FURNACE BRAZING

A Survey of Modern Processes and Plant

J. D. Boughton and P. M. Roberts

Johnson Matthey Metals Limited, London

Reprinted from Welding and Metal Fabrication March and April 1973

JOHNSON MATTHEY METALS LIMITED

FURNACE BRAZING
A Survey of Modern Processes and Plant J. D. Boughton and P. M. Roberts
Johnson Matthey Metals Limited, London

There is no simple and concise answer to the question What is furnace brazing ?. The term furnace brazing can be applied to any brazing process where a furnace is the heat source used to raise the parts to be joined to their brazing temperature. Consequently, in its simplest form it can be the brazing of two pieces of brass, where heating is applied by an air-containing, gas- or oil-fired muffle furnace, the joint being produced with a silver-copper-zinc-cadmium alloy in association with a fluoride-base flux; at the other end of the scale, it can be the brazing of alumina to niobium with titanium in a vacuum furnace, where the end product is intended to be used as a component in an inter-planetary vehicle. Thus, furnace brazing can reasonably be described as the most versatile of all the brazing processes in common use, encompassing as it does brazing applications from the mundane to the highly esoteric. While this survey is primarily concerned with protective atmosphere furnace brazing techniques, no review of furnace brazing processes can be considered to be complete without reference to brazing in muffle furnaces where brazing is carried out with conventional fluxes in an atmosphere of air. Muffle furnaces are discussed later in this survey in the section entitled Types of Furnaces. Although many different types of protective atmosphere can be used for brazing, for convenience they can be divided into two broad categories: Gaseous atmospheres. Vacuum.

contact with other gaseous elements which might react with the metals being joined to produce surface films which might inhibit flowing and wetting by the molten brazing alloy. Chemically active atmospheres which will react, during the brazing cycle, with any surface films present on either the parts to be joined, or the brazing alloy preform, removing them in the process. In either instance, the partial pressure of any oxygen present in the protective atmosphere will play an important part in the removal of any contaminating film which may be present on the component parts of the assembly when they are placed into the furnace. During the brazing cycle, the chemical activity of the atmosphere employed can promote removal of the solid films (particularly oxides) from the surface of the parts to be brazed either by decomposition, or by combining with the elements which make up the film to produce easily removable compounds. Such films may be simple or complex compounds of sul phides, borides, phosphides, oxides and other organic substances. However, for the purposes of this survey the formation and decomposition of oxide films only will be considered in detail. One of the prime requirements for any successful furnace brazing operation is to ensure that the surfaces of the metals being brazed are free from oxide, or other films, which may inhibit wetting when the brazing alloy becomes molten. Thus, the ease with which surface oxides can be removed from any given material is a function of the ease with which the oxygen ions can be detached from the metallic ions present in the oxide. Naturally, the degree of difficulty that is encountered when such separation is required to be accomplished depends upon the strength of the chemical bond existing between the oxygen ions and the metal involved. The strength

1. Brazing in Gaseous Atmospheres

There are two distinct types of gaseous atmospheres in use for brazing applications: Chemically inert atmospheres which protect the parts being brazed from coming into

of such a bond may be assessed in several different ways: By the heat of formation (H) of the particular oxide in question. (However, this will provide an approximate guide only) or, more accurately, By the change in free energy (F) in the system during the reaction. From the maximum energy obtainable from the general chemical reaction: m nMe + O2 2 +MenOm

where Me = metal and m = 1 Mole of oxygen. Table 1 presents some data on the heat of formation for a series of different oxides. As shown in the table, metals like gold, silver and palladium possess low values for heat of formation of their oxides. Thus, from what has been said above, it is clear that these oxides can be considered to be unstable and hence can be readily decomposed. The oxides of metals such as copper, cobalt, nickel, or cadmium, are higher on the stability scale and are hence more difficult to reduce. Higher still on the stability scale will be found the oxides of chromium, tantalum, aluminium, and beryllium. In fact, the various oxides of beryllium have a far higher degree of stability than those of virtually any other element.
Table 1 Heat of Formation of certain Oxides1
Type Of oxides Reaction of formation of oxides Heat of formation of oxides, related to 1 mole 02: in kcal

Au2O3 Ag2O PdO CuO Cu2O CoO Co3O4 H2O (liquid) H2O (gaseous) NiO CdO FeO Fe2O3 Fe3O4 MnO ZnO Cr2O3 Ta2Q5 TiO2 ZrO2 A12O3 BeO

2Au + 3/2O2 2Ag + 1/2O2 Pd + 1/2O2 Cu2O + 1/2O2 2Cu + 1/2O2 Co + 1/2O2 3Co +2O2 2 H + 1/2O2 2 H + 1/2O2 Ni + 1/2O2 Cd + 1/2O2 Fe + 1/2O2 2Fe + 3/2O2 3Fe + 2O2 Mn + 1/2O2 Zn + 1/2O2 2Cr + 3/2O2 2Ta + 5/2O2 Ti + O2 Zr+ O2 2Al + 3/2O2 Be + 1/2O2

-7.3 14.6 42.0 75.0 82 115.0 98.2 115.6 136.6 116.8 124.4 129.0 130.0 133.8 185.0 166.8 179.6 199.6 219.0 258.5 266.6 294.6

From this, it follows that metals and their alloys may be classified in groups according to the difficulty of separation of oxygen ions from the respective metallic ions. This in turn, of course, is directly related to the degree of difficulty that one might expect to experience when attempting to carry out a brazing operation when these materials are employed as the parent metals. For instance, the brazing of noble metals does not present any special difficulties while copper, cobalt or nickel are somewhat more difficult. Chromium, tantalum, or beryllium are extremely difficult to braze with furnace techniques due to the very great stability of their oxides. To complicate matters, it must be remembered that certain metals form more than one oxide and such oxides have varying stability. Consequently, it is necessary to consider not only the oxide present on the surface of the parent material when attempting to assess the difficulty of brazing, but also which particular oxide, or group of oxides, is present. Oxides which are formed on the surfaces of alloys are usually solid solutions of the oxides of the metals which comprise the alloy and not just a single oxide. Moreover, the heat of formation of oxides on the surface of pure metals will not necessarily be the same as that of oxides produced on alloys of the same metals. In consequence, it does not follow that, if it is relatively easy to braze a particular alloy, the brazing of the individual metals which go to make up that alloy will be equally easy to achieve. During any oxidation cycle, the surface of an alloy becomes covered with a heterogeneous oxide film, which frequently consists of layers of different oxides, having differing compositions. The type and composition of oxides present in such layers is dependent upon the temperature and time for which the component has been exposed to the oxidising environment. A typical example may be found in the range of chromium-bearing steels which are generally considered to be difficult items to furnace braze. The oxide of chromium, Cr2O3, forms a strong bond with the steel surface and, in addition, is not readily reduced to metallic ions. However, it is recognised that other more complex oxides such as FeCr2O3 and FeOCr2O3, will be produced on the surface of the steel during the oxidation cycle and that the ionic bonds of these oxides will be weaker than in the Cr2O3 layer, and hence easier to reduce. The diagram shown in Fig. 1 gives data on the temperature dependence of the free energy of certain oxides. Variation of free energy has been related to one mole of oxygen at a pressure equal to one atmosphere combined with the corresponding quantity of metal in the oxides.

Fig. 1 Variation with temperature of the free energy of certain oxides

2. Dissociation of Oxides
With increasing temperature, the free energy associated with the formation of oxides decreases. Hence dissociation of oxides becomes easier to accomplish as the temperature within the furnace increases (Fig. 2). The temperature at which the oxides dissociate depends directly on the partial pressure of the oxygen in the environment. If the partial pressure of oxygen in the surrounding atmosphere is 0.21 atmosphere or more, the dissociation pressure of the oxide will, in most known metals and alloys, exceed their respective melting points. It is clear, therefore, that under these conditions (where dissociation of the oxide coating is relied upon to provide an oxide-free surface over which the molten brazing alloy can wet and flow), brazing will be impossible. There are, fortunately, exceptions to this rule. These are the oxides of gold, silver and platinum or oxides of their alloys, where dissociation takes place at temperatures below their respective melting points. Thus, a decrease in the partial pressure of oxygen in the surrounding atmosphere tends to favour decomposition of oxides on these metals and their alloys, and so increases the likelihood that brazing can be completed successfully. Reduction of the partial pressure of oxygen contained in the gas atmosphere may be achieved in two ways:

By the formation of a vacuum in the vicinity of the parts to be brazed; or By filling the space surrounding the part to be brazed with an oxygen-free inert or reducing gas. In the first instance, the partial pressure of oxygen is reduced without altering the composition of the atmosphere, while, in the second instance, the composition of the gas atmosphere is changed. This second method of the reduction of partial pressures of oxygen mentioned above is being increasingly used in brazing operations. The joining of titanium and its alloys with silver-bearing brazing materials is a typical example. Difficulties associated with the brazing of titanium arise not only because titanium and its alloys have oxide films of a high stability but also because they tend to absorb both nitrogen and hydrogen from any atmosphere in their vicinity. Both titanium hydride and titanium nitride will embrittle titanium, and it is, therefore, of fundamental importance to ensure that when brazing titanium or its alloys one employs only vacuum brazing or an inert atmosphere of argon which is free of both these gases. Freedom from contamination by hydrogen and nitrogen may be achieved by passing the argon gas stream through titanium chips or sponge, heated to 900C, prior to the gas being fed into the brazing retort.

Fig. 2 Variation with temperature of the dissociation pressure of certain oxides.2

A further problem must also be overcome before brazing of titanium or its alloys can be achieved. It has been established that beneath the oxide films on titanium, a gas-rich layer (the so-called alpha layer) may be found. Brazing should only be carried out after the removal of this film. The surface of the titanium should be either mechanically or chemically cleaned prior to beginning the brazing operation. Once the material has been cleaned, usually by pickling, brazing should be carried out within fortyeight hours.

3. Brazing in Inert Gases

Brazing in an atmosphere of inert gas is normally carried out in special retorts, although in some specialised work muffle-type furnaces may be used. In these instances, the muffle itself is completely filled with an inert gas such as argon or helium. When argon is introduced into an air-filled retort, a certain amount of air is displaced. In consequence the partial pressure of the residual oxygen is reduced. By then evacuating the retort and again refilling with argon a further reduction in the partial pressure of oxygen can be achieved. By successive evacuation and refilling with argon, low values for partial pressure of oxygen may be readily achieved. It is this procedure which allows the brazing of such materials as stainless steel (even where the difficult-to-remove oxide of chromium, Cr2O3, is present) to be carried out under an atmosphere of argon. However, it must be remembered that if the inert gas atmosphere remains stagnant during the brazing cycle then the partial pressure of oxygen, attributable to the decomposition of the surface oxide films, can build up in the joint area. In such work, it is not unknown for this local build-up of oxygen to arrest the process of dissociation despite the otherwise favourable mean partial pressure of oxygen within the atmosphere. It is, therefore, essential to prevent accumulation of oxygen near the surface of the parts during the brazing cycle. This can be readily achieved by ensuring that there is a continuous flow of the inert gas over the parts being treated. By this means, complete dissociation of the oxide film can occur, and brazing can be completed.

oxygen, it is also required that hydrogen, or some other reducing gas, is present in the furnace atmosphere to assist in the decomposition of the oxides. One of the most widely used gases in industry today is hydrogen and this will reduce most metal oxides in accordance with the following general chemical reaction: MeO+H2 Me+H2O Since this is a reversible reaction it follows that the presence of too much water vapour in the furnace atmosphere will result in oxidation of the metal occurring. Consequently, the decomposition of the oxides, and hence the success of the brazing process, will be favoured if the partial pressure of water vapour contained in the hydrogen atmosphere is reduced below a definite value. The amount of water vapour present in an atmosphere may be conveniently expressed in terms of its dew point. Thus, if the gas has a dew point of, say, 40C (representing a level of 130 parts per million of water vapour in the gas), this level of water vapour will be present in that gas at all temperatures above 40C. An understanding of this fact is essential in recognising the principles which govern the successful brazing of metal parts in a reducing atmosphere. It is possible to produce individual curves for each metallic element showing the relationship between the dew point of the reducing atmosphere, temperature, and the reducing or oxidising potential of that atmosphere. Fig. 3 shows typical curves for several elements.

Significance of the Curves

It has been the experience of the authors that users of reducing atmosphere furnace brazing techniques

4. Brazing in Reducing Atmospheres

Successful brazing in a reducing atmosphere is based upon the fact that a chemical reaction occurs between the oxides on the surface of the metals to be joined and the surrounding gas resulting in the reduction of the oxide film. Unlike brazing in an inert atmosphere, decomposition of the oxides is not a spontaneous process that occurs by removal of

Fig. 3 Relationship of dew point to equilibrium temperature for the reduction of various metal oxides in hydrogen. At dew points above the curve oxidising conditions prevail, at dew points below the curve reducing conditions prevail.

rarely understand the significance of the curves shown in Fig. 3. A proper understanding of their significance will provide an answer to the problem of why, for example, mild steel can be successfully brazed with copper under an atmosphere of burnt propane while stainless steel cannot. Figure 4 shows the oxidation/reduction curve for Cr2O3, the hard-to-reduce oxide normally present on the surface of a stainless steel part when it is placed in a furnace. As has already been explained, for brazing to be possible, it is necessary that the reduction potential of the atmosphere is sufficiently high to ensure that the reduction reaction proceeds only as follows: Cr2O3+3H2 2Cr+3H2O
Fig. 4 Significance of dew point: temperature relationship with regard to the successful brazing of stainless steel under reducing atmosphere.

Reference to Fig. 4 indicates that there are only three possible cases that need to be considered when evaluating whether or not stainless steel can be brazed under a specific set of dew point and furnace temperature conditions, i.e., to the left of the Cr2O3 curve, on the curve, or to the right of it. Let us consider each of these cases in detail: Case A: Dew point of the gas atmosphere 40C, the furnace operating at 750C. In this particular case the reduction potential of the gas atmosphere is not high enough to cause reduction of the Cr2O3 and hence wetting and flowing of the brazing alloy cannot occur. Case B: Dew point of the gas atmosphere 40C, the furnace operating at 950C. In this case the conditions are such that the atmosphere is neither truly reducing nor truly oxidising. Consequently, it is possible that wetting and flowing by the brazing alloy may occur. However, only a marginal increase in the level of water vapour present in the joint area, due, for instance, to poor purging as a result of too narrow a joint gap, or to an insufficient gas flow rate into the furnace, will prevent brazing occurring. Case C: Dew point of the gas atmosphere 40C, the furnace operating at 1,080C. In this case, reducing conditions prevail and brazing will occur. These three cases serve to show the importance of the oxidation/reduction potential curves since, what is true for Cr2O3 is equally true for all other oxides. By studying these cases, it is possible to deduce one of the fundamentals of successful furnace brazing, namely, that for wetting and flowing of the brazing alloy to occur it is necessary that the point of intersection of perpendicular lines drawn respectively

from the dew point value of the atmosphere employed and the furnace operating temperature, must lie to the right of the curve relating to the most difficult-toreduce oxide in the system being considered. In general terms, only elements present in a system at levels in excess of about 1 per cent need be considered. Moreover, not only must one consider the elements present in the parent materials but those contained in the brazing alloy must also be taken into account. A second, and equally important, feature which has emerged from this appraisal is that not only can conditions in a furnace be made to change from oxidising to reducing by raising the operating temperature (assuming the dew point value of the gas atmosphere is held constant), but that a similar change can be effected by maintaining the furnace temperature constant and reducing the dew point of the atmosphere. (Point A will be in reducing conditions when the furnace temperature is maintained at 750C, and the dew point reduced to 60C.) In practice, however, this latter option is only selected when, for metallurgical reasons, it is either impossible or undesirable to use a furnace temperature above a certain value and where there is no chance of the atmosphere in the furnace being reducing with respect to the parts needing to be brazed due to the available gas atmosphere having too high a dew point. In general, it is easier, and far less expensive, simply to increase the operating temperature of the furnace. However, even in this instance, due regard must be paid to any deleterious effects, to either the selected brazing alloy or the parent metals, which may occur as a result. (See section 5 under Alloys and Fluxes.)

5. Parent Metal Brazing Alloy Atmosphere Interaction

Embrittlement. When brazing in a hydrogen atmosphere, interaction between the hydrogen and the metals or alloys being joined must also be taken into account. (For example, dissolution of hydrogen in the metals with the subsequent possible formation of embrittling hydrides, as in the case of titanium, or of the formation of water vapour due to reduction of entrapped metallic oxides which will lead to the well known phenomenon of hydrogen embrittlement (Fig. 5) such as occurs with tough-pitch copper, must be borne in mind.) In practice, however, pure hydrogen is only occasionally used for brazing purposes. The reducing atmospheres used for furnace brazing applications normally contain, in addition to hydrogen, nitrogen and sometimes carbon monoxide, carbon dioxide, ammonia and, depending upon the source of the gas, certain of the hydro-carbon series (see later). It is, therefore, necessary to consider the possible interaction between the constituent gases in the reducing atmosphere and the parent metals when considering any particular furnace brazing application. The degree of interaction between the components of the reducing atmosphere and the metals to be joined, depends, to a large extent, on the composition of the metals, the brazing temperature, and the pressure of the applied atmosphere. For example, heating some steels for one hour in a hydrogen atmosphere having a dew point of +30C at a temperature of 1,200C causes embrittlement due to absorption of hydrogen. Yet when heating the same steel for one hour in a hydrogen atmosphere, having an identical dew point, at a temperature of only 1,000C, no embrittlement occurs. A similar state of

affairs can exist with regard to the nitrogen component of an atmosphere and certain metallic elements. Decarburisation of Certain Steels. Decarburisation of high-carbon steels can occur during brazing in hydrogen-containing atmospheres according to the general reaction: Fe3C+2H2=Fe+CH4 Increasing the temperature, and maintaining the time at the higher temperature constant, favours decarburisation. It is of fundamental importance to note that the residual moisture content of the reducing atmosphere plays a significant part in this reaction. It is, therefore, axiomatic that to minimise the decarburisation potential of the atmosphere it is necessary to use gas atmospheres which possess a low dew point. However, complete elimination of the decarburising effect in furnaces where reducing atmospheres are present cannot be achieved. Alloys and Fluxes. To ensure that brazing is carried out satisfactorily, conditions in the furnace must be such that reducing conditions prevail at the joint interface for any of the metallic elements present in the furnace (i.e., the constituents of both the brazing alloy and the selected parent metals being joined must be considered when establishing dew point parameters or furnace temperature conditions). By considering the curves shown in Fig. 3, as has been explained earlier, it can be seen that when the furnace conditions are oxidising they can often be made reducing by the simple expedient of raising the temperature. It must be stressed, however, that raising the furnace temperature may result in it being necessary to change the brazing alloy selection. This is specifically so if the alloy originally selected contains an element, or elements, possessing relatively high vapour pressure at the higher furnace setting. For example, with a furnace atmosphere of suitable dew point brazing alloys containing cadmium or zinc can be effectively used. However, if the furnace temperature is raised above 750C, these elements will volatilise and difficulty will be experienced in effecting a joint. A secondary problem will also exist in that the cadmium and zinc vapours may attack the furnace lining, whether it be of refractory brick or metal construction. Many present-day furnaces utilise nickelbase liners (Nimonic or Inconel) and these materials are particularly prone to attack by cadmium and zinc. The form of attack frequently results in intercrystalline failure of the nickel-base alloy. If conditions in the furnace are such that a flux has to be used to effect a joint, it is almost always advisable to modify the conditions to permit fluxless brazing. This is because many of the fluxes used in

Fig. 5 Photomicrograph showing the hydrogen embrittlement of tough pitch copper. (Courtesy: The Copper Development Association).

brazing processes contain fluorides and, in consequence, their vapours are extremely corrosive. In a relatively short time, these vapours can cause damage to the heating element sheaths, the furnace liner, conveyor belt and any other metallic parts within the furnace chamber. Secondly, and equally important, one of the prime reasons for selecting a furnace brazing technique is quite often the need to eliminate post-braze cleaning operations. If a flux has been used, its residues have to be removed and the economic advantages of using a furnace brazing technique are frequently lost due to the cost involved in carrying out this flux residue removal process. It often happens that flux residues on components brazed in a hydrogen/ nitrogen atmosphere are, for some inexplicable reason, much more difficult to remove than flux residues formed after brazing identical components, under identical flux cover, in air.

Hydrogen. Undissociated hydrocarbons compositions. Carbon monoxide. Compounds of sulphur.

of

varying

6. Reducing Atmospheres in Common Use

As has already been shown, the prime essential of a reducing atmosphere is that it shall be capable of both removing the oxides on the workpiece and brazing alloy and maintain the surfaces of these materials in a clean condition throughout the duration of the heating cycle. These conditions facilitate the proper wetting of the work by the molten brazing material and also ensure that the work is clean and bright when it is removed from the furnace. Since far and away the greatest amount of furnace brazing involves the joining of mild steel parts with copper, the commonly used reducing atmospheres will be considered primarily in relation to this particular brazing process. In the United Kingdom, reducing atmospheres are most frequently derived from one of six sources: From ammonia: it being catalytically cracked into its two constituent elements, hydrogen and nitrogen. Partially burned fuel gas. Catalytically cracked fuel gas. Catalytic reformation of hydrocarbon vapours. Bottled hydrogen. Methanol-water hydrogen generators. The atmospheres obtained from these various sources will, therefore, contain some or all of the following gases unless special precautions are taken to remove those which might have a deleterious effect upon the brazing operation: Carbon dioxide. Water vapour. Nitrogen.

As has already been shown, the control of the level of water vapour present in a reducing atmosphere is of fundamental importance if brazing is to occur. By having too much water vapour present the reaction set up in the furnace tends to be oxidising. Sulphur compounds also promote oxidation. It is, therefore, desirable to control the quantities of both these products admitted to any furnace if successful brazing is to be achieved. Apart from the oxidising properties of sulphur compounds they also have a deleterious effect upon furnace heating elements which may contain nickel, and any other nickel alloys used in the furnace construction, promoting inter-granular cracking of those materials. Hydrogen, the hydrocarbon series, and carbon monoxide are reducing gases and it is upon these that the primary effect of reduction of oxides present on the workpieces and brazing alloy depend. As already mentioned, an atmosphere constituent which has a strong affinity for carbon will combine with carbon from the surface of steel to cause surface decarburisation, which, in some instances, is undesirable. The constituents of a protective atmosphere gas which will produce this phenomenon are carbon dioxide, water vapour, sulphur compounds and, under certain conditions, hydrogen itself. Catalytically Cracked Ammonia. Cracked ammonia is widely used as a protective atmosphere for brazing. The cracking process, endothermic in nature, proceeds in accordance with the general formula: 2NH3 3H3+N2 Unfortunately, this reaction never reaches equilibrium, with the result that the output gas from a cracker plant invariably carries with it trace quantities of uncracked ammonia. Thus, in cases where stainless steel is being brazed under an atmosphere of cracked ammonia, there is a risk, albeit small, of this residual ammonia causing a certain degree of nitriding of the steel. Nitriding of stainless steels can result if the protective atmosphere contains an appreciable amount of molecular nitrogen. Since nitriding of nickel-base alloys and certain classes of stainless steels heated under cracked ammonia is an established fact, the use of nitrogen-free atmospheres is clearly desirable. Moreover, it generally happens that the dew point of the gas as it leaves the cracker plant is about 40C. Consequently,

Fig. 6 Diagrammatic representation of a plant for the production of an exothermic gas atmosphere.3

cracked ammonia atmospheres can be considered to be powerfully reducing and can, therefore, be used for not only mild steel but alloys which contain such readily oxidisable constituents as chromium, manganese and silicon. Under these conditions of purity, the atmosphere can be considered to be virtually nondecarburising. However, it must be stressed that the important feature of this form of atmosphere with regard to decarburisation phenomena is that it must be kept pure and dry while it is inside the furnace, and not merely when it is ready to leave the crackerplant. The cost of cracked ammonia is high when compared to that of atmospheres derived from fuel gases. Thus the use of cracked ammonia for brazing applications is generally confined to relatively small furnaces, and particularly those where materials of high intrinsic value, or where the parts require an exceptionally reducing atmosphere to effect a brazed joint, are being dealt with. Partially Burned Fuel Gas. The reducing atmosphere most widely used for brazing is undoubtedly that known as burnt towns gas. Coal gas from the ordinary mains supply is partially burned with controlled quantities of air in a specially constructed plant which is in general accordance with that shown in the diagram in Fig. 6. After combustion, the gases are dried as thoroughly as is necessary and, since most fuel gases contain quantities of sulphur it is necessary to use some form of scrubber to remove this element. A simple, yet effective, scrubber is iron-oxide, and a box containing this material is usually placed in the outlet line from the combustion chamber to remove sulphur-bearing compounds. The composition of the resultant

atmosphere is capable of wide variations by adjusting the gas/air ratio in the combustion chamber. Within the range of air/gas ratios shown in Fig. 7, the heat generated during the combustion cycle is more than sufficient to maintain the temperature needed for burning. For this reason the word exothermic is used to distinguish these atmospheres from those which, as described later, require an external heat source for their production.

Fig. 7 Partially burnt coal gas. Composition ranges which are useful for brazing.4

10

In general terms, similar atmospheres to those obtained by burning coal gas can be derived by the partial combustion of hydrocarbon gases such as propane, butane or methane. A burnt towns gas atmosphere is relatively cheap and is satisfactory for brazing those parent metals whose oxides are not particularly stable and, in consequence, are easily reduced. It is specifically applicable to the brazing of mild- and low-carbon steels with copper, but it should be remembered that it is relatively highly decarburising. In consequence, if decarburisation of the part is to be avoided, it is probably better not to select burnt towns gas as the protective atmosphere. Catalytically Cracked Fuel Gas. When brazing medium- and high-carbon steels, or mild steel assemblies which have been carburised prior to brazing so that subsequent case-hardening of these components can be carried out, the need arises for a reducing atmosphere which can be produced cheaply and yet which can be adjusted to be non-carburising or, in certain instances, slightly carburising. Such an atmosphere can be derived by passing a mixture of hydrocarbon gas and a smaller amount of air than would be required for an exothermic atmosphere over a heated catalyst. The catalyst temperature and gas/air ratio are adjusted to promote break-down of the hydrocarbon present in the mixture without actual combustion of the hydrocarbon occurring. This prevents the formation of undesirable products such as water vapour, and carbon dioxide. The principal reaction may be expressed by the typical equation: 2CH4+O2 2C0 +4H2 By varying the gas/air ratio, it is possible to retain a small quantity of methane or carbon dioxide in the producer gas. By this means the decarburising or carburising tendency of the gas, its so-called carbon potential can be modified at will. Thus, in work where the brazing of steels of a known carbon content is to be carried out, it is possible to adjust the atmosphere to be either non-decarburising or, in some instances even slightly carburising, as may be necessary for the type of steel being brazed. The chemical reactions necessary to produce this type of atmosphere do not produce much heat and, in consequence, it is necessary to apply external heating to the catalyst chamber so as to maintain the temperature required for the reaction to proceed. For this reason, the word endothermic is used to distinguish these atmospheres from the better known burnt towns gas atmospheres which, as has been mentioned above are exothermic. Catalytically reformed Hydrocarbons. The reforming of hydrocarbons with water vapour is

relatively common since cheap starting materials are readily available. The reformer plant comprises a catalyst-filled vessel to which the liquefied hydrocarbon gas and water vapour is fed in precisely controlled proportions. Catalytic cracking, at approximately 1,000C occurs. The reaction occurring can be expressed by the general formula: CnH(2n+2) +nH2O nCO+(2n+1)H2

The carbon monoxide produced in this reaction is subsequently converted to carbon dioxide in a further catalytic reaction which can be represented by: nCO+nH2O nCO2+nH2

By using suitable scrubbing procedures, usually with monoethanolamine, the carbon dioxide component of this gas mixture can be removed. However, these chemical reactions rarely proceed to completion, and the hydrogen gas leaving the reformer is frequently contaminated with trace quantities of both CO and CO2. Sometimes this is not too critical, but in applications where the brazing of stainless steel is to be carried out, the presence of even small amounts of carbon in the atmosphere gas is highly undesirable since rapid carburisation of the steel, with a consequent loss of corrosion resistance, will inevitably occur. In such work, it is necessary to reduce the CO component to a level of about 0.00l and the CO2 level to about 0.0l volume per cent if the carburisation problem is to be avoided. Moreover, it should be remembered that carbon may also have an oxidising effect on the stainless steel. To reduce the level of these contaminant gases can be a very expensive operation, requiring considerable capital expenditure. Bottled Hydrogen. Commercial grade bottled hydrogen can be used as a protective atmosphere for furnace brazing applications. There is, however, one major disadvantage with gas derived from this source. The dew point of such gas is rarely better than 10C (although the major industrial gas suppliers can provide drier hydrogen at extra cost), which is, of course, far too wet for the successful brazing of most of the stainless steels or nickel-base alloys now in common use. In addition, due to the relatively high dew point of an atmosphere derived from this source, decarburisation of steels will be an ever-present hazard. It is apparent, therefore, that if the brazing of stainless steel is to be carried out in conditions that are free from the risk of decarburising or nitriding, conventional reducing atmosphere furnace brazing is seemingly inadmissible. Naturally, one can select vacuum furnace brazing as an alternative, accepting the inevitable high cost of installing suitable equipment,

11

which a methanol-water mixture is reacted to produce a mixture of carbon monoxide and hydrogen. The product of this exothermic reaction is conducted to a hydrogen diffusion unit contained within the generator where the hydrogen is separated from the mixture in an identical manner to that described in section 6 under Catalytically Cracked Fuel Gas. Not only does this provide an inexpensive hydrogen atmosphere, but users of such a system have as a bonus an atmosphere gas with a dew point of 80C, or better.

7. Types of Furnaces
Muffle Furnaces. In the United Kingdom, most muffle furnaces are fired by either coal-gas or electricity and, providing that heating is uniform over the whole extent of the chamber and the temperature can be controlled, satisfactory brazed joints can be achieved. A gas-fired muffle furnace will normally incorporate a refractory chamber so that the flames from the burner pass round the outside of the chamber and do not actually enter it. This arrangement is conducive to an even temperature in all parts of the chamber and, in addition, ensures that neither unburnt gas, nor the products of combustion, come into contact with the workpiece. With electrically heated muffle furnaces, it is essential that the heating elements, usually made of nickel-chromium, are not directly exposed to flux or to fumes evolved from the flux during the heating cycle. A refractory muffle insert will satisfy this requirement, but occasionally the furnace will be designed so that the elements are protected from contamination by inserting nickel-chromium plates between them and the workpiece. While this will protect the elements from accidental mechanical damage it does not, of course, protect them from contamination by flux fumes. In general terms, any furnace which can operate in the temperature range 7001,000C can be used for the brazing of steel, copper, and copper alloys, utilising copper-zinc brazing materials, or silver brazing alloys, typified by the 50 per cent silvercopper-cadmium-zinc alloy. While muffle furnaces are not recommended for large scale production runs, this does not mean that they cannot be used for this class of work, and this type of furnace is widely employed for small scale production runs, or for the brazing of assemblies which are too large to be introduced into protective atmosphere conveyor furnaces. They are also used for the development of furnace brazing techniques when this method is being investigated for medium or large scale applications.

Fig. 8 A hydrogen diffusion unit. This particular unit will provide an output of 14,000 litres an hour of hydrogen, the dew point of which being better than 80C.

or one can choose to use the ultra-dry hydrogen derived from a relatively inexpensive hydrogen diffusion unit

(Fig. 8). Ultra-pure Hydrogen. Until relatively recently, there has been no truly economic method of achieving dew points much below about 60C. With the development of inexpensive hydrogen diffusion units, which operate on the principle of selective diffusion of hydrogen atoms through heated membranes of a 23 per cent silver :77 per cent palladium alloy, dew points which are better than 80C can be readily achieved on a continuous basis. Diffusion units of this type are designed to operate under all manner of hydrogen-rich gases, but for brazing and heat-treatment applications the gas source is usually one of:

Catalytically cracked ammonia. Bottled hydrogen. Reformed hydrocarbons. Methanol-Water Hydrogen Generators. With the recent development of methanol-water hydrogen generators a cheap source of pure hydrogen has become available. These units incorporate a heated catalyst bed over

12

It is of paramount importance that intending users of muffle furnaces should realise that, as a general rule, brazing is carried out in air with a flux. Consequently, the same post-braze flux removal operation will have to be carried out as that required with other heating operations carried out in air. In some instances, portable boxes are employed which contain the assemblies required to be brazed, and which are so designed that a protective atmosphere can be admitted to their interiors while they are in the furnace. In this way, muffle furnaces can be used to carry out protective atmosphere brazing techniques. Unfortunately, the process is rather cumbersome and can really only be recommended for small scale batch production. The major problem in this instance being the difficulty in maintaining accurate temperature control of the parts contained within the box. Bell Furnaces. This type of furnace can be considered to be the logical development from the muffle furnace, but one that is intended to be used with a protective atmosphere. It is ideally suited for the brazing of single, bulky, components. The work to be brazed is placed on a hearth, covered with a gas-tight metal bell, and the bell purged with a protective atmosphere to remove all traces of air. An electrically heated outer furnace is lowered over the inner bell and remains there until the work reaches the required brazing temperature. Once this has been achieved, the outer furnace can be removed and placed over a second bell which has been previously prepared for heating. As the cooling cycle is almost always longer than the heating cycle, one furnace can be used to heat several bells. In this way, virtually continuous production can be achieved by loading, purging, heating and cooling, each bell in rotation. Continuous Furnaces. Modern brazing furnaces, intended for large-scale production are frequently of the continuous type where the work is fed in at one end and emerges brazed at the other. The majority of these furnaces utilise a protective atmosphere of one kind or another. There are, however, examples of this type of furnace being used with an atmosphere of normal air. Naturally, in such conditions, brazing is carried out in association with the appropriate flux. Most furnaces of this type are electrically heated to permit accurate control of temperature in the hot zone. For the high temperature necessary when brazing steel components with copper, (1,1201,150C), nickel-chromium elements are used despite the fact that the element will be operating near its maximum recommended temperature.

Fig. 9 A continuous-conveyor reducing atmosphere brazing furnace. (Courtesy: Birlec Ltd.)

The most popular type of continuous furnace is the belt conveyor (Fig. 9), which is ideally suited for the brazing of large numbers of components. The belt is almost always fabricated from a nickel-chromium alloy made in the form of a mesh or as a continuous sheet. In general terms, the work should be placed directly on the moving furnace belt so as to maintain economical production rates during the brazing cycle by ensuring rapid heat transfer to the parts. In some types of work it is necessary to use trays in which the parts to be brazed are placed. This is particularly so when there is a danger of molten brazing alloy falling from the component on to the belt during the furnace cycle. The lengths of the heating and cooling chambers are arranged so that the workpiece cools to a temperature low enough to avoid oxidation of the part when it emerges from the furnace. The cooling chamber is surrounded by a water-jacket to ensure that the length of the cooling chamber, and hence the furnace, is kept to a minimum. To ensure that satisfactorily brazed joints are produced, it is essential that the protective atmosphere should fill the entire furnace. This is achieved by maintaining a positive pressure of gas within the furnace so that ingress of air into the heating and cooling chambers is avoided. The excess gas flowing from either end of the furnace is invariably ignited. Where the opening of a furnace is large, and where it is difficult to maintain a gas flow rate sufficient to prevent the ingress of air, adjustable doors are fitted. These doors usually have a contoured hole

13

cut into them which will permit the entry of the parts to be brazed, but which can be efficiently purged with the protective gas. Again, the gas issuing from the furnace doors is ignited. Alternatively, where it is either uneconomic or impossible, because of the variety of parts to be brazed, to use contoured doors, a curtain of asbestos string at the entry and exit can be used. While most continuous furnaces maintain the belt in a horizontal plane, there are furnaces in which the heating zone, and hence brazing zone, is raised a foot or so above the entry and exit doors of the furnace. This design is claimed to minimise the ingress of air to the heating zone. This type of furnace is referred to as a hump-back type (Fig. 10). With these furnaces, the angle of the belt track is rarely greater than 15 from the horizontal on the entry side and, normally, the angle of the belt track on the exit side of the furnace is shallower than this. This arrangement is necessary to ensure that there is sufficient time for the brazed part to cool to a temperature where, as with continuous furnaces, it will not oxidise once it leaves the cooling chamber. Pusher Furnaces. Pusher furnaces (Fig. 11) are generally similar to continuous furnaces. While continuous furnaces have open ends and a moving belt on which to place the parts, the pusher furnace comprises a purging chamber immediately adjacent to the entry to the furnace heating chamber, and a second purging chamber at the exit. The parts to be brazed are loaded into heat-resisting metal trays. These trays are placed on a platform at the side of, and level with, the furnace track and the furnace cycle is then commenced. On initiation of the cycle, the outer door of the purging chamber opens, a hydraulic ram fitted to the loading table pushes the tray into the purging chamber, the door closes, and purging is carried out. Once the purging cycle has been completed, the door between the purging chamber and the furnace is opened, a second hydraulic ram pushes the tray into the throat of the furnace, and the door closes. The furnace cycle then continues automatically with loaded trays being pushed into the purging chamber, purging being carried out and the purged material being admitted to the furnace. Every time the furnace door opens and a further tray is pushed into the throat of the furnace, all other trays already in the furnace are pushed along by a distance equal to the length of individual trays making up the furnace load. At the exit from the furnace, the procedure is slightly different. In this instance, there is not usually a door at the exit of the furnace chamber, only a door at the side of the purging chamber. The

Fig. 10 These hump-back mesh belt conveyor furnaces are used for the brazing of electronic components in a hydrogen atmosphere. (Courtesy: Birlec Ltd.)

trays are removed from the furnace by a hydraulic ram which is activated by the same electrical signal which operates the loading ram at the far end of the furnace. Thus, as one tray containing unbrazed parts is loaded into the purging chamber, at the exit end of the furnace a tray containing brazed parts is ejected. The total length of the furnace is, naturally, equal to a multiple of the length of individual trays used to carry the parts through it so that the hydraulic ram removing the parts from the furnace makes contact with the centre of the tray.

Fig. 11. A single track pusher furnace. (Courtesy: Birlec Ltd.)

14

By utilising this form of approach to a furnace brazing problem one is able to control the quality of the furnace atmosphere with far greater precision than is possible with open-ended continuous furnaces although the output rate of brazed parts is usually somewhat lower than that achieved with the latter type. Hydrogen Quench Furnaces. In essence, the hydrogen quench furnace is similar to a conventional batch furnace in that it comprises a hearth on which the parts to be brazed are situated and a movable lid which contains the electrical heating elements and the protective gas inlet (Fig. 12). In addition, such furnaces are normally provided with a connection to a vacuum pumping system. In operation, the furnace hearth is loaded with the parts to be brazed, the furnace lid is placed in position, provision being made to give a completely gas-tight seal between the hearth and the furnace lid. Once the seal has been effectively made, the furnace is connected to the vacuum pumping system and to a source of hydrogen (which is used as the protective atmosphere in this class of furnace). To initiate the furnace cycle, it is first necessary to evacuate the furnace chamber to a pressure of approximately 100 torr, and then switch off the vacuum system. Hydrogen is admitted to the furnace until the pressure reading within the furnace shows about 400 mm of mercury. The hydrogen source is turned off, and the vacuum pump reactivated until the pressure again reads 100 torr. This back filling and evacuation cycle is carried out three or four times to ensure removal of the air that was trapped in the furnace when the seal between the lid and the hearth was made. On completion of the purging cycles, hydrogen is again admitted to the furnace until the pressure of hydrogen is between 400600 mm of mercury. The heating cycle is then commenced. Hydrogen quench furnaces are heated by electricity, the heat being transmitted to the parts by a combination of radiation from the elements themselves and the excellent conducting properties of the hydrogen gas contained within the furnace. The rate of temperature increase is extremely good and such furnaces can be controlled with an accuracy of 05C at temperatures up to l,300C. Once the assemblies within the furnace attain brazing temperature, measured by thermocouples in contact with the workpieces, the electrical power is disconnected and the quench cycle is started. Quenching is carried out by admitting large quantities of hydrogen into the furnace and, by using a fan, forcing the hydrogen round the furnace, over the heated parts, through a water-cooled heat-exchanger, and back into the furnace. Such a quenching method is highly efficient, and cooling

Fig. 12 This specialised hydrogen quench furnace is about to be used for the simultaneous brazing of several hundred mild steel assemblies. (Courtesy: Kepston Ltd.)

rates of 900C/min. have been recorded. The hydrogen quench furnace is probably the most efficient type of protective atmosphere furnace currently available, because not only can it be used for brazing but it also has many applications for the heat-treatment of special steels and nickel-base alloys of the Nimonic and Inconel type where rapid rates of cooling are essential to maintain the metallurgical properties developed during the heat-treatment cycle.

8. Vacuum Brazing
Vacuum is defined as a state which exists in a completely sealed space from which all gases and vapours have been removed. No method of producing absolute vacuum has yet been devised and, even the so-called vacuum of outer space (found to be about 1 x 1027 torr), cannot be considered to be a true vacuum since even in this environment one finds concentrations of several hundreds of molecules per cubic metre of space. Thus, progress towards the goal of a true vacuum must be described in various degrees of vacuum. Clearly, the pressure attained is limited by the materials chosen to enclose the space, the nature of the gases and vapours to be removed from the space, and, the method of pumping employed. The degree of vacuum attained in various systems bears a definite relation to atmospheric pressure. (At sea level, this pressure is taken to be

15

Table 2 The Relationship between the Degree of Vacuum and Pressure5 Condition Low vacuum Medium vacuum Fine vacuum High vacuum Very high vacuum Ultra high vacuum Pressure Range 760 to 25 torr 25 to 1.0 torr 1.0 to 10 -3 torr 1.0 x 10 -3 to 1.0 to 10 -6 torr 1.0 x 10 -6 to 1.0 to 10 -9 torr 1.0 x 10 -9 torr and below

Table 3 Relationship between Pressure and the Magnitude of the Mean Free Path5 Pressure (Torr) 760 1.0 x 10-7 No. of Molecules per cm3 2.7 x 1019 2.7 x 109 Mean Free Path (mm) 9.5 x 16-5 14 x 103

760 mm of mercury.) Table 2 shows the relationship existing between the degree of vacuum and the pressure. In general terms, it can be stated that the behaviour of gases and vapours become more complex as conditions of temperature and pressure change. Ideal gases conform to both Boyles and Charles Law, but non-condensable gases and vapours do not, and in any range of vacuum being used, one is normally dealing with a combination of a variety of gases and vapours. Table 3 shows the relationship between the number of molecules present in one cubic centimetre of gas at atmospheric pressure and at a pressure of 10-7 torr. Clearly, due to the far fewer numbers of molecules of gas present at the lower pressure, it automatically follows that the distance that individual molecules have to travel before they collide with each other (known as the mean free path), also increases by a large factor. The average distances for both one atmosphere pressure and a pressure of 10-7 torr are given in Table 3. Pumping Systems. Several major factors need to be considered when designing a suitable pumping system for a vacuum furnace. These are the time required to attain the required operational pressure, the value of the operational pressure, and the ability of the system to maintain the pumping speed at the operational pressure. Clearly, the time taken to pump down the chamber to the required level of vacuum for any given job is an important factor in the economics of vacuum brazing because extended pumping times will increase the cost of processing parts which may only need, from the theoretical stand-point, short heating cycles. Thus, the creation of a vacuum for brazing applications is almost

always carried out by a pumping system. When pumping is applied to a system initially held at atmospheric pressure, gas flows from the chamber being evacuated to the pump. The gas extracted expands into the pumping chamber and is compressed until it is finally ejected at an outlet valve. The entire mechanism is usually submerged in a bath of special oil to prevent back diffusion of air into the chamber which is being evacuated. However, a point is reached where the pressure in the chamber is so low that the molecular movement within the chamber becomes random and is no longer disposed towards the outlet orifice of the vacuum pump. It is then only possible to reduce the pressure remaining in the chamber by using a diffusion pump. The principles by which the diffusion pump operates are simple. When a liquid, oil or mercury, is boiled, its vapour rises. Convection currents cause the vapour to move upwards in the vacuum system and eventually it is forced against the walls of the vacuum chamber. The walls of the chamber are kept cool by a coil arrangement so that the vapour condenses to a liquid. Any molecules in the gas chamber that, by virtue of their random motion, wander into this liquid stream are caught and taken back towards the base of the pump in the liquid. Here, the pressure of gas so caught builds up to a point where a conventional mechanical pump can remove it. It is, therefore, clear that one can consider the diffusion pump to be acting, in effect, as a gas compressor.

9. Vacuum Brazing Furnaces

Vacuum brazing, as a production technique, has been in use for a little over twenty years. However, in the United Kingdom the process is not widely used. This is almost certainly due to the relatively high capital cost of equipment coupled with the relative complexity of operation. Recent developments attributed to manufacturers of vacuum brazing equipment have, however, resulted in substantial reductions in the cost of furnace equipment coupled with simplification of the operating procedure. For certain applications, such as the brazing of super-alloys and metals where the needs are to eliminate such gases as hydrogen and nitrogen, for the brazing of certain nickel-base alloys and stainless steels for aerospace applications, and for the brazing of some electronic components where all traces of oxygen must be excluded, vacuum brazing frequently offers the only solution. As has been mentioned earlier in this survey, hydrogen, and other reducing atmospheres, have the effect of reducing the metallic oxides which are present on the workpiece and/or the brazing alloy

16

during the heating cycles. It has also been pointed out that the amount of water vapour present in a gas is a critical parameter when considering furnace brazing applications which are to be carried out without the use of additional fluxing agents. In general terms, it has been shown that it is necessary for the more specialized furnace brazing applications to maintain the dew point of the gas atmosphere at levels below 40C. Another, and equally important factor, is the presence of gases known to have a deleterious effect, from the metallurgical point of view on the materials being brazed or ones which form films on the surface of the parent metal and/or brazing alloy, thus inhibiting the wetting and flowing of brazing alloy when it becomes molten. Both of these factors, when considered in relation to vacuum as a furnace atmosphere, are significantly reduced. For example, the equivalent dew point of the residual water vapour at a pressure of 1 x 10-4 torr is 90C (assuming that the residual atmosphere contains 70 per cent of water vapour by volume). Again, the concentration of oxygen at a pressure of 1 x 10-3 torr is approximately l.3 parts per million of oxygen. This compares most favourably with the residual oxygen content of ultra-pure argon, though not with ultra-pure hydrogen derived from the diffusion units described earlier. With a properly designed leakproof system, it is normal to arrive at the situation in a vacuum furnace where the oxygen content is somewhat lower than 0.01 parts per million. Even in instances where the presence of oxygen and/ or nitrogen is only deleterious because they will produce film on the workpiece, and hence inhibit wetting and flowing of the molten brazing alloy, the use of vacuum as an atmosphere can frequently be supported. This is specifically so when brazing complex workpieces since, if pure, dry, hydrogen or other reducing gas, is used as the furnace atmosphere, it can happen that the purging action through restricted capillary paths will not be effective in removing the trapped impurities. On the other hand, vacuum will effectively remove these pockets, thus facilitating the subsequent wetting and flowing by the molten brazing alloy. It is not unusual to find that modern vacuum furnaces are capable of removing by pumping over 1,000 1 of gas a second. Clearly, this is far in excess of the rate of removal of impurities by any known purging action.

slow heating and cooling rates which the parts being treated experience, and the problem of ensuring that the material from which the retorts are fabricated is physically strong enough to withstand the applied external pressure (due to atmospheric pressure), at its operating temperature. These factors, coupled with the requirements for higher operating temperatures, as well as the need for faster heating and cooling rates, have resulted in this type of furnace becoming virtually obsolete.

Cold-wall Vacuum Furnaces

With the cold-wall vacuum furnace, the heating elements, reflector plates, and the work itself are all enclosed in a water-cooled vacuum chamber. With more advanced types of furnace, movable baffles, internal heat-exchangers, and high velocity cooling gas circulating fans are also provided within the vacuum chamber. The reflector plates, designed to reflect the heat generated by the furnace elements back into the furnace, normally comprise multiple layers of polished molybdenum. The effectiveness of these plates depends almost entirely on their reflectivity, and in consequence their tarnishing will lead to a substantial fall in the furnace heating efficiency. In many instances, and where tarnishing is only slight, cleaning of the plates can be accomplished by pumping the furnace down to its lowest rated pressure, and operating it at its maximum rated temperature. Sometimes cleaning can be achieved more readily by admitting a partial pressure of pure, dry, hydrogen into the furnace during the heating cycle; this has the effect of reducing oxides which are difficult to remove by dissociation - dissolution phenomena. Radiation shield furnaces are nearly always employed where operating temperatures in excess of 1,400C are required. For temperatures below 1,400C, the insulated furnace, where thermal insulation is achieved by employing a refractory blanket faced with molybdenum, is often used. Since thermal insulating furnaces are substantially cheaper than the radiation shield type, the majority of the cold-wall furnaces built in recent years have been of this type. Moreover, this type of furnace is more suitable for run-of-the-mill vacuum brazing operations, where it is rarely necessary to employ furnace temperatures in excess of about 1,250C because they are less liable to damage than radiation shield types and require considerably less power to maintain any given temperature. However, for specialised high temperature applications, such as the brazing of tungsten with molybdenum-vanadium alloys, radiation shield furnaces are recommended.

Hot-Wall Vacuum Furnaces

The earliest types of vacuum furnace in use were the hot-wall variety. In essence, these were simply metal retorts, containing the work load, which were sealed, evacuated, and placed in a conventional furnace for heating. Obviously this approach has several major limitations. Among these are the relatively

17

Fig. 13 Relationship between vapour pressure and temperature of elements commonly employed in brazing filler materials.6

18

From what has already been said, it is clear that contamination of vacuum furnaces can result in a marked decrease in efficiency. In consequence, great care should be taken to ensure that contamination is kept to a minimum. For example, foreign matter such as lubricants used in deep drawing operations, notably silicone oils, volatile metals, or even such unexpected materials as industrial gloves have been inadvertently carried into vacuum chambers with resultant gross damage to the radiation shields. This has inevitably resulted in a very expensive repair being necessary in order to clean and/or repair the shields. As far as insulated furnaces are concerned, the heating effect in which heating rate does not depend on reflectivity, a simple outgassing process is usually able to return the furnace to a usable state within a few hours. The heating elements used in radiation-type vacuum furnaces are usually fabricated from molybdenum, tungsten, or less frequently, tantalum. With insulated furnaces, graphite as well as refractory metal elements can be employed. One minor disadvantage with graphite is that there is a certain amount of outgassing, mainly water vapour, which occurs during the initial runs. However, once this has completely outgassed no further problems should be experienced from this source.

Fig. 14 This vacuum furnace incorporates a device for the automatic introduction of a partial pressure of an inert atmosphere so as to minimise the evaporation of such elements as silver from the parent metal or the brazing alloy during the brazing cycle. (Courtesy: Wentgate Engineers Ltd.)

11.

Recent Developments

10. Vapour Pressure

Vapour pressure is the pressure exerted when a substance is in equilibrium with its own vapour, and is a function of the temperature and pressure to which it is exposed. Fig. 13 shows vapour pressure versus temperature for a number of pure metals. It will be noted, for example, that if pure gold is heated to l,100C at an applied pressure of 1 x 10-5 torr, the material will start to vaporise. Clearly, if either the temperature were raised, or the applied pressure reduced, an appreciable amount of gold would be vaporised and this could tend to condense on cool parts of the furnace. It is therefore necessary to pay due regard to vapour pressure phenomena when considering vacuum brazing operations. Consequently, should the selected temperature and pressure be such that appreciable volatilisation can be expected, provision should be made to introduce a partial pressure of a pure, dry, gas into the furnace chamber to minimise the effect (Fig. 14). Naturally, the presence of either oxygen or water vapour in a gas intended for either fast cooling of treated parts, or for partial pressures, could result in the work becoming discoloured and the radiation shields, if used, badly oxidised, thus negating the advantages of processing the work in a vacuum furnace.

Until comparatively recently, vacuum furnace operation was relatively unsophisticated because it was necessary to load the furnace, close the door, pump down, heat, cool, open the door, and remove the parts. Recently, however, vacuum furnace manufacturers have made great strides, improving vacuum technology almost beyond recognition when compared to the early models. Now, for example, it is possible to purchase vacuum equipment which is virtually continuous in operation and, in certain instances, contains facilities for oil quenching of the finished parts. Such a furnace comprises three separate chambers. The outer chambers can be loaded independently of each other and, more importantly, of the central (heating) chamber which can be maintained permanently under vacuum conditions. As will be realised, parts can be loaded, treated, and removed on a semi-continuous basis, thus effectively halving the cycle time of the more usual, single chamber furnace. If oil quenching of the parts is necessary, this can be done by moving the treated parts from the central to the right-hand chamber, introducing a partial pressure of a pure dry gas so as to minimise the vaporisation of the oil, and then, by using conventional drop-hearth techniques, depositing the parts in the oil. Even more advanced types of furnaces are on the drawing board and it is confidently anticipated that fully continuous vacuum brazing furnaces will be available within the next few years.

19

Table 4 A Representative List of the More Important Industrial Brazing Alloys Nominal Melting Range C 410 - 550 550 - 570 620 - 630 612 - 668 616 - 735 644 - 740 644 - 700 634 - 656 639 - 668 1090 - 1100 965 - 995 600 - 711 689 - 788 960 725 - 785 70S - 723 695 - 715 703 - 730 633 - 705 1083 1081 - 1101 1060 1100 778 856 - 880 9S0 - 980 950 1237 1769 900*

No.

Specification or Description

Nominal Composition

Typical Uses

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 BS 1942/2 BS 1845 Type AG1 BS 1845 Type CP2 BS 1845 Type CP1 BS1845 Type AG5 DIN 8513 L-Ag 85 DIN 1735 L-Ag 67 9 carat gold solder 14 carat gold solder 18 carat gold solder Pure copper BS 1845 Type N16 BS 1845 Type N18 BS1845 Type AG7(v) BS1845 Type PD4(v) BS 1845 Type AU5(v) 85 184S Type PD14 (v) Platinum Ti-Cored Ag/Cu

83 Mg-12 Al-5 Zn-(Be) 88 AI-12 Si 50 Ag-Cu-Zn-Cd 34 Ag-Cu-Zn-Cd 23 Ag-Cu-Zn-Cd 92 Cu-2 Ag-6 P 80 Cu-15 Sg-S P 50 Ag-Cu-Zn-Cd-Ni 50 Ag-Cu-Zn-Cd-Ni-Mn 96 Cu-Ni-Si 85 Cu-Ni-Mn 56 Ag-In-Cu-Ni 43 Ag-Cu-Zn 85 Ag-15 Mn 80 Ag-20 Zn 67 Ag-Cu-Zn 37.5 Au-Ag-Cu-Zn-Cd 58.3 Au-Ag-Cu-Zn-Cd 75.0 Au-Ag-Cu-Zn-Cd 100 Cu 97 Cu-Ni-B 73 Ni-Cr-Fe-Si-B-C 81 Ni-Si-Cr-C 71 Ag-29 Cu 15 Pd-Ag-Cu 68 Au-Cu-Ni-Cr-B 82.5 Au-Ni 60 Pd -40 Ni 100 Pt S per cent Ti-Ag-Cu

Brazing magnesium alloys. Brazing aluminium alloys. General purpose low melting-point alloys for brazing ferrous and non ferrous engineering materials other than aluminium and magnesium. Fluxless brazing of copper in air. Fabrication of cemented carbide-tipped tools and rock drills.

Brazing of stainless steel to produce joints resistant to interface corrosion. Brazing of steam turbine blading and parts for marine service (No. 13 only). Brazing of parts operating in contact with ammonia. Brazing of silver. Brazing of hallmarked jewellery articles.

Furnace brazing of closely fitting steel parts. Furnace brazing of steel parts with joint gaps too wide for brazing with copper. Brazing for service at elevated temperatures and for nuclear energy applications (No. 23 only). Brazing of vacuum tubes. Brazing for service in ultra-high vacuum and for strength and oxidation resistance at elevated temperatures. Brazing for high strength and oxidation resistance at elevated temperatures. Brazing molybdenum and tungsten for service at ultra-high temperatures. Direct brazing of metals to alumina ceramics.

* Working temperature.

20

12.

Brazing Alloy Selection

Anyone familiar with brazing practice will be aware that there are many hundreds of different brazing alloys commercially available. While it is not possible, in an survey of this type, to offer specific recommendations regarding the selection of an alloy for any particular purpose, one can certainly delineate the fundamental considerations affecting the selection of a brazing alloy. The service conditions of the finished joint are always the prime consideration, as it is this feature which will dictate the properties that the brazed joint must possess. As a result of this, the choice of brazing alloy is almost always determined by one or more of the following factors: The strength and ductility of the finished joint under the specific conditions of temperature at which it will operate. Some physical property dictated by the specific service environment (for example resistance of the joint to oxidation or corrosion, or its ability to operate at elevated temperatures in an evacuated environment). Some specific physical properties of the brazing alloy, such as its electrical or thermal conductivity. Statutory requirements (for example, the restriction on the use of lead- and cadmiumcontaining brazing alloys for use in foodhandling equipment). Aesthetic considerations (for example colour matching of the brazing alloy with the parent materials for jewellery and other decorative applications). Table 4 lists thirty different brazing alloys which are widely used in modern industry. However, it should be noted that while all of the alloys listed can be used for either reducing or neutral atmosphere furnace brazing not all of them are suitable for use in vacuum brazing applications. In certain instances, where the development of a furnace brazing technique is being undertaken, difficulties can arise. These almost always occur because the user fails to appreciate the fact that not only must the brazing alloy selected meet the service requirements but it must also be compatible with the base materials being brazed as well as with the specific joint design which has been selected. For a brazing alloy to be compatible with any particular parent metal combination it must meet the following requirements: The melting point must be lower than that of either parent metal.

It must be capable of wetting the parent metal at brazing temperature. It must not produce excessive erosion of the parent metal during the brazing cycle by interalloying effects. It must be capable of producing a joint at a temperature which will not create undesirable effects in the metallurgical structure of the parent materials. It must not contain either major proportions, or trace quantities, of elements which might alloy with the parent materials to produce brittle joints. When considering the compatibility of brazing alloys with brazing methods the following points should be remembered: As has already been mentioned, while both zinc- and cadmium-bearing alloys are widely used for furnace brazing both with and without the application of brazing fluxes due care will have to be taken to prevent any harmful effects on the furnace equipment of the cadmium, zinc, and flux fumes. When the joint design employed demands the use of a preplaced brazing alloy, it is desirable to use alloys that do not have an extended melting range. This is particularly true if the rate of heating through the melting range of the brazing alloy is relatively slow. Under these conditions, liquation, the gradual separation of the molten portion of the brazing alloy from its solid fraction, can be a hazard which may prevent the formation of a completely filled joint. Close control of the furnace temperature will be necessary when the difference between the liquidus of the brazing alloy and the solidus of one or other of the parent materials is less than 100C. If close control is not exercised the situation can arise where melting of the parent metals may occur. Due to the relatively high vapour pressure of both cadmium and zinc, alloys containing either of these elements must not be used for vacuum brazing applications (Fig. 13). For certain vacuum brazing applications, alloys containing silver are employed. While some loss of silver from the molten brazing alloy can take place due to volatilisation if too high a brazing temperature is obtained, this problem can be avoided by using a vacuum technique during the early stages of heating, and subsequently introducing into the furnace chamber a partial pressure of dry argon, or

21

Table 5 Suitability of Various Brazing Alloy/Parent Metal Combinations for Furnace Brazing in Reducing or Neutral Atmospheres7

Parent Metals Cemented Carbides Magnesium Alloys Aluminium Alloys Stainless Steels Titanium Alloys

Cobalt Alloys

Molybdenum

Nickel Alloys

Silver Alloys

Gold Alloys

Tungsten

Tantalum N N N N N P P P N N P P P R R P

Brazing Alloys

Carbon Steels

Copper Alloys

No.

Composition

1 2 3,4,5,8,9 13,16 6,7 12 10,20,21 14 15 17,18,19 22,23 24 25 28 26,27 29

Notation: O N P R = = = =

Mg-Al-Zn Al-Si Ag-Cu-Zn-Cd-(Ni,Mn) Ag-Cu-Zn Ag-Cu-P Ag-Cu-In-Ni Cu(Ni-Si,B) Ag-Mn Ag-Zn Au-Ag-Cu-Zn-Cd Ni-Cr-Si-B-C Ag-Cu Ag-Cu-Pd Pd-Ni Au-Ni(Cu-Cr-B) Pt

R O O O O O O O O O O O O O O O

P R O O O O O O O O O O O O O O

N N R R R P O N P P O R R O P O

N N R R R P O N P P O R R O P O

N N R R R P O O P P O P P O O O

N N P P P P O N P R O P P O P O

N N R R N P R P P P P P P P P O

N N R R N R R R R P R R R R R O

N N R R N P R R P P P P P P P O

N N R R N P R R R P R R R R R O

N N P P N P P P P P P P P P P O

N P N N N N N N N N N P R N P O

N N P P P P R P P P R P R R R R

N N P P P P P P P P R P R R R R

Impossible Not recommended Possible but seldom used Recommended and known to produce satsifactory results.

Notes: 1. Brazing fluxes may have to be used in addition to a protective atmosphere when the parent metals brazed contain alloy constituents forming refractory oxides (e.g. Cr, Ti, Al, Zn. etc.). 2. It is not recommended to furnace braze tantalum, niobium, and tough pitch or oxidised copper in hydrogen-bearing atmospheres.

helium, to minimise the rate of evaporation. In some work, particularly with vacuum furnace brazing, the brazing alloy may be maintained in the molten state for a considerable period of time. Under these circumstances the possibility of erosion of parent materials by the molten brazing alloy is an ever-present hazard. Due

regard must be paid to this possibility when vacuum brazing is the selected heating method. The data presented in Tables 5 and 6 illustrate how the characteristics discussed above affect the suitability of the alloys listed in Table 4 for the brazing of a wide variety of parent metals by either reducing or neutral atmosphere, or vacuum furnace brazing.

22

Niobium N N N N N P P P N N P P P P P P

Copper

Table 6 Suitability of Various Brazing Alloy / Parent Metal Combinations for Vacuum Brazing7

Parent Metals Cemented Carbides Magnesium Alloys Aluminium Alloys Stainless Steels Titanium Alloys

Cobalt Alloys

Molybdenum

Nickel Alloys

Silver Alloys

Gold Alloys

Tungsten

Tantalum N N N N N P R P N N P P P R R P

Brazing Alloys

Carbon Steels

Copper Alloys

No.

Composition

1 2 3,4,5,8,9 13,16 6,7 12 10,20,21 14 15 17,18,19 22,23 24 25 28 26,27 29

Notation: O N P R = = = =

Mg-Al-Zn Al-Si Ag-Cu-Zn-Cd-(Ni,Mn) Ag-Cu-Zn Cu-Ag-P Ag-Cu-In-Ni Cu(Ni-Si,B) Ag-Mn Ag-Zn Au-Ag-Cu-Zn-Cd Ni-Cr-Si-B-C Ag-Cu Ag-Cu-Pd Pd-Ni Au-Ni(Cu-Cr-B) Pt

N O O O O O O O O O O O O O O O

N P O O O O O O O O O O O O O O

N N N N P P O N N N O P P O P O

N N N N P P O N N N O P P O P O

N N N N P P O O N N O P P O O O

N N N N P P O N N N O P P O P O

N N N N N P R P N N P P P P P O

N N N N N R R P N N R P P R R O

N N N N N P R P N N P P P P P O

N N N N N P R P N N R P P R R O

N N N N N P P P N N P P P P P O

N P N N N N N N N N N P P N P O

N N N N P P P P N N R P P R R R

N N N N P P P P N N R P P R R R

Impossible Not recommended Possible but seldom used Recommended and known to produce satisfactory results

So far as the compatibility of brazing alloys with the joint design is concerned, there is a fundamental rule that should be observed. Where joint gaps presented are small, the brazing alloy selected should have as low a viscosity as possible and, moreover, a short melting range. Ideally, a single melting point is to be preferred. In addition, the alloy should readily wet the particular parent metal, and its free-flowing characteristics should not be affected by inter-alloying with the parent metals during the brazing cycle. Materials possessing these characteristics cannot, of

course, be used when the joint gap presented is large, since this configuration requires alloys that are either sluggish or have a relatively extended melting range. It is difficult to give more specific recommendations because the properties of any particular brazing alloy which determine the optimum joint design may vary from workpiece to workpiece, depending on the parent metals and brazing technique employed. For example, when furnace brazing mild steel with pure copper in a reducing atmosphere, interference fits or joint clearances in the order of 0025 mm will

Niobium N N N N N P P P N N P P P P P P

Copper

23

give the best results. However, if brazing of mild steel components with an alloy typified by that shown as number 3 in Table 4, and where a flux will be required to be used, the joint gap presented should lie in the range 0.0250.1 mm. This is because the joint gap presented must be made sufficiently large to permit access to the brazing flux without which the capillary flow of the molten brazing alloy would bound to be inhibited by the presence of the surface oxide films. With stainless steel, where the surface oxides are difficult to remove unless very dry reducing atmospheres are used, it is necessary to employ fairly wide joint gaps. Typical joint gaps for the furnace brazing of stainless steel, utilising copper as the filler material are 0.0250.075 mm. It will be noted that the upper limit of this gap size range is really too high for the successful use of copper. When nickel-base alloys are to be brazed with copper, joint clearances in the range 0.0500.130mm may need to be employed. This is because molten copper has a marked tendency to dissolve nickel from the base material resulting in the formation of coppernickel alloys. With such alloys, increasing dissolution of nickel results in the solidus value of the alloy also increasing. Thus, to ensure good capillary flow of this molten copper-nickel alloy through the joint at any given brazing temperature, the nickel concentration in the molten alloy must be kept as low as possible. The longer the joint that the copper has to fill by the mechanism of capillary flow, the wider must be the joint clearance so that the effects of inter-alloying between the copper and the base material are kept to a minimum. Further information regarding the selection of

brazing alloys for a variety of applications such as brazing for service in vacuum (Table 7), brazing nonmetallic materials, brazing for strength and oxidation resistance at elevated temperatures, will be found in an article by M. H. Sloboda in the October 1966 issue of this journal.
Table 7 Composition of Several Brazing Filler Materials Suitable for the Step Brazing of Vacuum Equipment8 Usual Joint Gaps mm 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0750.2 0.0750.2 0.0750.2 0.0750.2 0.0750.2 0.0750.2 0.0750.2 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0250.1 0.0750.2

Composition

Melting Range

Conforms to BS 1845

71

Ag-Cu Ag Au Pd Pt 5 Pd-Ag-Cu 10 Pd-Ag-Cu 10 Pd-Ag-Cu 15 Pd-Ag-Cu 20 Pd-Ag-Cu 25 Pd-Ag-Cu 5 Pd-Ag 18 Pd-Cu 30 Pd-Ag 60 Pd-Ni 80 Au-Cu-Fe 62.5 Au-Cu 37.5 Au-Cu 30 Au-Cu 70 Au-Cu 82.5 Au-Ni 68 Au-Cu-Ni-Cr-B 75 Au-Ni

778 962 1064 1552 1768 807810 830840 824850 856880 876900 901950 9701010 10801090 11501225 1237 908910 930940 980998 9961018 10301040 950 950980 950990

AG 7V AG 8 PD 1v PD 3V PD 2V PD 4V PD 5V PD 6V PD 7V PD 8V PD 14V AU 1V AU 2V AU 3V AU 4V AU 5V AU 6V

REFERENCES 1 Kubashevskii, 0., Evans, E.: Metallurgical Thermochemistry IL. 1954. (Translation from the Russian.) 2 Lustman, B.: Resistance of Metals to Scaling, Metal Progress, 50, No. 5, 850, 1946. 3 Brooker, H. R. and Beatson, E. V.: Industrial Brazing, p. 58. 4 Hancock, P. F.: Metal Industry, February 11th and February 18th, 1949. 5 Schwartz, M. M.: Modern Metal Joining Techniques. WileyInterscience, 1967. 6 AWS Brazing Manual, 1963. 7 Sloboda, M. H.: The Selection of Brazing Alloys, Welding and Metal Fabrication, October 1966. 8 Johnson Matthey Metals Ltd. Data Sheet 1100:200.

24

25

JOHNSON MATTHEY METALS LIMITED 81 Hatton Garden, London EC1P 1AE, England

26
Printed in England by Staples Printers Limited at The Priory Press, St Albans Hertfordshire