Tungsten Carbide
This article reviews the development of the filler metals and fluxes used when brazing tungsten carbide.
Tungsten Carbide
By Jack Willingham, Manager Quality & Technical Service Johnson Matthey Metal Joining
Tungsten Carbide
Contents Brazing filler metals - The background Brazing filler metals - The historical perspective Brazing filler metals - The technical considerations Brazing fluxes - The technical considerations Brazing filler metals - The common applications 22 17 9 5 3
Tungsten Carbide
Tungsten Carbide
to be subject to tensile-, shear- or compoundbending stresses. In most applications involving the brazing of tungsten carbide, preventing it from cracking by accommodating the cooling stress is the primary consideration. Figure 2: Example of a joint that cracked on cooling
Figure 3: Example of a joint where tip has come off during cooling
manganese enhance the filler metals wetting and bonding onto tungsten carbide.
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Tungsten Carbide
Tungsten Carbide
heat-treated shanks, as the short duration of the brazing operation only had a minimal effect on the already heat treated properties of the shank material. As already mentioned, pure copper was one of the first brazing filler metals used to braze tungsten carbide, although it has not been possible to uncover any evidence that pure copper was used to braze rock-drills. Some evidence suggests that copper nickel filler metals were used and certainly prior to 1967 a 96.9% copper-2.5% nickel-0.6% silicon alloy, widely known as Corson Bronze, was in extensive use. Since this material already existed as a precipitation hardenable copperbase filler metal it seems likely that brazing tests carried out with it showed that it worked acceptably. The high brazing temperature and properties of this filler metal, while not ideal, did allow for simultaneous brazing and air hardening of the shank material, followed by a lower temperature tempering heat treatment. As indicated, the copper-nickel-silicon filler metal is of a composition that can be subject to precipitation hardening and there are some suggestions that the high strength and hardness of the filler metal prolonged the life of drills used in certain drilling environments. While the copper-nickel-silicon filler metal was reasonably successful, it was not ideal. It was found to be hot short on cooling, and go through a ductile, brittle transition at around 600C. On larger diameter drills this was known to cause internal cracking of the filler metal due to the stresses that developed during post-braze cooling of the joint, and this resulted in premature service failure of the drills due to fatigue.
the copper- nickel-silicon filler material, while also helping to minimise the cooling stress. The manganese in the filler metal acted as a melting point depressant while also providing good filler metal wetting. Cobalt was added to the filler metal composition, as opposed to nickel, as it appeared that cobalt interalloyed with the cobalt-bonded matrix of the tungsten carbide more freely than nickel did. In the finished braze joint, the cobalt is present as a fine cobalt rich phase dispersed throughout the filler metal, and this is said to produce joints with a high resistance to fatigue failure together with a good level of ductility. While the copper-manganese-cobalt filler metal overcame many of the shortcomings of the copper- nickel-silicon filler metal, ideally the rock-drill manufacturers were seeking inexpensive brazing filler materials with brazing temperatures as close to 850C as possible. Brazing temperatures around 850C more closely match the heat treatment temperature of the steel shank and minimise the cooling stresses. This requirement eventually resulted in the early 1970s in the development of a brass type brazing filler metal with additions of manganese and cobalt. The filler metal produced joints, which greatly extended the life of drills compared to those that had been brazed with the previously used types of copper-base filler metal. A further important development in the field of brazing tungsten carbide was the sandwich or tri-metal product. These filler materials have a central core of material metallurgically bonded on either side with a layer of brazing filler material. In the early 1950s it was common practice when brazing large sections of carbide to form these types of product in situ. Either a plain sheet of material, woven soft iron wire gauze or a corrugated metal foil was used to thicken the brazed joint. The joint was prepared by first laying a section of fluxed brazing filler metal in foil form onto the joint area, then the
Rock drills The failings of the copper-nickel-silicon filler metal prompted the development of coppermanganese- cobalt filler metals. Their lower brazing temperatures reduced the amount of deterioration suffered by the shank material as a result of the high brazing temperatures of
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Tungsten Carbide
interlayer material, and finally by another piece of fluxed brazing filler metal foil on top. The reason for thickening the joint by introducing a spacing layer was to allow the joint to deform more readily such that it could dissipate the greater levels of cooling stresses that occur when brazing large sections of carbide. It has not been possible to establish precisely when purpose made tri-metal products, where the brazing filler metal had been pre-bonded to the interlayer, first became commercially available. However, the 1st Edition of the AWS Brazing Manual from 1955 states that A special brazing sheet is available for making sandwich brazes. This consists of a copper core clad on both sides with a thin layer of nickel-bearing BAg filler metal. By the mid 1960s such products were in common use. Typically, the product consisted of a copper or copper, nickel interlayer, with a silver-base brazing filler metal bonded on either side. Some of the high temperature copper-base filler metals were also available as tri-metal products, with gauze woven from nickel wire being used as the interlayer material. Today copper in the form of a solid sheet of material is most commonly used as the core or interlayer material in most tri-metal products. Copper is used not only because it is soft and ductile and can deform easily to dissipate the cooling stresses, but also because it makes for easy bonding of the brazing filler metal layers during production of the products. The common ratio of the layers in the products is 1:2:1. For example, in a 0.4 mm thick product the first layer of brazing filler metal will be 0.1 mm thick, followed by the interlayer with a thickness of 0.2 mm and then another layer of filler metal 0.1 mm thick. Other ratios with a thicker interlayer or thicker brazing filler metal layers are also available. Recently there has been a re-emergence of tri-metal products with copper alloy cores. Products with a copper-nickel core had traditionally
been available up until the later 1970s, early 1980s, but they have now started to re-appear with cores described as copper alloy. The products would seem to offer joints with higher shear strengths, as the copper alloy core will be stronger than products using the more common pure copper core. This additional strength is seen as being advantageous in applications where carbide tips are subject to high impact service loads. It is also possible to obtain what are commonly referred to as tri-metal brazing pastes. This description is used to describe brazing pastes that produce joints with a thick layer of filler metal, similar to the tri-metal products by introducing into the paste formulation a metallic powder that is not easily dissolved and taken into solution when the brazing filler is molten. Typically nickel powder is used for this. Circular saw blade
Tungsten Carbide
The most recently developed filler metals are silver containing, and are free from both zinc and cadmium. These have been developed for use when the tungsten carbide and its backing are to be coated using a Physical Vapour Deposition (PVD) process to apply TiN (titanium nitride) and similar types of coatings (See Figure 5). Under the coating conditions, if present, the cadmium and zinc will tend to vaporise out of the brazing filler metal affecting the coating process. They act as melting point depressants within the filler metals and while it is possible to have silver-copper-nickel-manganese filler metals without these volatile elements, their brazing temperatures are quite high. Filler metals with lower brazing temperatures, but still containing the beneficial elements nickel and/ or manganese, have been produced where indium or tin have been added as melting
point depressants. (See Argo-braze 64 and Argo-braze 57 in Table 4). While both tin and indium are low melting point elements they have high vaporisation temperatures. The above comments cannot be considered all inclusive, but they do at least chart the major filler metal product developments made in connection with the need to braze tungsten carbide while attempting to attribute some approximate dates and chronological order to those developments. It is interesting to note that most of the brazing filler metals and products specially developed for the brazing of tungsten carbide are still being used today. However, the use of the cadmium-bearing filler metals is in major decline due to the health and safety issues that arise from their use and environmental pressures.
metal wetting and bonding on tungsten carbides having low cobalt contents.
Tungsten Carbide
Figure 6: Colour comparison AWS A5.8 B-Ag24 manganese free and EN 1044 AG502 manganese containing filler metals
Tungsten Carbide
brazing filler metals for use on tungsten carbide) existed in relation to the additions of nickel and subsequently manganese. It would seem that their beneficial effects were established on an empirical basis early on and this information was then used to formulate subsequent filler metal compositions. When selecting a brazing filler metal for a tungsten carbide brazing operation it is established practice to use filler metals that at least have an addition of nickel or better still additions of nickel and manganese. However, some resistance does exist to the use of the manganese bearing filler metals. This is sometimes as a result of the surface finish of the filler metal that can have a rough and dark reddish brown appearance (See Figure 6). Some operators dislike these filler metals, as they are more sticky than those that are manganese-free. In many tungsten carbide brazing operations an operator is required to move the tungsten carbide tip around when Figure 7: Example of a wetting test
the brazing filler metal is in its molten state to help remove any flux and gas trapped in the joint before finally positioning the tip in its correct location. The term sticky is a reference to the fact that the tungsten carbide tips do not float and move so easily on the molten brazing filler metal, so making it difficult for the operator to move and position them. Some do not like the nickel bearing filler metals either, since they do not flow as well as the straight quaternary silver-copper-zinccadmium or the cadmium-free silver-copperzinc-tin filler metals. It is easy to check how a particular filler metal and flux combination will wet onto a piece of tungsten carbide. Simply clean the face of the tungsten carbide piece that would be brazed in the normal way. Flux the surface, and then cut a section of brazing filler metal foil, rod or wire and place it on top of the fluxed surface of the tungsten carbide. Finally apply more flux over the top of the cut section of filler
Most specialist tungsten carbide brazing filler metals contain at least an addition of nickel, and many contain additions of both nickel and manganese or cobalt and manganese.
Position 1. EN1044 AG305 & standard flux EN1045 Type FH10 Position 2. EN1044 AG103 & boron modified flux EN1045 Type FH12 Position 3. A5.8 B-Ag24 & standard flux EN1045 Type FH10 Position 4. EN 1044 AG103 & standard flux EN1045 Type FH10
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Tungsten Carbide
metal. It is then simply a question of heating the tungsten carbide until the filler metal melts. Once the piece of tungsten carbide has cooled down remove the flux residues. A visual assessment shows how well the filler metal has wetted and spread. By using different filler metal and flux combinations it would be possible to determine which combination gives the best results for the carbide in question. (See Figure 7)
This very basic test can throw up issues when the pieces of tungsten carbide start coming off rather than finding there is a problem when a whole batch of parts has been brazed and is in use. By using a controlled size and shape of filler metal this standard wetting test can be used as a pre-production check on batches of tungsten carbide. It can also be used to check the effectiveness of the pre-braze cleaning of the tungsten carbide.
wants to contract faster and further than the piece of tungsten carbide to which it is now securely brazed. (See Figure 8) This mismatch results in the development of shear stresses within the joint. If the brazing filler metal has a high strength it will transmit these stresses directly into the relatively brittle tungsten carbide and cause it to crack. What is required is brazing filler metal that has a low yield point that will deform plastically allowing the stress to be dissipated. Unfortunately, the strength
Figure 8: Diagram depicting mismatch in expansion between a tungsten carbide tip and its support backing at brazing temperature
Expansion of Tungsten Carbide
Tungsten Carbide
Backing of Material
Expansion of Backing
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Tungsten Carbide
Figure 9: Results of tensile tests showing how joint clearance and the strength of the parent materials affects joint strength.
a U.T.S of Drill Rod E 70 Tensile Strength Kgf/mm2 E 56 F G A B C D U.T.S of 1020 Steel H I B C D A F G H U.T.S of 1020 Steel b U.T.S of Drill Rod
84
42
28
0.127
0.254
0.267
0.508
0.635 0
0.127
0.254
0.267
0.508
0.635
Joint Thickness mm
Joint Thickness mm
The effect of joint gap (joint thickness) on the tensile strength of brazed butt joints (after Bredzs). The strength of silver (a) and copper (b) brazed joints in steel 1020 is represented by curves ABCD, curves EFGH relating to joints brazed in drill rod steel. The U.T.S. of silver, copper and parent metals is indicated in the graphs of brazing filler metal in a brazed joint is not primarily a function of the strength of that filler metal, but the strength of the parent materials and the thickness of the brazing filler metal layer within the joint. Practical testing has shown that if, for example, an ordinary carbon steel and high strength carbon steel are brazed with the same brazing filler metal, the ordinary carbon steel joint will be weaker than that made in the high strength steel (See Figure 9). It is also understood that the thickness of brazing filler metal in a joint has a strong influence on the strength of a brazed joint - the thinner the joint the higher its strength. It is possible to develop joint strengths that are 2 to 3 times greater than that of the as cast strength of
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the brazing filler material. The situation that is found in a typical brazed joint is that there is a thin layer of a relatively weak, ductile, filler metal bonded securely to two much stronger, less ductile parent materials. When such a joint is subjected to a tensile load, if the load applied to the joint is above the yield point of the brazing filler metal, then the filler metal would be expected to begin to deform in the same manner as a tensile test specimen by necking in. (See Figure 10) However, the thin layer of filler metal is securely bonded to the two parent materials, which prevents it from doing so. Brazed joints therefore typically fail under tri-axial stress conditions and show very little ductile deformation, failing in an almost brittle mode.
Tungsten Carbide
Taking the above into account, the normal perception that a strong joint is required when brazing tungsten carbide could be questioned. It can be understood that if too strong a joint is produced it will not be able to deform to dissipate the cooling stresses. If the filler metal is too strong it will simply transmit the stress into the component causing it to distort or the piece of tungsten carbide to crack to relieve the stresses that have developed. If the levels of stress developed during cooling are extremely high, and the component sufficiently robust such that it cannot distort or crack, the brazing filler metal itself can rupture resulting in the piece of tungsten carbide becoming detached. It is also possible in circumstances where the component is sufficiently robust for the stresses developed on cooling to be contained as residual stresses within the component. The residual stresses locked up in the joint only show themselves when some additional stress is added to the component by the application of some external force,
either a physical mechanical load or thermally generated stresses. It follows from the preceding text, that when brazing tungsten carbide, joints with a good level of ductility are required, such that they can deform readily and allow the stresses that arise on cooling to be dissipated. It also follows, that strong joints, where only a thin layer of brazing filler metal is present between the tungsten carbide and its backing material, will not allow the brazing filler metal to deform in a ductile fashion, and therefore will not allow dissipation of the cooling stresses. Joints that have a thick layer of brazing filler metal between the tungsten carbide and the backing material will be more able to deform and therefore allow dissipation of the cooling stresses. In essence ductile joints are required, which usually means thick joints, which in turn means joints are going to be lower in strength than might be the case for other joints. when brazing tungsten carbide, joints with a good level of ductility are required, such that they can deform readily and allow the stresses that arise on cooling to be dissipated.
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Tungsten Carbide
From the need to produce ductile joints three approaches in relation to the selection of brazing filler metal for applications involving the brazing of tungsten carbide have evolved: These three approaches are particularly applied in the case of selecting silver-base filler metals, where some general rules have been developed, based on the size of carbide that can be brazed successfully.
1.
2.
The use of filler metals that produce joints with thicker than normal layers of filler metal.
3.
The use of products or methods that produce artificially thick brazed joints.
that can be brazed successfully. A further advantage of these filler metals is their low brazing temperatures, which help to minimise the amount of differential expansion developed between the tungsten carbide and the backing material. The high silver content cadmium-bearing filler metals tend to have higher levels of ductility than the cadmium-free filler metals, and therefore may be capable of brazing a wider range of sizes and shapes of tungsten carbide than cadmium-free filler metals.
rod. Pre-placing the filler metal in the joint allows it to produce the thickest possible joints, so allowing the filler metals to be used to their full potential. The additions of nickel and manganese to the filler metals increase their as cast strengths, which to some extent are offset by the thicker joints they produce. In a few cases problems have been encountered when changing from the cadmium-bearing filler metals with additions of nickel and manganese to the cadmium-free filler metals containing nickel and manganese. While there had been no problems using the cadmium-bearing filler metals, with the change to cadmium-free materials
Tungsten Carbide
2.
cracking problems started to occur. These problems tended to be in applications that were at the extreme of the capabilities of the cadmium-bearing filler metals. It was clear that the filler metal, EN 1044 AG502 (49% silver with nickel and manganese) was stronger and less ductile than the cadmium-bearing filler metals previously used. While the AG502 filler metal with its high levels of nickel and manganese is the filler metal most widely used for brazing tungsten carbide in Europe and other
parts of the world, the AWS A5.8 BAg-24 filler metal (50% silver-copper-zinc-nickel) is equally common in the United States. As previously mentioned the nickel and manganese bearing AG502 filler metal is disliked by some due to the colour of the finished braze - a dark red brown, and it is sticky making it difficult to move and position pieces of tungsten carbide. The BAg-24 filler metal does not contain manganese and therefore does not exhibit these characteristics, and as a result some users in Europe are now favouring it.
3.
Where the largest dimension of the tungsten carbide is greater than 20 mm then the use of the tri-metal products is recommended. The interlayer in the tri-metal products produces a thick, ductile joint capable of dissipating significant amounts of stress. The tri-metal products come in various thicknesses; the thickness used in any application being a function of the size of the piece of tungsten carbide. i.e the larger the piece of tungsten carbide, the greater the thickness of tri-metal. In the past, the tri-metal products were coated with the cadmium containing filler metals, EN 1044 AG301 or the nickel containing AG351. By far the most commonly used product today is the cadmium-free 49% silver-copper-zinc alloy containing additions of nickel and manganese. The filler metal used is a modified version of the EN 1044 AG502, where the nickel and manganese
contents have been significantly reduced. The reason why this modified filler metal is used, as opposed to high nickel and manganese AG502 filler metal is to facilitate manufacture of the product. When the need arose for cadmium-free tri-metal products, attempts were first made to use the standard AG502 filler metal. However, problems with de-lamination of the layers and edge cracking during rolling (due to the different work hardening characteristics of the copper interlayer and the filler metal) resulted in the development of the modified filler metal. As previously mentioned, the manganese containing filler metals are disliked by some due to the colour of the finished braze and their stickiness. Tri-metals using the manganese free AWS A5.8 BAg-24 are available and are now preferred in some cases.
The above can only be seen as general guidelines to the selection of a filler metal, as they are based only on the size of the piece of tungsten carbide. Another factor that also needs to be considered is the ductility of the tungsten carbide. This is a function of the cobalt content of the tungsten carbide,
the higher it is the more ductile it will be. The thickness of the tungsten carbide is also important as the thicker it is the more robust it will be. The shape of the tip is also important, since if it has a complex shape with changes in width, thickness and includes sharp corners, as for example in certain router bits,
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Tungsten Carbide
then these changes in form can be points of stress concentration, increasing the likelihood of the tungsten carbide cracking. These additional factors may mean that although it is possible to braze the piece of tungsten carbide based simply on its size with say a standard ductile filler metal, due to its shape it would be prudent to use a nickel bearing filler metal that produces a thicker joint with more stress dissipating capacity. A tri-metal product could be used, although the size of the piece of tungsten carbide does not really warrant its use, in applications where the tungsten carbide in use experiences impact or percussive loads. In these applications the tri-metal can act to cushion the loads applied to the tungsten carbide and stop it from cracking. In some applications, while it prevents cracking of the tungsten carbide, deformation of the interlayer under the service loads can result in cracking problems or joint failures. In such circumstances the use of a tri-metal product with a copper alloy interlayer,
as opposed to a pure copper one, is likely to prove beneficial. In addition to using specific brazing filler metals or products as an aid to dissipating the cooling stresses, slow controlled cooling of joints following brazing is important. Also of importance are those methods that seek to produce thick layers of brazing filler metal between the tungsten carbide and its backing material. As already mentioned, joints were historically thickened by using a layer of woven wire mesh or foil and while tri-metal products are commercially available, the do it yourself approach could be considered if a suitable commercial product is not available. Simple spacer wires can also be used to provide a controlled and thick joint clearance. Raised bars or pips formed on either the tungsten carbide or the backing can be another way in which to produce a suitably large, yet controlled, joint clearance.
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Tungsten Carbide
Removing the oxides from the parent materials and filler metal
It is perhaps obvious that a flux should remove the oxides found and formed on the parent materials. However, not all fluxes are capable of removing all oxides. For example, traditional borax, boric acid type fluxes are not good at removing nickel, zinc or refractory metal oxides.
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Tungsten Carbide
oxides. There is also some practical evidence that boron containing brazing fluxes aid the wetting of filler metals where the parent materials contain some free graphite, which as previously explained can be present in some tungsten carbides. Tungsten carbides with low cobalt contents also exhibit improved wetting when brazed using boron-modified fluxes. One criticism of the boron-modified fluxes is that their dark colour prevents operators from seeing what is happening during the brazing operation, masking the flow of the filler metal. Many of those engaged in the brazing of tungsten carbide will use nothing other than the boron-modified fluxes. The combination of a nickel and manganese bearing filler metal together with a boron-modified flux will give the best wetting and bonding performance whether the carbide is straightforward tungsten carbide, a carbide with a low cobalt content, one that contains additions of titanium and tantalum carbide or one where free graphite is present.
use with the silver brazing filler metals being used with the brass brazing filler metals. The upper active range of the silver brazing filler metals fluxes tends to be in the order of 800C, but the brass brazing filler metals have brazing temperatures around 900C.
Tungsten Carbide
layer that remains on the work when the filler material melts will impede the wetting and flow of the molten filler material.
Time-temperature stability
It is commonly understood that fluxes remove the oxides from the parent material and then prevent further oxidation from taking place. However, this is not strictly the case. While fluxes do remove oxides from the parent materials they do not prevent further oxidation of the parent materials taking place. In fact there is a continual process during a brazing operation of oxygen diffusing through the layer of molten flux, oxidising the parent materials beneath and the flux removing the oxide that has been formed. Molten fluxes do tend to act as a partial barrier to the diffusion of oxygen, but this is a variable characteristic dependent upon the flux formulation and its temperature. This continual process of oxygen diffusing through the molten flux and the flux removing the oxide that has been formed eventually results in the flux becoming spent / exhausted, as it becomes saturated with oxides and so unable to remove any more. Clearly, if the flux has become spent or is losing its ability to remove oxides efficiently before the filler metal is molten, the filler metal will not wet the parent materials successfully. The time-temperature stability of a flux is not something that can be defined numerically, but is rather a concept to explain a characteristic of a flux. For example, if a standard flux with an active range of 550 to 800oC is used with a silver brazing filler metal with a brazing temperature of 750oC, then immediately the joint starts to be heated the parent materials will begin to oxidise. When the flux becomes active at 550C it starts to remove the oxides that have formed up to that point, and more are still continuing to form. The phase is then reached where oxygen diffuses through the molten flux, oxidation of the parent material continues, and the flux continues to remove the oxides as they form. This continual process of oxygen diffusing through
the molten flux and the flux removing the oxide that has been formed eventually results in the flux becoming spent / exhausted, as it becomes saturated with oxides and so unable to remove any more.
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Tungsten Carbide
It can be understood that more oxide will be formed if it takes 5 minutes to get to the brazing temperature of 750C as opposed to 2 minutes. If after 4 minutes, the flux has become loaded with oxide and has become exhausted, then when the brazing filler metal melts the surface will not be oxide-free and will not wet successfully. In such an example, the use of a filler metal with a brazing temperature of 650C would be possible, assuming that the joint could be heated to 650C in less than 4 minutes. The speed at which a flux will become exhausted is a function of how much oxide is formed during a brazing operation. If the
Flux selection
Unlike brazing filler metals there are no standard flux compositions. Fluxes are all made to proprietary formulations and will therefore all have different properties and characteristics. EN 1045 Brazing Fluxes for brazing Classification and technical delivery conditions is, as it indicates, a means by which manufacturers can apply some standard classification to their flux products, but the standard does not go beyond specifying some basic flux characteristics and uses. In manufacturers literature, where reference is made to EN1045, many fluxes are given the same classification, yet they clearly have different properties and characteristics. Unlike a brazing filler metal, where it is an easy matter to conduct a chemical analysis to determine its make up, it is not possible to do this with fluxes. A chemical analysis will not be able to determine the specific chemical compounds that have been used to formulate the flux, as many of the compounds react during manufacture, and it is how they are proportioned and reacted together that determines the components, properties and characteristics of the finished flux. In selecting a flux for any particular application the above points need to be considered. Most manufacturers provide information in their literature about the active range of the flux and give some indication about its life or overheat resistance. There may also be additional information related to some special characteristics of the flux, for example its suitability of use when using HF induction heating. This basic information should allow anyone to select a flux suitable for an application. However, a discussion with the flux manufacturer is likely to be beneficial as they will be aware of the subtle differences in their products and may, based on the details of the application, be able to suggest a flux that offers specific advantages in that application. Rather than just selecting one flux
Unlike brazing filler metals there are no standard flux compositions. Fluxes are all made to proprietary formulations and will therefore all have different properties and characteristics.
thermal masses of the parts to be heated are significant and it takes an extended period to achieve the brazing temperature then the flux will be required to remove oxides from the parent materials over an extended period. It can be appreciated that heating a joint may not involve a linear temperature rise. For example, while it might be possible to heat a component to a temperature of 500C in two minutes, it may take a further 4 minutes to achieve a temperature of 750C. Furthermore, since oxide formation is a chemical reaction, the higher the temperature the faster it goes. In simple terms this means that a flux when used at the lower end of its active range will have a longer life than at the higher end of its temperature range. In practical terms this means that while a flux with an upper active range of 800C could be used to make a joint with a filler metal melting at 800C, there would only be seconds available to make the joint. This might be possible for small parts using HF induction heating. In general, a flux with an upper active range of 800C should not be considered for use with filler metals melting above 750C. Applying this restriction means that the flux will still have some useful life available when the filler material melts and flows.
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Tungsten Carbide
from a manufacturers range, it could well be worth testing two or three that appear to be suitable, to see which provides the best onthe-job performance. The fact that fluxes are proprietary formulations often causes problems if one wants to change from one manufacturers product to anothers. Operators will say that the flux does not work as well. This could be the case, but in many cases what the operator is really saying is that it works differently or perhaps more likely that it reacts differently when heated. This is to be expected, as each formulation will result in a flux with different characteristics. What must be assessed is whether the differences are good, bad or indifferent, and whether the joints produced are of an acceptable quality.
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Tungsten Carbide
Most of the brazing filler metals and products specially developed for the brazing of tungsten carbide are still being used today. However, the use of the cadmium-bearing filler metals is in major decline due to the health and safety issues that arise from their use and environmental pressures.
in the manufacture of any electrical or electronic equipment, since a maximum cadmium level of 0.01% has been imposed on any materials used in the manufacture of such items. It has to be considered how long it will be before other EU Directives or legislation prevent their use in other applications or completely bans the sale of cadmium-bearing filler metals. In addition to the Directives and legislation, the growing interest by major companies in the subject of Product Stewardship is leading to individual companies applying their own restrictions based upon the Directives and legislation already in place. As a supplier or manufacturer it may, for example, not be possible to supply a company with a cutting tool that has been brazed with a cadmium-bearing filler metal.
Table 1: Nominal compositions of the common silver-base, cadmiumbearing filler metals used for the brazing of tungsten carbide
Filler Metal Silver % Copper % Zinc % Cadmium % Nickel % Manganese % Melting Range C EN 1044
50 45 42 40 50 50
15 15 17 19 15.5 13.5
16 16 16 21 15.5 15.5
19 24 25 20 16 16
3 3
Tungsten Carbide
the cooling stresses, is much more likely to result than when hand feeding rod or wire. Mattibraze 45, Easy-flo No. 2 and DIN Argo-flo represent less expensive alternatives to Easy-flo, but due to their lower ductility (particularly DIN Argo-flo) there is some restriction on the size of tungsten carbide that can be brazed in comparison to those that might be brazed with Easy-flo.
reduce their flow properties, which can be best described as sluggish. They therefore exhibit limited capacity for capillary flow. Thus to fully utilise their ability to braze larger sections of tungsten carbide they need to be pre-placed in the joint as pieces of foil, as opposed to being hand fed to the joint. Easy-flo No. 3 and Argo-braze 50 find particular use in the brazing of large diameter rock-drills. Easy-flo No. 3 would also be chosen where
For applications involving pieces of tungsten carbide, with dimensions greater than 10mm, but less than 20mm, Easy-flo No. 3 and Argo-braze 50 are the natural choice. They would also be chosen where one of the more difficult to wet grades of tungsten carbide is to be brazed, this being particularly the case with Argo-braze 50 since it contains manganese. The nickel and manganese additions to these filler metals significantly
tungsten carbide is to be brazed to stainless steel and the finished joint is likely to be exposed to a wet or damp service environment where interfacial corrosion would be a service hazard. Clearly, in brazing tungsten carbide to stainless steel a whole set of new rules (due to the much greater difference in the expansion coefficients between tungsten carbide and stainless steel) needs to be applied.
A* Silver-flo 56 Silver-flo 55
56 56 55
19 22 21
17 17 22
5 5 2
3 -
* This filler metal currently not available from Johnson Matthey The standard cadmium-free filler metals, Silver-flo 56 and Silver-flo 55, are the ones that have replaced the first four cadmiumbearing filler metals in Table 1. However, their ductility is generally lower than the cadmium containing filler metals, typically in the order of 20-25% in the as cast condition. This means that the sizes of tungsten carbide that they will be able to braze successfully are likely be somewhat less than those than for the cadmium-bearing filler metals. The general rule of the tip being less than 10mm in size can however still be applied. Filler metal A has a patented and proprietary composition, and was developed to have a melting range / brazing temperature close to that of the cadmium containing filler metals. Silver-flo 56 and Silver-flo 55, while having marginally higher brazing temperatures than the cadmium containing filler metals, have been
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All three filler metals listed in Table 2 have relatively low brazing temperatures and free flowing properties. The general comments made against the free flowing cadmiumbearing filler metals are also applicable here.
Tungsten Carbide
for many years the accepted replacements for the first four filler metals in Table 1. There are of course a number of lower silver content silver-copper-zinc and silvercopper-zinc-tin filler metals available that could potentially be used for the purpose of brazing tungsten carbide but none appear to be in common use and hence they are not included in Table 2. If seeking a less expensive alternative to the relatively high silver content filler metals of this group, it is important to appreciate that while filler metals may be of a similar composition, their properties, particularly their ductility, could well be significantly less. For example, Silver-flo 56 and Silver-flo 55 are both members of the silver-copper-
zinc-tin family and might seem very similar to a filler metal with only 45% silver and 3% tin, however, the lower silver content, silvercopper-zinc-tin filler metals go through a ductile, brittle transition at about 300C. This transition could result in cracks forming in the filler metal on cooling as it tries to dissipate the cooling stresses. Likewise, while some silver-copper-zinc filler metals are very ductile, others are not. A filler metals ductility cannot be assessed just by its silver content, as it is the combination / percentages of silver, copper and zinc that determine this property. If a less expensive product is required then this should be discussed with a brazing filler metal supplier, as they will have experience and knowledge of which products within their range exhibit the required properties.
Table 3: Nominal compositions of the common cadmium-free nickel and manganese containing filler metals
Filler Metal Silver % Copper % Zinc % Nickel % Manganese % Melting Range C EN 1044
Argo-braze 502 Argo-braze 49H Argo-braze 49LM Argo-braze 40 Argo-braze 27 Argo-braze 25 = AWS A5.8 BAg-24
50 49 49 40 27 25
20 16 27.5 30 39 38
28 23 20.5 28 22 33
670-750 680-705 670-710 670-780 680-830 710-810 AG503 Prop AG502 Prop
= AWS A5.8 BAg-4 as those carbides that are more difficult to wet, due to them having a low cobalt-content, containing titanium or tantalum carbides, or free graphite. None of the filler metals are free flowing and as a general rule need to be preplaced in the joint as a foil pre-form to achieve the best results. Argo-braze 49H can be seen as a replacement for cadmium-containing filler
The filler metals in Table 3, (or at least the first 4) are the most commonly used for the brazing of tungsten carbide. In Europe, Argo-braze 49H is by far the most common, and therefore can currently be regarded as the standard filler metal used for brazing tungsten carbide. All the filler metals listed contain nickel, and the majority also contain manganese. They are therefore suitable for brazing pieces of tungsten carbide with dimensions up to 20 mm as well
24
Tungsten Carbide
metals, Easy-flo No. 3 and Argo-braze 50 in Table 1. However, Argo-braze 49H is stronger and less ductile than both of them, and this can lead to some problems when moving from one of the cadmium-containing filler metals to Argo-braze 49H. The high strength and lower ductility of this filler metal can sometimes result in cracking problems in applications where no such problems existed when using a cadmium-bearing filler metal. A solution to such problems can often be found by using Argo-braze 502 or Argo-braze 49LM. Argo-braze 49H is disliked by some users due to the finished colour of the filler metal and its sticky feel when attempting to move tips around. The solution to both of these issues is to use Argo-braze 502. One advantage that Argo-braze 49H has over similar filler metals is that it offers improved elevated temperature properties. Where most silver based filler metals tend to start losing strength at around 200C, Argo-braze 49H extends this drop off temperature to around 300C. This can be useful when tools are being made that could be subject to elevated temperatures in service. Argo-braze 49H is used as the brazing filler metal in applications ranging from the manufacture of rock-drills to dental burrs, lathe tools to mining tools and router bits to tungsten carbide tipped circular saws. It is currently the first choice filler metal for most tungsten carbide brazing applications where the size of the tip is less than 20 mm. It would also be the first choice in applications where the grade of tungsten carbide was one identified as being difficult to wet, due to its low cobalt content, having additions of titanium and or tantalum carbide or where free graphite was present. Argo-braze 502 is free from manganese and is seen by some to offer certain advantages. This filler metal is commonly used in the United States and is listed within the AWS A5.8
specification (as indicated in Table 3). One of its main advantages is that it is more free flowing than Argo-braze 49H and as a result is often preferred by operators. It can be used in most applications where using Argo-braze 49H would be considered, but as it does not contain manganese, this would exclude it from being used on the more difficult to wet grades of tungsten carbide. Some disadvantage is also seen due to its slightly higher brazing temperature. Argo-braze 49LM was developed as a modified version of Argo-braze 49H for use in the manufacture of a cadmium-free tri-metal product. Although it was developed specifically for this application, it can be used as a filler metal in its own right. Its lower nickel and manganese levels compared to Argo-braze 49H result in a filler metal that is less strong and more ductile. In certain applications, where cracking problems have been experienced with Argo-braze 49H it can provide a solution. Where a tri-metal product coated with Argo-braze 49H is being used and a need arises for some additional filler metal to be added to the joint then it would be logical to use this filler metal if available. However, it is also acceptable to use Argo-braze 49H in such circumstances. Although it is lower in nickel and manganese, the filler metal still shows improved wetting characteristics over the manganese free filler metals in the table. Argo-braze 40 (another AWS A5.8 listed filler metal) represents a more economic filler metal for use when brazing tungsten carbide than the first three filler metals in this table because it contains only 40% silver. Its nickel content provides enhanced wetting characteristics and joint thickening properties making it suitable for many of the applications where Argobraze 502 might be used. Its main drawback is its higher brazing temperature, which makes it less user-friendly than the first three filler Argo-braze 49H is the first choice
filler metal for most tungsten carbide brazing applications where the size of the tip is less than 20 mm and also for applications where the grade of tungsten carbide is difficult to wet, due to its low cobalt content, having additions of titanium and or tantalum carbide or where free graphite was present.
25
Tungsten Carbide
metals in Table 3. Nevertheless where a need exists for a less expensive filler metal then Argo-braze 40 would be a good choice. Argo-braze 27 was developed as a less expensive alternative to Argo-braze 49H. However, its high brazing temperature and long melting range make it much less user friendly than Argo-braze 49H, and even though it is a less expensive alternative it is not extensively employed. Argo-braze 25 was originally developed as a lower cost rock-drill brazing filler
metal. However, the success of the silverfree copper-zinc-cobalt-manganese filler metal for the same application means that currently this filler metal is rarely used. It provides a less expensive alternative to Argobraze 49H, while still offering very good wetting characteristics due to its nickel and manganese contents. Its slightly lower brazing temperature, narrow melting range and lower nickel and manganese content mean that it will flow more freely than Argo-braze 27 and therefore may prove somewhat easier to use.
Argo-braze 85 B* Argo-braze 64 C*
85 65 64 57.5
28 26 32.5
Indium 6 Tin 7
2 2 -
15 5 2 3
* These filler metals currently not available from Johnson Matthey Argo-braze 85 was a filler metal originally suggested for use in applications requiring the simultaneous heat treatment of a backing Argo-braze 85 was a filler metal originally suggested for use in applications requiring the simultaneous heat treatment of a backing material, and it was also identified as having enhanced wetting capabilities on difficult to wet carbides.
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subject to a Physical Vapour Deposition (PVD) coating with TiN (titanium nitride) and other similar types of coating. They contain no elements such as cadmium and zinc that are likely to volatilise during the coating process. The nickel and manganese additions obviously impart the required characteristics for the brazing of tungsten carbide, and indium or tin are used as melting point depressants. Filler metal B might also be considered for use in applications where the joints would be subject to elevated service temperatures.
material, and it was also identified as having enhanced wetting capabilities on difficult to wet carbides. Additionally, the filler metal has good elevated temperature properties up to 400oC and can be used in applications where joints are exposed to elevated temperature conditions in service. However, the filler metal is rarely used as the development of copper based filler metals with similar brazing temperatures and enhanced elevated temperature strength has replaced it. Filler metal B and Argo-braze 64 can or have been specially formulated for use when brazing tungsten carbide items that will be
Tungsten Carbide
Table 5: Nominal compositions of some common copper based brazing filler metals
Filler Metal Copper % Zinc % Cobalt Nickel Manganese % % % Others % Melting Range C EN 1044
Copper B Bronze A Bronze C Bronze D Bronze J Bronze Argentel No. 1 F Bronze D* E* H Bronze Argentel = AMS 4764
39.75 38 35 25 42.25
4 2 -
1083 Boron 0.035 1081-1101 Silicon 0.6 1090-1101 965-995 980-1030 925-955 875-895 890-930 880-920 855-915 880-920 870-890
CU103 CU105 Prop Prop Prop Prop CU301 Prop Prop Prop CU306
* These filler metals currently not available from Johnson Matthey to use copper. Its nickel and boron additions give it better wetting characteristics, and will also allow the formation of joints containing a thicker layer of brazing filler metal. B Bronze has the ability to bridge gaps up to 0.5 mm and is able to fill joints where spacer wires or other means have been used to create a larger controlled joint clearance. This means that it is possible to braze quite large sections of tungsten carbide, since it is possible to produce relatively thick ductile joints with this filler metal. A Bronze was extensively used for the
Pure copper will wet and bond with tungsten carbide very successfully and together with brass was one of the first filler metals to be used for the brazing of tungsten carbide. Its use today is as an inexpensive filler metal for reducing atmosphere or vacuum furnace brazing of tungsten carbide. However, its natural ability to produce joints with a thin layer of brazing filler metal limits its use to applications where small sections of carbide need to be brazed. A typical application could be the brazing of tungsten carbide tips into drills to be sold in the DIY market. B Bronze is another filler metal for use in reducing atmosphere or vacuum furnace brazing of tungsten carbide. It was originally developed to be a filler metal with improved gap filling properties that could be used in reducing atmosphere furnace brazing applications where the joint fits were too large
brazing of rock-drills and is still used in some cases for that type of application. It is used in air with a flux and induction heating. While it could be used for other applications involving the brazing of tungsten carbide it has never been widely used.
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Tungsten Carbide
C Bronze was originally developed to allow for step or sequential furnace brazing of steel components, where pure copper was used as the first step brazing filler metal. The nickel and manganese contents of this filler metal make it highly suitable for the brazing of tungsten carbide, and its melting range makes it suitable for the brazing and simultaneous heat treatment of certain grades of steel. It is used in reducing atmosphere furnace brazing applications, but due to its manganese content, low dew point atmospheres must be used to reduce the manganese oxide and prevent the formation of further quantities
low cost, DIY market, tungsten carbide tipped drills and circular saw blades. Brazing with this filler metal is often carried out using HF induction - the filler metal being applied to the joint in the form of a flux-bearing brazing paste. Flame brazing using a separate flux and automatic feeding of the joint with wire is also widely practiced. Due to the fact that it produces joints containing a relatively thin layer of brazing filler metal its use is restricted to brazing relatively small pieces of tungsten carbide. F Bronze is another filler metal specifically developed for the brazing of rock-drills, but unlike some of the other filler metals developed for this purpose it has found a wider application for brazing tungsten carbide. It is typically applied in air using HF induction heating and a separate flux. The filler metal is most commonly pre-placed in the joint as a main mass and allowed to flow through the joint. Hand torch brazing is also possible with this filler metal. Filler metals D and E are based on the classic nickel silver / bronze welding filler metal composition of Argentel where an addition of manganese has been made to the basic copper-zinc-nickel composition to enhance their wetting performance. These two filler metals represent low cost, high strength materials for torch brazing applications. H Bronze is similar to J Bronze but its high manganese content makes for a lower brazing temperature. This filler metal is recommended for use in elevated temperature applications up to 400C and in the field of brazing tungsten carbide has been used to produce joints that will be exposed to such temperature. It has found use in the brazing of road-planing tools. Argentel is the copper-zinc-nickel-silicon filler metal widely used for bronze welding.
F Bronze is another filler metal specifically developed for the brazing of rock-drills, but unlike some of the other filler metals developed for this purpose it has found a wider application for brazing tungsten carbide.
during the brazing process. It is also used in vacuum brazing applications, but it needs to be used with a partial pressure brazing technique to suppress the volatilisation of the manganese. This filler metal has found extensive use in the brazing of tungsten carbide tipped drills for use by professional trades people, where brazing of the tip and heat treatment of the shank are carried out in one operation. D Bronze is another filler metal specifically developed for the brazing of rock-drills. It has found little or no use outside of this area. J Bronze with its high manganese content, provides filler metal with a lower brazing temperature, and which is higher in strength than C Bronze. Some manufacturers of professional type tungsten carbide tipped drills use it in preference to C Bronze since it is said to offer good wear resistance. At the same time it has a brazing temperature which matches the heat treatment of the high strength steel frequently used as the shank material. Argentel No.1 represents the classic brass brazing filler metal, a 60-40 copper-zinc filler metal with a small addition of silicon. This filler metal tends to be used in the manufacture of
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Tungsten Carbide
Table 6: Nominal compositions of the brazing filler metals used on the common tri-metal products
Filler Metal Silver Copper % % Zinc % Other % Nickel Manganese Melting % % Range C Core Material
64 50 50 50 49 -
16
Indium 6 Cadmium 19
2 3 2 0.5 -
2 2.5 -
730-780
Copper
Also available with copper alloy core and nickel mesh core With nickel mesh core ** Obsolete alloy for Johnson Matthey * These filler metals currently not available from Johnson Matthey The filler metals detailed in Table 6 are those that can be found in the form of tri-metal products, primarily with a copper core and supplied in a ratio of 1:2:1. The characteristics of the individual filler metals have been covered in the relevant tables above. By far the most commonly used products these days are the ones coated with Argo-braze 49LM. The product coated with Filler metal F is obviously intended for use in applications where Physical Vapour Deposition (PVD), TiN (titanium nitride) coatings or similar are to be applied to the part. The products coated with the cadmium containing filler metals, Easy-flo and Easy-flo No.3, are rarely used for the reasons previously mentioned. The cadmiumfree product coated with Argo-braze 502 provides a manganese-free alternative to Argo-braze 49LM, and is preferred by some users as it allows for easier movement and positioning of tips. It is recommended when using the tri-metal products to move and slide the tips around when the filler metal is in the molten condition to reduce flux and gas entrapment in the joints. Filler metal G with a nickel mesh core is a furnace brazing filler
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metal with the ability to braze larger sections of tungsten carbide. As indicated in the table, Argo-braze 49LM while commonly supplied with a copper core can also be supplied with a copper alloy core. The alloy core, often a copper-nickel alloy, provides joints with a higher level of toughness able to cope more adequately with impact loads in service.
Tungsten Carbide
Pallabraze 1120 Pallabraze 830 Orobraze 1004 H* Orobraze 1052 Orobraze 1013 Orobraze 950 Pallabraze 851
75 66.5 -
35 31 25 25 82 -
20 5 10 9.75 15 15 47
2 14 9.75 18 10 18 47
5 2 9.5 16 11 13 -
* These filler metals currently not available from Johnson Matthey The filler metals listed in Table 7 find use in The filler metals listed in Table 7 find use in applications where joints of extremely high strength are required or where the joints need to exhibit high strength at elevated temperatures. Many of the applications are considered confidential so it is not possible to provide any specific details or information about their uses. applications where joints of extremely high strength are required or where the joints need to exhibit high strength at elevated temperatures. Many are patented or have their applications patented. Some are used for making carbide-to-carbide joints, whereas others are used because they allow for simultaneous heat treatment and vacuum brazing of parts. Many of the applications in which such filler metals are used are considered confidential so it is not possible to provide any specific details or information about their uses. Pallabraze 830 was a filler metal developed for the brazing of PCDs where the finished joints were going to be subject to service at elevated temperature. The requirement was for a filler metal to have the lowest possible brazing temperature to minimise the damage to the diamond layer, but have adequate high temperature properties. Filler metal screening suggested the standardised silver-copper- 5% palladium filler metal EN 1044 PD106 would be a possible candidate. However, when this was tested it showed very poor wetting on
30
the tungsten carbide backing of the PCD. This was surprising, since palladium is an element known to improve the wetting characteristics of filler metals. Modified filler metals, with additions of nickel and nickel and manganese were produced and tested. While the nickel containing filler metal showed an improvement in wetting, the nickel and manganese bearing filler metal was by far superior.
Tungsten Carbide
Table 8: EN 1045 Flux classes for use when brazing tungsten carbide
EN 1045 Classification Type FH10 Temperature Range C 500 to 800 For Brazing Above C 600 Composition Type Boron compounds Simple & complex fluorides
Comments Compatible for use with most low temperature silver brazing filler metals. Suitable for use in most applications involving the brazing of tungsten carbide, except in those applications where the tungsten carbide contains titanium of tantalum carbides or has a low cobalt content.
Type FH12
550 to 850
600
Boron compounds Simple & complex fluorides with the addition of elemental boron
Compatible for use with most low temperature silver brazing filler metals. Suitable for use in most applications involving the brazing of tungsten carbide, especially in those applications where the tungsten carbide contains titanium of tantalum carbides, has a low cobalt content or contains free graphite. Compatible for use with the medium temperature brass and nickel silver type filler metals. Flux will not be suitable for brazing tungsten carbides where titanium or tantalum carbides are present.
Type FH20
700 to 1000
750
Type FH21
750 to 1000
800
Boron compounds
Compatible with the high temperature copper based filler metals. Flux will not be suitable for brazing tungsten carbides where titanium or tantalum carbides are present.
Type FH30
+1000
+1000
Compatible with the high temperature copper based filler metals. Flux will not be suitable for brazing tungsten carbides where titanium or tantalum carbides are present.
31
Tungsten Carbide
Metal Joining
the products and services that we can offer email Metal Joining on mj@matthey.com or visit our website at www.jm-metaljoining.com for more information, or contact us on + 44(0)1763 253200.
Johnson Matthey plc cannot anticipate all conditions under which this information and our products or the products of other manufacturers in combination with our products will be used. This information relates only to the specific material designated and may not be valid for such material used in combination with any other materials or in any process. Such information is given in good faith, being based on the latest information available to Johnson Matthey Plc and is, to the best of Johnson Matthey plcs knowledge and belief, accurate and reliable at the time of preparation. However, no representation, warranty or guarantee is made as to the accuracy or completeness of the information and Johnson Matthey plc assumes no responsibility therefore and disclaims any liability for any loss, damage or injury howsoever arising (including in respect of any claim brought by any third party) incurred using this information. The product is supplied on the condition that the user accepts responsibility to satisfy himself as to the suitability and completeness of such information for his own particular use. Freedom from patent or any other proprietary rights of any third party must not be assumed. The text and images on this document are Copyright and property of Johnson Matthey. This datasheet may only be reproduced as information, for use with or for resale of Johnson Matthey products. The JM logo, Johnson Matthey name and product names referred to in this document are trademarks of Johnson Matthey. Easy-flo and Silver-flo are registered to JM in the EU. Sil-fos is registered to JM in the UK and certain other countries but is marketed as Mattiphos in Germany and the USA.
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