the reaction mixture. In another embodiment, metal compounds of the subgroup elements are elements with atomic numbers 21 to 30 inclusive, atomic numbers 39 to 47 inclusive and / or atomic numbers 57 to 79 inclusive, preferably in the form of their salts, in particular their halides, nitrates, carbonates and / or oxides added to the reaction mixture. Suitable compounds of the subgroup elements are, for example, compounds of zirconium, niobium, cerium, yttrium or lanthanum.

The metal compounds can be used both individually or in combination with one another, e.g. in the form of mixtures in the reaction system. The use of complex metal compounds, e.g. ^ ZrF, ^ TiFß and / or mixtures of these with each other is also possible.

In general it can be said that all metal compounds of the main and sub-group elements, which are electrochemically more noble than the component to be soldered made of aluminum or aluminum alloys, are suitable for functionalizing the component surface. The functionalization of the surface arises from the fact that, due to the electrochemical series of voltages, the metal ion contained in the flux reacts with the less noble surface of the component activated by the flux and is reduced to metal during the melting process. This redox reaction is probably not to be regarded as a priority when using metal compounds of the 2nd main group, since other effects, e.g. Lowering the surface energy.

It is also conceivable that the ionically bonded metal is reduced and "alloyed" during the melting process.

Functionalization in the sense of the invention is e.g. to understand:

- Changing the surface properties - Improving the surface quality - Improving the solder flow - Inhibiting the growth of microorganisms

The time of addition of the main and / or subgroup compounds mentioned can be varied. The addition to the hydrogen fluoride, which is advantageous when using poorly soluble metal compounds, or after the formation of the fluoroaluminic acid, is made here in the mixture of alumina hydrate and fluorine. Hydrogen. It is also possible to add the metal compound to the reaction mixture of hydrogen fluoride, alumina hydrate and alkali compound.

In a preferred embodiment of the invention, the metal compounds are introduced into the reaction mixture after the formation of the fluoroaluminic acid and before the addition of the alkali compound.

Alkali salts or alkali metal hydroxides are used as the alkali compound, as individual substances or as alkali salt or alkali hydroxide mixtures in the form of their solutions or as solids, alkali representing lithium, sodium, potassium, rubidium or cesium, preferably potassium.

Appropriately, the procedure is such that an aqueous hydrogen fluoride solution is initially introduced, alumina hydrate (aluminum oxide trihydrate) and main and / or subgroup metal compound are added, and then alkali metal hydroxide, preferably potassium hydroxide, is added. The precipitated crystalline product is separated off and dried.

The term “alkali fluoroaluminate” refers in particular to alkali tetrafluoroaluminate, alkali pentafluoroaluminate and alkali hexafluoroaluminate, and their hydrates. Alkali stands for lithium, sodium, potassium, cesium or rubidium, preferably for potassium. By combining the alkali metals, the properties of the alkali fluoroaluminates can be Flux can be changed, for example, by incorporating cesium into a potassium aluminum fluoride matrix, the magnesium tolerance of the flux can be increased.

In a preferred embodiment, e.g. Zirconium oxide, niobium oxide, lanthanum oxide, yttrium oxide or cerium oxide introduced. These oxides are mixed into the reaction mixture, preferably before adding the potassium hydroxide solution.

In another embodiment, the metal compound is brought into contact with the hydrogen fluoride presented, that is to say introduced into the reaction mixture before the alumina is added.

The metal compounds are used in amounts of up to 30% by weight, preferably 0.01 to 20% by weight, based on the alkali metal fluorate. The amount of metal compound added depends on the degree of functionalization of the surfaces, depending on the application.

It is possible to choose the addition amount of the metal compounds so that the aluminum in the flux can be completely substituted.

Depending on the time of adding the metal compounds e.g. of the metal oxides to the reactants, the metals are chemically bound in the form of their metallates or are contained in the form of admixtures.

It has been found that the metal ions are incorporated into the potassium aluminum fluoride crystal lattice if the metal compounds are introduced into the reaction system before the addition of the alkali compound, preferably alkali hydroxide, in particular potassium hydroxide solution.

The addition of the metal compounds as the last reactant gives rise to more physical mixtures of the potassium fluoroaluminates with the partial formation of metal oxyfluorides, which, however, are not as effective because, due to their inhomogeneity, hygroscopicity or different solubility, these can lead to inhomogeneous surface functionalizations ,

A mechanical mixture of the metal compounds with the alkali aluminum fluorides or alkali fluoroaluminates is also possible, but very inhomogeneous element-specific hygroscopic mixtures with indifferent solubilities are obtained.

By varying the proportion of the metal compounds e.g. of the oxide content and combinations of the various metal compounds, the performance properties of the auxiliary according to the invention can be varied and controlled so that a specific property profile can be set.

It has been found that when the auxiliaries according to the invention are used as the flux, the flux, in addition to its known effect, namely cleaning the surface by removing the oxide layer, is capable of the flux activity, for example by influencing the viscosity and influencing the surface tension of the solder metal, positively to change. For example, the smoothness of the surface can be improved. This effect can probably be explained by the fact that the metallates built into the alkali fluoroaluminate undergo an electro-chemical reaction with the cleaned or activated surface of the aluminum components to be soldered during the soldering process, so that a surface change (functionalization) is brought about. This functionalized surface can in turn lead to an improvement in the solder flow (increased solder activity), a reduced roughness of the solidified flux after the soldering process, or even a surface coating, which make a subsequent “conversion coating” unnecessary.

The flux can be applied to the aluminum or aluminum alloy components to be connected in a manner known per se, e.g. by spraying, brushing or dipping, in the form of aqueous or organic suspensions.

The flux can also be applied to the components to be soldered using modern technologies, such as plasma or high-speed spray coating.

Dry application using electrostatic spray technology is also possible.

The flux can also be applied in the form of aqueous or organic suspensions, as a varnish or as a paste to the components to be connected.

Aqueous or organic slurries advantageously contain 10 to 75% by weight of the flux. The substances normally used as organic solvents, such as alcohols, in particular methanol, ethanol, propanol or isopropanol and polyols, can be used as organic liquids. Other suitable organic liquids are e.g. pyrrolidones or ethers, e.g. Diethylene glycol monobutyl ether, or ketones such as acetone, or esters of alcohols, diols or polyols.

When used as a paste, binders are added to the flux e.g. Ethyl cellulose added.

By means of film formers, usually polymers, which are soluble in organic solvents, for example acetone, if necessary, solder metal or solder metal precursors can be applied to the workpiece simultaneously with the flux. Suitable polymers are, for example Acrylates, polyvinyls, polyamines, polyenes, polyisoprenes or similar compounds with correspondingly functionalized organic radicals. Most of these organic compounds, known as film formers, evaporate during the soldering process.

As solder metal z. B. zinc, silicon, copper, aluminum zinc, aluminum silicon alloys or their combinations or solder metal precursors such as e.g. Metal hexafluorosilicate may be contained or used in the flux,

The soldering temperature depends on the solder used or the solder-forming metal. Soldering is preferably carried out above the melting point of the solder or the conversion phases of the flux or its mixtures.

Below a solder metal liquidus temperature of 450 ° C, one speaks by definition of "soft soldering", moreover of "hard soldering". There are low melting solders, e.g. Zinc-aluminum solders that melt from 390 ° C or pure zinc solder that can be used from 420 ° C for soldering. It is preferred to solder at 390 to 620 ° C, with ambient pressure.

Flame soldering or furnace soldering, especially under an inert atmosphere (e.g. nitrogen) are suitable process processes.

The auxiliary according to the invention is suitable as a flux for soldering components made of aluminum or aluminum alloys both in the presence of solder and without the addition of solder if the corresponding solder metal precursor is added.

The auxiliary according to the invention can also be used to alloy the corresponding metals in aluminum melts or aluminum alloys. Here, during the melting or liquefaction of the aluminum due to the redox potential of the metallate, it is reduced to the metal and thus made available to the aluminum as an alloying agent.

The following examples are intended to illustrate the invention without restricting its scope. Example 1: Production of a functional flux, here: NOCOLOK®-lanthanum

Execution:

Hydrofluoric acid was placed in a suitable container which can be thermostatted from the outside, provided with a stirrer and dropping funnel and appropriate protection against loss of evaporation of hydrogen fluoride, and diluted with 100 g of water. The appropriate amount of Al (OH) 3 and additional water to control the exotherm were added to this acid solution with stirring using the dropping funnel. Then the lanthanum oxide was added in portions, followed by the addition of the potassium hydroxide solution. This reaction solution was stirred for a further 30 minutes and then filtered. The filter residue after drying at 200 ° C gave a white powder with a weight of 71 grams with 0.73% lanthanum.

Evaluation:

The differential thermal analysis (DTA), the X-ray diffraction spectrum (XRD) and also a scanning electron microscope (SEM) surface analysis were used for the analytical characterization of the new flux. The values were compared with the values of the well-known NOCOLOK® fluxes.

Comments on the XRD:

The XRD analysis primarily showed the presence of the potassium aluminum phases, KAIF4 and the so-called phase 1, which are also known from the NOCOLOK®. Comments on the DTA:

The DAT for NOCOLOK-lanthanum showed an endothermicity (melting range) known for NOCOLOK® and a characteristic curve that allows conclusions to be drawn about the analogous melting behavior and solderability.

Example 2: Production of a functional flux, here: NOCOLOK® zirconium

chemicals

HF VE 50.1% 89.45 g

VE dilution (HF dilution) 135.4 ml

Al (OH) ₃ alumina hydrate 39.0 g

K ₂ ZrF ₆ 5.86 g

KOH 44.6% 73.6 g

Demineralized water (dilution KOH) 52.56 ml

Demineralized water (cooling water) 50 ml

execution

Hydrofluoric acid was weighed into a suitable vessel and diluted with 135.4 ml of deionized water. 39 g of Al (OH) _{3 were then} carefully metered into the dilute HF solution with stirring at about 170 rpm under temperature control. The KOH solution was then metered in via a dropping funnel. After a reaction time of about 30 minutes, the K ₂ ZrF _{6 was} added in portions and the mixture was stirred for a further 30 minutes. The precipitated solid was filtered off.

The filter residue after drying at 180 ° C gave a white powder with a weight of 77 grams with 0.42% zirconium. Comments on the XRD:

As in the Lathan compound of Example 1, this XRD evaluation primarily showed the presence of the potassium aluminum phases, KAIF4 and the so-called phase 1, which are known as the NOCOLOK® phase.

Comments on the DTA:

The DAT for NOCOLOK zirconium also showed an endothermicity (melting range) known for NOCOLOK®.

Example 3: Production of a functional flux, here: NOCOLOK® bismuth

chemicals

89.3g HF 50.2%

100g demineralized water

39.0g AI (OH) ₃ WW

71.5g KOH 44.7

0.85g Bi ₂ O ₃

80g cooling water

48g dilution water (before KOH)

execution

89.3 g HF were weighed into a suitable vessel and diluted with 100 g demineralized water. 0.85 g of Bi ₂ O _{3 was} added with stirring, followed by 39.0 g of Al (OH) ₃ accompanied by 80 g of cooling water.

Then the precipitation to NOCOLOK®-Bi was carried out with KOH. After a reaction time of 30 minutes, the precipitated solid was filtered off. After drying at 200 ° C., 75.1 grams of a white powder with a bismuth content of 0.75% were obtained. Comments on the XRD:

This XRD evaluation also primarily showed the presence of the potassium aluminum phases, KAIF4 and the so-called phase 1, which are known as the NOCOLOK® phase.

Comments on the DTA:

The DAT for NOCOLOK®-bismuth also showed an endothermia (melting range) known for NOCOLOK®.

Use of flux

For the results shown below, 99.9% aluminum platelets (Type 3003) of the dimension 25 x 25 mm at 1 mm thickness were coated with the corresponding new NOCOLOC metallates (5 or 10 g / m ² ) and in one Laboratory furnace is soldered using the well-known NOCOLOK® CAB process.

SEM surface analysis:

Comparative surface analysis, which was carried out after soldering, showed that less roughness and crystallite formation occurred when using NOCOLOK®-lanthanum or also NOCOLOK®-zirconium than with parts soldered with standardized NOCOLOK®.

It has been found that the auxiliaries according to the invention, when used as fluxes (NOCOLOK® metallates), produce a smoother surface and thus cause a reduced microorganism attack on, for example, soldered capacitors. The formation of nest structures (accumulation of microorganisms) is suppressed or even prevented by the smooth surface. The growth of the microorganisms is additionally inhibited or suppressed by the intrinsically cytokinetic effect of the transition metal ions. All in all, this can result in improved hygiene in air-conditioning operation. Comparative spreading test (activity test):

In this test, a defined amount (5 g / m ² ) of the compound to be examined was placed on an aluminum sheet (type 3003) of defined dimensions (25 x 25 mm) and in the laboratory furnace under defined and constant heating conditions (NOCOLOK® "Controlled Atmosphere Brazing "[CAB] conditions) melted. The spreading area of the re-solidified flux melt resulting after the soldering cycle was compared and measured.

In comparison to standardized NOCOLOK®, the fluxes according to the invention (NOCOLOK® metallates) clearly showed a quantitatively larger spreading area, which can be interpreted with an improved flux activity (lower surface tension).

For practical use, this enlargement of the spreading area means that smaller amounts of the flux according to the invention are required, with additional functionalization of the surface to be soldered being achieved, for example in the form of a metallization of the surface.

Claims

claims

1. Non-corrosive auxiliaries for aluminum soldering and / or for refining aluminum alloys based on alkali fluorine aluminates, characterized by a content of precipitated metalates.

2. Non-corrosive auxiliaries according to claim 1, characterized by a content of admixed metallates.

3. Non-corrosive auxiliaries according to claim 1 and 2, characterized in that compounds of the elements of the 2nd to 5th main group of the PSE, in particular those of strontium, indium, tin, antimony and / or bismuth are contained as metalates.

4. Non-corrosive auxiliaries according to claim 1 and 2, characterized in that contain as metalates compounds of the subgroup elements with atomic numbers 21 to 30, 39 to 47 and / or 57 to 79, in particular zirconium, niobium, cerium, lanthanum and / or yttrium are.

5. A process for the preparation of non-corrosive auxiliaries for aluminum soldering and for the refinement of aluminum alloys based on alkali metal fluoroaluminates, characterized in that metal compounds from the group of compounds of the elements of the 2nd to 5th main group of the PSE and / or compounds of the subgroup elements with the atomic numbers 21 to 30, 39 to 47 and / or 57 to 79 are brought into contact with at least one of the reactants alumina hydrate, hydrogen fluoride and / or alkali compound.

6. A process for the preparation of auxiliaries according to claim 5, characterized in that the metal compounds in the form of their salts, preferably their halides, nitrates, carbonates, sulfates, borates, phosphates or hexafluorosilicates or their oxides, both as individual compounds, as mixtures or in the form of complex metal compounds can be used.

7. A process for the preparation of auxiliaries according to claim 5 and 6, characterized in that strontium, indium, tin, antimony and / or bismuth compounds are used in the form of their halides, nitrates, carbonates and / or oxides.

8. A process for the preparation of auxiliaries according to claim 5 and 6, characterized in that zirconium, niobium, cerium, lanthanum and / or yttrium compounds are used in the form of their halides, nitrates, carbonates and / or oxides.

9. A process for the preparation of auxiliaries according to claim 5, characterized in that lithium, sodium, potassium, rubidium and / or cesium compounds or mixtures thereof are used as the alkali compound.

10. A process for the preparation of auxiliaries according to claim 9, characterized in that alkali metal hydroxide, in particular potassium hydroxide, is used as the alkali metal compound.

11. A process for the preparation of auxiliaries according to claim 5, characterized in that the metal compounds are used in amounts of up to 30% by weight, preferably 0.01 to 20% by weight, based on alkali metal fluoride.

12. A process for the preparation of auxiliaries according to claim 5 to 11, characterized in that the metal compound is introduced into the reaction mixture of alumina hydrate and hydrogen fluoride.

13. A process for the preparation of auxiliaries according to claim 5 to 11, characterized in that the metal compound is introduced into the reaction mixture of alumina hydrate, hydrogen fluoride and alkali hydroxide.

14. A process for the preparation of auxiliaries according to claim 5 to 11, characterized in that the metal compound is reacted with the hydrogen fluoride and then alumina hydrate and alkali metal hydroxide are added.

15. A process for the preparation of auxiliaries according to claim 5, characterized in that the metal compounds are mixed mechanically with alkali metal fluoride.

16. Use of the auxiliaries according to claims 1 to 4 as a flux for soldering components made of aluminum and / or aluminum alloys or as an additive in the production of aluminum or as an additive for refining the aluminum alloys.

17. Use of the auxiliaries according to claim 16 as a flux for soldering components made of aluminum and / or aluminum alloys, these being applied as an aqueous or organic suspension, as a varnish, paste or as a dry substance.

18. Use of the auxiliaries according to claim 16 as an additive for alloy refinement, the auxiliaries being used as dry matter.

19. Use of the auxiliaries according to claim 17 for functionalizing the surfaces of the components to be soldered.