CN209627846U - A kind of composite metallic material - Google Patents
A kind of composite metallic material Download PDFInfo
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- CN209627846U CN209627846U CN201822071787.7U CN201822071787U CN209627846U CN 209627846 U CN209627846 U CN 209627846U CN 201822071787 U CN201822071787 U CN 201822071787U CN 209627846 U CN209627846 U CN 209627846U
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Abstract
The utility model relates to field of material technology, disclose a kind of composite metallic material, including carrier layer, barrier layer, peeling layer and metal foil layer；Carrier layer, barrier layer, peeling layer and metal foil layer are cascading, barrier layer includes the metal bonding coating and high-temperature-resistant layer being stacked, metal bonding coating is set between carrier layer and high-temperature-resistant layer, by the way that peeling layer is arranged between carrier layer and metal foil layer, in order to remove carrier layer, and by the way that barrier layer is arranged between carrier layer and metal foil layer, to avoid carrier layer, phase counterdiffusion causes to bond at high temperature with metal foil layer, so that carrier layer is easily peeled off with metal foil layer；In addition, by the way that metal bonding coating is arranged between carrier layer and high-temperature-resistant layer, so that barrier layer is not easy to separate with carrier layer, to prevent peeling-off between barrier layer and carrier layer.
Description
Technical field
The utility model relates to field of material technology, more particularly to a kind of composite metallic material.
Background technique
Currently, substrate is the processing material of flexible printed-circuit board (Flexible Printed Circuit board, FPC)
Material is usually made of flexible insulating basement membrane and composite metallic material.It, usually first will be compound when preparing substrate in the prior art
Metal foil (including carrier layer and metal foil layer) is equipped with the side of metal foil layer and flexible insulating basement membrane is pressed, to obtain
Substrate needs to remove carrier layer when using substrate.But since composite metallic material and flexible insulating basement membrane are pressed
When need under the high temperature conditions, and carrier layer is easy to happen phase counterdiffusion with metal foil layer under the high temperature conditions, so as to cause load
Body layer and metal foil layer bond, so that being difficult to remove between carrier layer and metal foil layer.
Utility model content
The purpose of the utility model embodiment is to provide a kind of composite metallic material, can be avoided the carrier of composite metallic material
Phase counterdiffusion causes to bond layer at high temperature with the metal foil layer of composite metallic material, so that carrier layer is easy to metal foil layer
Removing.
In order to solve the above-mentioned technical problem, the utility model embodiment provides a kind of composite metallic material, including carrier layer, resistance
Interlayer, peeling layer and metal foil layer；
The carrier layer, the barrier layer, the peeling layer and the metal foil layer are cascading, the barrier layer
Including the metal bonding coating and high-temperature-resistant layer being stacked, the metal bonding coating is set to the carrier layer and the high-temperature-resistant layer
Between.
Preferably, at a temperature of 20-400 DEG C, the peel strength between the carrier layer and the barrier layer is big
Peel strength between the peeling layer and the metal foil layer.
Preferably, the hundred lattice test grade between the carrier layer and the barrier layer is 0 or 1 or 2, the stripping
Peel strength between absciss layer and the metal foil layer is 0.001-2N/cm.
Preferably, the peel strength between the peeling layer and the metal foil layer is greater than or equal to the removing
Peel strength between layer and the barrier layer.
Preferably, the high-temperature-resistant layer be organic high temperature-resistant layer, alternatively, the high-temperature-resistant layer by tungsten, chromium, zirconium,
Any one material in titanium, nickel, molybdenum, cobalt and graphite is made.
Preferably, the high-temperature-resistant layer is single layer alloy structure；Or, the high-temperature-resistant layer is that single material layer is constituted
Multilayered structure or the multilayered structure that constitutes of alloy-layer and single material layer, wherein the list material layer is by same chemical element
It is made.
Preferably, the metal bonding coating is made of any one material in the first metalloid；Alternatively, the gold
Belong to adhesive layer to be made of any one material in the second metalloid；Wherein, first metalloid is to be easy to and the carrier layer
The metal of bonding, second metalloid are the metal for being easy to bond with the high-temperature-resistant layer.
Preferably, first metalloid is copper or zinc, and second metalloid is nickel or iron or manganese.
Preferably, the metal bonding coating is single layer alloy knot made of the first metalloid and the second metalloid
Structure；Wherein, first metalloid be easy to the carrier layer bond metal, second metalloid be easy to it is described
The metal of high-temperature-resistant layer bonding.
Preferably, the metal bonding coating includes the list for being made of first kind metal and connecting with the carrier layer
Metal layer, the metal bonding coating further include the single metal layer for being made of the second metalloid and connecting with the high-temperature-resistant layer；Its
In, first metalloid is the metal for being easy to bond with the carrier layer, and second metalloid is to be easy to and the resistance to height
The metal of warm layer bonding.
Preferably, the metal bonding coating includes the multilayered structure that alloy-layer and single metal layer are constituted；Wherein, institute
The alloy-layer for stating metal bonding coating is made of the first metalloid and the second metalloid, and the single metal layer of the metal bonding coating is by
One metalloid or the second metalloid are made；Wherein, first metalloid is the metal for being easy to bond with the carrier layer, described
Second metalloid is the metal for being easy to bond with the high-temperature-resistant layer.
Preferably, the peeling layer is made of any one material in nickel, silicon, molybdenum, graphite, titanium and niobium；Or,
The peeling layer is made of high-molecular organic material.
Preferably, the thickness of the metal foil layer is less than or equal to 9 μm.
Preferably, the metal foil layer is copper foil or aluminium foil；And/or the carrier layer is carrier copper or carrier
Aluminium or organic film.
Preferably, the carrier layer is less than or equal to 5 μ close to the roughness Rz of the one side of the metal foil layer
m；And/or the roughness Rz of one side of the metal foil layer far from the carrier layer is less than or equal to 3.0 μm.
Preferably, the carrier layer is equipped with the first antioxidation coating close to the side of the barrier layer；And/or
The metal foil layer is equipped with the second antioxidation coating far from the side of the barrier layer.
A kind of composite metallic material provided by the embodiment of the utility model, including be cascading carrier layer, barrier layer,
Peeling layer and metal foil layer, barrier layer include the metal bonding coating and high-temperature-resistant layer being stacked, and metal bonding coating is set to carrier
Between layer and high-temperature-resistant layer, by the way that peeling layer is arranged between carrier layer and metal foil layer, in order to remove carrier layer, and pass through
Barrier layer is set between carrier layer and metal foil layer, and to avoid carrier layer, phase counterdiffusion causes to glue at high temperature with metal foil layer
Knot, so that carrier layer is easily peeled off with metal foil layer；In addition, viscous by the way that metal is arranged between carrier layer and high-temperature-resistant layer
Layer is tied, so that barrier layer is not easy to separate with carrier layer, to prevent peeling-off between barrier layer and carrier layer.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of one embodiment of composite metallic material provided by the utility model；
Fig. 2 is the structural schematic diagram of another embodiment of composite metallic material provided by the utility model；
Fig. 3 is the removing schematic diagram of the embodiment of composite metallic material provided by the utility model；
Fig. 4 is another removing schematic diagram of the embodiment of composite metallic material provided by the utility model；
Fig. 5 is the flow diagram of one embodiment of the preparation method of composite metallic material provided by the utility model；
Wherein, 1, carrier layer；2, barrier layer；21, high-temperature-resistant layer；22, metal bonding coating；221, first kind metal single layer knot
Structure；222, the second metalloid single layer structure；3, peeling layer；4, metal foil layer.
Specific embodiment
The following will be combined with the drawings in the embodiments of the present invention, carries out the technical scheme in the embodiment of the utility model
Clearly and completely describe, it is clear that the described embodiments are only a part of the embodiments of the utility model, rather than whole
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts
Every other embodiment obtained, fall within the protection scope of the utility model.
Refering to Figure 1, in order to solve the above-mentioned technical problem, the utility model embodiment provides a kind of composition metal
Foil, including carrier layer 1, barrier layer 2, peeling layer 3 and metal foil layer 4；
The carrier layer 1, the barrier layer 2, the peeling layer 3 and the metal foil layer 4 are cascading, the resistance
Interlayer 2 includes the metal bonding coating 22 and high-temperature-resistant layer 21 being stacked, and the metal bonding coating 22 is set to 1 He of carrier layer
Between the high-temperature-resistant layer 21.
In the utility model embodiment, by the way that peeling layer 3 is arranged between carrier layer 1 and metal foil layer 4, in order to shell
From carrier layer 1, and by the way that barrier layer 2 is arranged between carrier layer 1 and metal foil layer 4, to avoid carrier layer 1 and metal foil layer 4
Phase counterdiffusion causes to bond at high temperature, so that carrier layer 1 is easily peeled off with metal foil layer 4；In addition, by carrier layer
Metal bonding coating 22 is set between 1 and high-temperature-resistant layer 21, so that barrier layer 2 is not easy to separate with carrier layer 1, to prevent from hindering
It is peeling-off between interlayer 2 and carrier layer 1.
In the utility model embodiment, in order to ensure when using the composite metallic material by carrier layer 1, barrier layer 2
It is removed simultaneously with peeling layer 3, at a temperature of 20-400 DEG C, the peel strength between the carrier layer 1 and the barrier layer 2 is greater than
Peel strength between the peeling layer 3 and the metal foil layer 4.Preferably, between the carrier layer 1 and the barrier layer 2
Hundred lattice test grade be 0 or 1 or 2, peel strength between the peeling layer 3 and the metal foil layer 4 is 0.001-2N/
cm.Hundred lattice test grade in the present embodiment is ISO grade, can refer to standard " GBT9286-1998 paint and varnish paint
The cross cut test of film ", in addition, the hundred lattice test grade in the present embodiment can correspond to ASTM grade, for example hundred lattice test grade
Corresponding to ASTM grade for 0 is 5B, and hundred lattice test grade is that 1 to correspond to ASTM grade be 4B, and so on, it does not do herein more
Repeat.Hundred lattice test grade can embody the peel strength between the carrier layer 1 and the barrier layer 2, and more forward grade,
Peel strength then between the carrier layer 1 and the barrier layer 2 is bigger.Hundred between the carrier layer 1 and the barrier layer 2
Adhesive force of the lattice test grade all between preceding three-level, i.e., the described carrier layer 1 and the barrier layer 2 is bigger, and the removing
Peel strength between layer 3 and the metal foil layer 4 is very small, so that between the carrier layer 1 and the barrier layer 2
Peel strength is far longer than the peel strength between the peeling layer 3 and the metal foil layer 4 always, therefore, described in use
It, can be easily by the carrier layer 1, the barrier layer 2 and the peeling layer 3 simultaneously from the metal foil when composite metallic material
It is removed on layer 4.
As shown in figure 3, the removing between the peeling layer 3 and the metal foil layer 4 is strong in the utility model embodiment
Degree is greater than or equal to the peel strength between the peeling layer 3 and the barrier layer 2.Due to the peeling layer 3 and the metal
Therefore the peel strength that peel strength between layers of foil 4 is greater than or equal between the peeling layer 3 and the barrier layer 2 is being shelled
When from the composite metallic material, the peeling layer 3 can be stayed in partly or entirely on the metal foil layer 4, so as to prevent
The metal foil layer 4 aoxidizes, and then is effectively protected the metal foil layer 4.Certainly, the peeling layer 3 and the metal foil
Peel strength between layer 4 might be less that the peel strength between the peeling layer 3 and the barrier layer 2, so that shelling
When from the composite metallic material, the peeling layer 3 can be stayed in partly or entirely on the barrier layer 2, and with the carrier
Layer 1 and the barrier layer 2 are removed from the metal foil layer 4 simultaneously, are more repeated as shown in figure 4, not doing herein.
Refering to Figure 1, the thickness of the barrier layer 2 is greater than or equal toPreferably, the thickness of the barrier layer 2
Degree is preferablyWherein, the high-temperature-resistant layer 21 is organic high temperature-resistant layer 21；Alternatively, the high-temperature-resistant layer 21 by tungsten,
Any one or more material in chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite is made.Preferably, the high-temperature-resistant layer 21 is single layer
Alloy structure；Or, the high-temperature-resistant layer 21 be the multilayered structure that single material layer is constituted or alloy-layer and single material layer constitute it is more
Layer structure, wherein the list material layer is made of same chemical element.Specifically, the single layer alloy structure is by alloy
Single layer structure made of material, for example, single layer structure made of tungsten-evanohm；The high-temperature-resistant layer 21 is that single material layer is constituted
Multilayered structure or the multilayered structure that constitutes of alloy-layer and single material layer, for example, the multilayer that tungsten metal layer and chromium metal layer are constituted
Structure, alternatively, the multilayered structure that tungsten-chromium alloy layer and zirconium metal layer are constituted.
Referring to figs. 1 and 2, stripping layering, the gold between the barrier layer 2 and the carrier layer 1 in order to prevent
Belong to adhesive layer 22 to be made of any one or more material in the first metalloid；Alternatively, the metal bonding coating 22 is by the second class
Any one or more material is made in metal；Alternatively, the metal bonding coating 22 is by any one in the first metalloid or more
Any one or more material is made in kind material and the second metalloid；Wherein, first metalloid is to be easy to and the load
The metal of body layer bonding, second metalloid is the metal for being easy to bond with the high-temperature-resistant layer 21, to prevent from carrier
It is removed between layer 1 and barrier layer 2.Preferably, first metalloid is copper or zinc, second metalloid be nickel or iron or
Manganese.By the way that the metal bonding coating 22 is arranged, so that the barrier layer 2 can securely be connect with the carrier layer 1, thus
It prevents peeling-off between the barrier layer 2 and the carrier layer 1.Further, since between the first metalloid and the carrier layer 1
Cohesive force it is stronger, the second metalloid is stronger with the cohesive force between the high-temperature-resistant layer 21, therefore by will be by first
Single metal layer made of metalloid is connect with the carrier layer 1, at the same will the single metal layer made of the second metalloid with it is described
High-temperature-resistant layer 21 connects, so that the barrier layer 2 is not easy to separate with the carrier layer 1.
In the utility model embodiment, the structure of the metal bonding coating 22 may include but be not limited to following several feelings
Condition: (1) metal bonding coating 22 is single metal layer made of the first kind metal；(2) metal bonding coating 22 is institute
It states the second metalloid and single metal layer is made；(3) metal bonding coating 22 is first metalloid and second metalloid
Manufactured single layer alloy structure, such as single layer alloy structure made of copper-nickel alloy；(4) metal bonding coating 22 include by
The single metal layer that first kind metal is made and connect with the carrier layer 1, the metal bonding coating 22 further include by the second eka-gold
Belong to the single metal layer for being made and connecting with the high-temperature-resistant layer 21, for example, the multilayered structure that copper metal layer and nickel metal layer are constituted,
And copper metal layer is connect with the carrier layer 1, nickel metal layer is connect with the high-temperature-resistant layer 21；(5) metal bonding coating 22
The multilayered structure constituted including alloy-layer and single metal layer；Wherein, the alloy-layer of the metal bonding coating 22 is by the first kind
Metal and second metalloid are made, and the single metal layer of the metal bonding coating 22 is by first metalloid or described second
Metalloid is made；For example, single metal layer made of alloy-layer and manganese made of copper-nickel alloy.
The structure of the metal bonding coating 22 is described in detail with above-mentioned situation (4) below, please refers to Fig. 2 institute
Show, in the present embodiment, the metal bonding coating 22 is by first kind metal single layer structure 221 and the second metalloid single layer structure
222 are made, wherein the first kind metal single layer structure 221 is made of first kind metal and connect with the carrier layer 1
Single metal layer, the second metalloid single layer structure 222 are made of the second metalloid and connect with the high-temperature-resistant layer 21
Single metal layer.
In the utility model embodiment, in the first kind metal single layer structure 221 and the second metalloid single layer structure
It can also be arranged between 222 and be made of the single layer structure of first metalloid and/or the single layer structure of second metalloid
Structure.By being arranged between the first kind metal single layer structure 221 and the second metalloid single layer structure 222 by described the
Structure made of the single layer structure of the single layer structure of one metalloid and/or second metalloid, to further increase the resistance
The fixing connected between interlayer 2 and the carrier layer 1, to further prevent between the barrier layer 2 and the carrier layer 1
It is peeling-off.
In the utility model embodiment, the peeling layer 3 by nickel, silicon, molybdenum, graphite, titanium and niobium any one or
Multiple material is made；Or, the peeling layer 3 is made of high-molecular organic material.Wherein, the thickness of the peeling layer 3 is preferablyUniform metal foil layer 4 is formed due to being difficult to when the peeling layer 3 is blocked up, to be easy to cause metal foil layer 4
It is upper to generate a large amount of pin holes (when having pin hole on metal foil layer 4, after it is etched into route, breaking phenomena is easy to appear)；
When the peeling layer 3 is excessively thin, it is easy to cause to be difficult to remove between metal foil layer 4；Therefore by by the peeling layer 3
Thickness is preferablyIt ensures that and is capable of forming uniform metal foil layer 4, avoid and generated on metal foil layer 4
A large amount of pin holes, while to be easily peeled off between the peeling layer 3 and the metal foil layer 4.
In the present embodiment, the thickness of the metal foil layer 4 is less than or equal to 9 μm.To meet wiring board microfine circuit system
The requirement of work, it is preferable that the thickness of the metal foil layer 4 can be 6 μm, 5 μm, 4 μm or 2 μm etc., to be advantageously formed
The very thin metal foil layer 4 of microfine circuit wiring board.In addition, in order to which to obtain pin hole few and completely for removing from carrier layer 1
Very thin metal foil layer 4 (especially with a thickness of 2 μm, 4 μm etc. of metal foil layer) is provided with metal bonding coating in the present embodiment
22, to not only make that there is stronger peel strength between barrier layer 2 and carrier layer 1 using metal bonding coating 22, effectively really
Having protected carrier layer 1 can steadily strip down from metal foil layer 4, and then obtain complete very thin metal foil layer 4, but also
It is handled using surface of the metal bonding coating 22 to carrier layer 1, so that the whole surface of carrier layer 1 is more uniform, causes
It is close, so that being conducive to the removing from carrier layer 1 obtains the less very thin metal foil layer 4 of pin hole, and then be conducive to subsequent conditioning circuit
Production.In addition, the metal foil layer 4 is preferably copper foil or aluminium foil；The carrier layer 1 can be carrier copper, carrier aluminum or organic
Film etc., since carrier layer 1 mainly plays carrying, it is therefore desirable to certain thickness, when the carrier layer 1 is carrier copper or load
When body aluminium, the thickness of the carrier layer 1 is preferably 9-50 μm；When the carrier layer 1 is organic film, the carrier layer 1
Thickness is preferably 20-100 μm.
In the utility model embodiment, the carrier layer 1 is small close to the roughness Rz of the one side of the metal foil layer 4
In or equal to 5 μm；And/or the roughness Rz of one side of the metal foil layer 4 far from the carrier layer 1 is less than or equal to 3.0
μm.When metal foil layer 4 is copper foil, the roughness of copper foil is bigger, and the cohesive force between other materials is bigger, but works as copper
The roughness of foil is excessive, will be unable to apply in high frequency signal transmission wiring board, therefore the roughness Rz of general copper foil
It is 0.5-3.0 μm；When copper foil is in frequency applications, by the way that the roughness of copper foil is set smaller than 0.5 μm, thus ensuring copper
Under the premise of cohesive force between foil and other materials, so that copper foil can be applied to high frequency signal transmission wiring board.
In the utility model embodiment, the carrier layer 1 is aoxidized in order to prevent, the carrier layer 1 in the present embodiment
The first antioxidation coating is equipped with close to the side of the barrier layer 2；By in the carrier layer 1 close to the barrier layer 2 one
Side is equipped with the first antioxidation coating, to prevent the carrier layer 1 from aoxidizing, to protect the carrier layer 1.The gold in order to prevent
Belong to layers of foil 4 to aoxidize, the metal foil layer 4 is equipped with the second antioxidation coating far from the side of the barrier layer 2, by the gold
Belong to layers of foil 4 and be equipped with the second antioxidation coating far from the side of the barrier layer 2, to prevent the metal foil layer 4 from aoxidizing, to protect
Protect the metal foil layer 4.
It please refers to shown in Fig. 5, in order to solve identical technical problem, the utility model embodiment also provides a kind of for making
The preparation method of the standby composite metallic material, comprising the following steps:
S11 forms carrier layer 1；
S12 forms metal bonding coating 22 on the side of the carrier layer 1；
S13 forms high-temperature-resistant layer 21, the metal bonding coating 22 and the high-temperature-resistant layer on the metal bonding coating 22
21 constitute barrier layer 2；
S14 forms peeling layer 3 on the barrier layer 2；
S15 forms metal foil layer 4 on the peeling layer 3.
It, can be easily by the carrier layer 1,2 and of the barrier layer in order to ensure when using the composite metallic material
The peeling layer 3 is removed from the metal foil layer 4 simultaneously, in the utility model embodiment, at a temperature of 20-400 DEG C, and institute
State the removing that the peel strength between carrier layer 1 and the barrier layer 2 is greater than between the peeling layer 3 and the metal foil layer 4
Intensity.Preferably, at a temperature of 20-400 DEG C, hundred lattice between the carrier layer and barrier layer test grade be 0 or 1 or
2, the peel strength between the peeling layer 3 and the metal foil layer 4 is 0.001-2N/cm.
In the utility model embodiment, the first metalloid is the metal for being easy to bond with the carrier layer 1, the second eka-gold
Belong to be easy to the metal bonded with the high-temperature-resistant layer 21, it is preferable that first metalloid is copper or zinc, second eka-gold
Belong to is nickel or iron or manganese.
Electricity when due to being easy to cause the roughness of the barrier layer 2 and the peeling layer 3 to be electroplated using plating mode
The influence of stream, so that the surface roughness for forming the barrier layer 2 and the peeling layer 3 is very inhomogenous, so as to cause
The surface roughness for being subsequently formed the metal foil layer 4 is also inhomogenous, is then unfavorable for forming excellent removing stability and needle
Hole number, while being also unfavorable for the production of subsequent conditioning circuit.Based on this, in the utility model embodiment, the step S12, institute
State step S13 and step S14 preferably in the manner of sputtering, the electric current for sputtering mode preferably uses 6-12A, and voltage preferably uses
300-500V.The metal bonding coating 22 and the high-temperature-resistant layer 21 formed by sputtering constitutes the barrier layer 2, to ensure
The barrier layer 2 of even compact is obtained, and forms the peeling layer 3 of even compact by sputtering, to be conducive to improve composition metal
The removing stability of foil and the quantity that pin hole can be efficiently reduced；In addition, the metal foil layer 4 is preferably using the side of plating
Formula is formed, and before forming the metal foil layer 4, the barrier layer 2 and peeling layer 3 of even compact is formed by sputtering, favorably
In 4 uniformly-coating of metal foil layer, so that the surface roughness of the metal foil layer 4 formed is than more uniform, in turn
Be conducive to the production of subsequent conditioning circuit, and be conducive to make the thinner metal foil layer 4.
In the utility model embodiment, metal bonding coating 22 is formed on the side of the carrier layer 1 specifically: in institute
It states and forms single metal layer on the side of carrier layer 1；Wherein, the single metal layer formed on the side of the carrier layer 1 is by first
Metalloid or the second metalloid are made.
In the utility model embodiment, forming metal bonding coating 22 on the side of the carrier layer 1 specifically can be with
It is: forms single layer alloy structure on the side of the carrier layer 1；Wherein, the single layer formed on the side of the carrier layer 1
Alloy structure is made of the first metalloid and the second metalloid.
In the utility model embodiment, forming metal bonding coating 22 on the side of the carrier layer 1 specifically can be with
It is: forms multilayered structure on the side of the carrier layer 1；Wherein, the multilayered structure formed on the side of the carrier layer 1
Including the single metal layer for being made of first kind metal and being connect with the carrier layer 1, formed on the side of the carrier layer 1
Multilayered structure further includes the single metal layer for being made of the second metalloid and connecting with the high-temperature-resistant layer 21.
In the utility model embodiment, forming metal bonding coating 22 on the side of the carrier layer 1 specifically can be with
It is: forms multilayered structure on the side of the carrier layer；Wherein, the multilayered structure formed on the side of the carrier layer 1
Including alloy-layer and single metal layer, the alloy-layer of the multilayered structure formed on the side of the carrier layer 1 is by the first metalloid
Be made with the second metalloid, the single metal layer of the multilayered structure formed on the side of the carrier layer 1 by the first metalloid or
Second metalloid is made.
The high-temperature-resistant layer 21 can be organic high temperature-resistant layer 21；Or, high-temperature-resistant layer described in the high-temperature-resistant layer 21 is single
Layer alloy structure；Or, the high-temperature-resistant layer 21 is that the multilayered structure that single material layer is constituted or alloy-layer and single material layer are constituted
Multilayered structure, the list material layer are made of same chemical element；Wherein, the high-temperature-resistant layer 21 is organic high temperature-resistant layer,
Alternatively, the high-temperature-resistant layer 21 is made of any one or more material in tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite.
It is further comprising the steps of after the formation carrier layer 1 in the utility model embodiment:
S111, the carrier layer 1 is roughened, the carrier layer 1 after being roughened；
S112 forms the first antioxidation coating in carrier layer 1 in the roughened；
Wherein, the carrier layer 1 can be carrier copper or carrier aluminum.The carrier layer 1 can be formed using plating, shape
Plating solution at the carrier layer 1 may include copper-bath, wherein form the copper content of the plating solution of the carrier layer 1 are as follows:
15-25g/L, pH value 6-9；The plating solution for forming the carrier layer 1 further includes additive, and the additive includes brightener sulfonic acid
The mass fraction of sodium, leveling agent thiocarbamide and wetting agent polyethylene glycol, the brightener sodium sulfonate is preferably 0.1-2g/L, described whole
The mass fraction of flat agent thiocarbamide is preferably 0.01-1g/L, and the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5g/L.
The carrier layer 1 is roughened, it can be by way of acid electroplating, wherein the plating solution for acid copper-plating can wrap
Copper-bath is included, the copper content of the plating solution for acid copper-plating is 10-15g/L, acid content 90-100g/L, and molybdenum content is
600-800PPM.Wherein, the form of zinc-nickel alloy can be used by forming first antioxidation coating；In addition, in the roughened
Carrier layer 1 on form the first antioxidation coating after, can also to first antioxidation coating carry out plasma cleaning (plasma),
Wherein, voltage when carrying out plasma cleaning preferably uses 1500-2500V, and electric current preferably uses 0.1-1.5A.
In the utility model embodiment, in order to further prevent bonding between carrier layer 1 and metal foil layer 4, this
After the formation carrier layer 1 in embodiment further include:
S113 makes annealing treatment the carrier layer 1 with heat treatment condition；Wherein, the heat treatment condition are as follows: at heat
Managing temperature is 200-300 DEG C, and heating time is 30-300 minutes.Preferably, the heating time is 1 hour.By will be described
Carrier layer 1 is made annealing treatment with heat treatment condition, to inhibit the crystalline growth of the carrier layer 1 in heating process, to postpone
The diffusion of carrier layer 1 in heating process, and then further prevent bonding between carrier layer 1 and metal foil layer 4.
In the utility model embodiment, the peeling layer 3 can be by any one in nickel, silicon, molybdenum, graphite, titanium and niobium
Kind or multiple material are made.
In the utility model embodiment, the metal foil layer 4 can be copper foil or aluminium foil.The metal foil layer 4 can be with
It is formed using plating, the plating solution for forming the metal foil layer 4 may include copper-bath, wherein form the metal foil
The copper content of the plating solution of layer 4 are as follows: 15-25g/L, pH value 6-9；The plating solution for forming the metal foil layer 4 includes additive, described
Additive includes brightener sodium sulfonate, leveling agent thiocarbamide and wetting agent polyethylene glycol, the mass fraction of the brightener sodium sulfonate
The mass fraction of preferably 0.1-2g/L, the leveling agent thiocarbamide are preferably 0.01-1g/L, the matter of the wetting agent polyethylene glycol
Measuring score is preferably 0.1-5g/L.It, will in the present embodiment in order to avoid composite metallic material warpage in the utility model embodiment
The plating solution for preparing the carrier layer 1 and the metal foil layer 4 is set as identical, so that the carrier layer 1 and the metal foil
The stress of layer 4 is identical with pulling force effect, so that the carrier layer 1 is identical with the bending degree of the metal foil layer 4, into
And avoid composite metallic material warpage.
In the utility model embodiment, the preparation method of the composite metallic material is further comprised the steps of:
S31, by the metal foil layer 4 being roughened on one side far from the carrier layer 1.
S32 forms the second antioxidation coating in one side of the metal foil layer 4 far from the carrier layer 1 in the roughened.
Wherein, being roughened on one side far from the carrier layer 1 by the metal foil layer 4, can pass through
The mode of acid electroplating, wherein the plating solution for acid copper-plating may include copper-bath, the plating solution for acid copper-plating
Copper content is 10-15g/L, acid content 90-100g/L, molybdenum content 600-800PPM；Wherein, it is anti-oxidation to form described second
Layer can use the form of zinc-nickel alloy；In addition, after forming the second antioxidation coating, it can also be to second antioxidation coating
It carries out plasma cleaning (plasma), wherein voltage when carrying out plasma cleaning preferably uses 1500-2500V, and electric current is preferred
Using 0.1-1.5A.
Following preparation methods that following embodiment is provided and is used to illustrate composite metallic material, specific as follows:
Embodiment 1
S41 forms carrier layer 1 using plating mode, then the carrier layer 1 is roughened, then in carrier layer 1
The first antioxidation coating is formed, and the carrier layer 1 is made annealing treatment with heat treatment condition；Wherein, the heat treatment condition
Are as follows: heat treatment temperature is 250 DEG C, and heating time is 1 hour；The carrier layer 1 is carrier copper, forms the plating of the carrier layer 1
Liquid includes copper-bath, wherein forms the copper content of the plating solution of the carrier layer 1 are as follows: 20g/L, pH value 7；Described in formation
The plating solution of carrier layer 1 further includes additive, and the additive includes brightener sodium sulfonate, leveling agent thiocarbamide and the poly- second two of wetting agent
Alcohol, the mass fraction of the brightener sodium sulfonate are 0.8g/L, and the mass fraction of the leveling agent thiocarbamide is 0.5g/L, the profit
The mass fraction of humectant polyethylene glycol is 3g/L.In addition, the carrier layer 1 is roughened, acid electroplating can be passed through
Mode, wherein the plating solution for acid copper-plating includes copper-bath, and the copper content of the plating solution for acid copper-plating is 13g/L,
Acid content is 95g/L, molybdenum content 700PPM.Wherein, the form that first antioxidation coating uses zinc-nickel alloy is formed.
S42 forms metal bonding coating 22 on the side by sputtering at the carrier layer 1；Wherein, the metal bonding coating
22 structures constituted for copper metal layer and nickel metal layer, and copper metal layer is connect with the carrier layer 1, nickel metal layer with it is described resistance to
Heat zone 21 connects；
S43 forms high-temperature-resistant layer 21, the metal bonding coating 22 and described by sputtering on the metal bonding coating 22
High-temperature-resistant layer 21 constitutes barrier layer 2；Wherein, the high-temperature-resistant layer 21 is single layer alloy structure made of tungsten-titanium alloy；
S44 forms peeling layer 3 by sputtering on the barrier layer 2；Wherein, the peeling layer 3 is graphite linings；
S45 forms metal foil layer 4 using plating mode on the peeling layer 3；Wherein, the metal foil layer 4 is copper
Foil；It is identical as the plating solution that the carrier layer 1 uses to form the plating solution that the metal foil layer 4 uses；
S46 by the metal foil layer 4 being roughened on one side far from the carrier layer 1, and uses acid electroplating
Mode one side of the metal foil layer 4 far from the carrier layer 1 in the roughened on form the second antioxidation coating；Wherein,
Plating solution for acid copper-plating includes copper-bath, and the copper content of the plating solution for acid copper-plating is 13g/L, and acid content is
95g/L, molybdenum content 700PPM；Wherein, the form of zinc-nickel alloy can be used by forming second antioxidation coating.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be tungsten-nickel alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 3
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be tungsten-molybdenum alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 4
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be chromium-nickel alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 5
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be zirconium-titanium alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 6
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be titanium-nickel alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 7
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be titanium-molybdenum alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 8
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be titanium-cobalt alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 9
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be nickel-molybdenum alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 10
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 be molybdenum-cobalt alloy made of single layer alloy knot
Structure.Other techniques and step of the present embodiment are same as Example 1, do not do more repeat herein.
Embodiment 11
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is knot made of tungsten metal layer and graphite linings
Structure, and tungsten metal layer is connect with the metal bonding coating 22, graphite linings are connect with the peeling layer 3.Other works of the present embodiment
Skill and step are same as Example 1, do not do more repeat herein.
Embodiment 12
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is knot made of chromium metal layer and graphite linings
Structure, and chromium metal layer is connect with the metal bonding coating 22, graphite linings are connect with the peeling layer 3.Other works of the present embodiment
Skill and step are same as Example 1, do not do more repeat herein.
Embodiment 13
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is knot made of nickel metal layer and graphite linings
Structure, and nickel metal layer is connect with the metal bonding coating 22, graphite linings are connect with the peeling layer 3.Other works of the present embodiment
Skill and step are same as Example 1, do not do more repeat herein.
Embodiment 14
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is made of tungsten-nickel alloy and chromium metal layer
Structure, and tungsten-nickel alloy is connect with the metal bonding coating 22, chromium metal layer is connect with the peeling layer 3.The present embodiment its
Its technique and step are same as Example 1, do not do more repeat herein.
Embodiment 15
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is made of nickel-molybdenum alloy and chromium metal layer
Structure, and nickel-molybdenum alloy is connect with the metal bonding coating 22, chromium metal layer is connect with the peeling layer 3.The present embodiment its
Its technique and step are same as Example 1, do not do more repeat herein.
Embodiment 16
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is made of molybdenum-cobalt alloy and chromium metal layer
Structure, and molybdenum-cobalt alloy is connect with the metal bonding coating 22, chromium metal layer is connect with the peeling layer 3.The present embodiment its
Its technique and step are same as Example 1, do not do more repeat herein.
Embodiment 17
The present embodiment the difference from embodiment 1 is that, the high-temperature-resistant layer 21 is made of titanium-nickel alloy and chromium metal layer
Structure, and titanium-nickel alloy is connect with the metal bonding coating 22, chromium metal layer is connect with the peeling layer 3.The present embodiment its
Its technique and step are same as Example 1, do not do more repeat herein.
Comparative example 1
The present embodiment the difference from embodiment 1 is that, after forming the carrier layer 1, do not make the barrier layer 2,
But peeling layer 3 is formed directly in the carrier layer 1.Other techniques and step of the present embodiment are same as Example 1, herein
It does not do and more repeats.
Comparative example 2
The present embodiment the difference from embodiment 1 is that, after forming the metal bonding coating 22, do not make the resistance to height
Warm layer 21, but peeling layer 3 is formed directly on the metal bonding coating 22.Other techniques and step of the present embodiment and implementation
Example 1 is identical, does not do more repeat herein.
Comparative example 3
The present embodiment the difference from embodiment 1 is that, after forming the carrier layer 1, do not make the metal bonding
Layer 22, but high-temperature-resistant layer 21 is formed directly in the carrier layer 1.Other techniques and step and embodiment 1 of the present embodiment
It is identical, it does not do more repeat herein.
Table 1 be to composite metallic material prepared by embodiment 1-17 directly under normal temperature conditions (such as 16-27 DEG C, with 25
For DEG C) repeatedly tested, or (200 DEG C and 340 DEG C) are pressed with flexible insulating basement membrane at different temperatures respectively
Afterwards, then under normal temperature conditions the test result repeatedly tested, between the carrier layer 1 measured and the barrier layer 2
Peel strength between peel strength and the peeling layer 3 and the metal foil layer 4.
Table 1
Since a degree of phase counterdiffusion can occur under the high temperature conditions for the carrier layer 1 and the metal foil layer 4, from
And cause the carrier layer 1 that a degree of bonding occurs with the metal foil layer 4, and therefore, the carrier layer 1 and the barrier
Layer 2 between peel strength and the peeling layer 3 and the metal foil layer 4 between peel strength as the temperature rises and
Increase, still, as can be seen from Table 1, the composite metallic material prepared by embodiment 1-17 regardless of under room temperature or hot conditions,
Hundred lattice test grade between the carrier layer 1 and the barrier layer 2 is all in preceding three-level, i.e., the described carrier layer 1 and the barrier
Adhesive force between layer 2 is bigger, and the peel strength between the peeling layer 3 and the metal foil layer 4 is very small, therefore makes
It obtains the peel strength between the carrier layer 1 and the barrier layer 2 and is far longer than the peeling layer 3 and the metal foil layer always
Peel strength between 4 therefore, can be easily by the carrier layer 1, the barrier when using the composite metallic material
Layer 2 and the peeling layer 3 are removed from the metal foil layer 4 simultaneously.And the composite metallic material of comparative example 1-3 preparation is in high temperature item
The mutual spread condition occurred under part causes the carrier layer 1 to occur largely with the metal foil layer 4 than more serious
Bonding be not easy to so as to cause when using the composite metallic material by the carrier layer 1, the barrier layer 2 and the stripping
Absciss layer 3 is removed from the metal foil layer 4 simultaneously.
To sum up, a kind of composite metallic material provided by the embodiment of the utility model and preparation method thereof, wherein composite metallic material
Including carrier layer 1, barrier layer 2, peeling layer 3 and the metal foil layer 4 being cascading, barrier layer 2 includes the gold being stacked
Belong to adhesive layer 22 and high-temperature-resistant layer 21, metal bonding coating 22 is set between carrier layer 1 and high-temperature-resistant layer 21, by carrier layer 1
Peeling layer 3 is set between metal foil layer 4, in order to remove carrier layer 1, and by setting between carrier layer 1 and metal foil layer 4
Set barrier layer 2, to avoid carrier layer 1, phase counterdiffusion causes to bond at high temperature with metal foil layer 4 so that carrier layer 1 with
Metal foil layer 4 is easily peeled off；In addition, by the way that metal bonding coating 22 is arranged between carrier layer 1 and high-temperature-resistant layer 21, so that resistance
Interlayer 2 is not easy to separate with carrier layer 1, to prevent peeling-off between barrier layer 2 and carrier layer 1.
The above is only the preferred embodiment of the utility model, it is noted that for the common skill of the art
For art personnel, without deviating from the technical principle of the utility model, several improvement and replacement can also be made, these change
It also should be regarded as the protection scope of the utility model into replacement.
Claims (16)
1. a kind of composite metallic material, which is characterized in that including carrier layer, barrier layer, peeling layer and metal foil layer；
The carrier layer, the barrier layer, the peeling layer and the metal foil layer are cascading, and the barrier layer includes
The metal bonding coating and high-temperature-resistant layer being stacked, the metal bonding coating be set to the carrier layer and the high-temperature-resistant layer it
Between.
2. composite metallic material as described in claim 1, which is characterized in that at a temperature of 20-400 DEG C, the carrier layer and institute
State the peel strength that the peel strength between barrier layer is greater than between the peeling layer and the metal foil layer.
3. composite metallic material as claimed in claim 2, which is characterized in that hundred lattice between the carrier layer and the barrier layer
Testing grade is 0 or 1 or 2, and the peel strength between the peeling layer and the metal foil layer is 0.001-2N/cm.
4. composite metallic material as described in claim 1, which is characterized in that the stripping between the peeling layer and the metal foil layer
It is greater than or equal to the peel strength between the peeling layer and the barrier layer from intensity.
5. composite metallic material as described in claim 1, which is characterized in that the high-temperature-resistant layer is organic high temperature-resistant layer, alternatively,
The high-temperature-resistant layer is made of any one material in tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite.
6. composite metallic material as described in claim 1, which is characterized in that the high-temperature-resistant layer is single layer alloy structure；Or, institute
Stating high-temperature-resistant layer is multilayered structure or alloy-layer that single material layer is constituted and the multilayered structure that single material layer is constituted, wherein described
Single material layer is made of same chemical element.
7. composite metallic material as described in claim 1, which is characterized in that the metal bonding coating is by any in the first metalloid
A kind of material is made；Alternatively, the metal bonding coating is made of any one material in the second metalloid；Wherein, described first
Metalloid is the metal for being easy to bond with the carrier layer, and second metalloid is the gold for being easy to bond with the high-temperature-resistant layer
Belong to.
8. composite metallic material as claimed in claim 7, which is characterized in that first metalloid be copper or zinc, described second
Metalloid is nickel or iron or manganese.
9. composite metallic material as described in claim 1, which is characterized in that the metal bonding coating is the first metalloid and second
Single layer alloy structure made of metalloid；Wherein, first metalloid is the metal for being easy to bond with the carrier layer, described
Second metalloid is the metal for being easy to bond with the high-temperature-resistant layer.
10. composite metallic material as described in claim 1, which is characterized in that the metal bonding coating includes by the first metalloid
The single metal layer for being made and being connect with the carrier layer, the metal bonding coating further include be made of the second metalloid and with it is described
The single metal layer of high-temperature-resistant layer connection；Wherein, first metalloid is the metal for being easy to bond with the carrier layer, described the
Two metalloids are the metal for being easy to bond with the high-temperature-resistant layer.
11. composite metallic material as described in claim 1, which is characterized in that the metal bonding coating includes alloy-layer and Dan Jin
Belong to the multilayered structure that layer is constituted；Wherein, the alloy-layer of the metal bonding coating is made of the first metalloid and the second metalloid, institute
The single metal layer for stating metal bonding coating is made of the first metalloid or the second metalloid；Wherein, first metalloid is to be easy to
With the metal of carrier layer bonding, second metalloid is the metal for being easy to bond with the high-temperature-resistant layer.
12. such as the described in any item composite metallic materials of claim 1-11, which is characterized in that the peeling layer by nickel, silicon, molybdenum,
Any one material in graphite, titanium and niobium is made；Or, the peeling layer is made of high-molecular organic material.
13. such as the described in any item composite metallic materials of claim 1-11, which is characterized in that the thickness of the metal foil layer is less than
Or it is equal to 9 μm.
14. such as the described in any item composite metallic materials of claim 1-11, which is characterized in that the metal foil layer is copper foil or aluminium
Foil；And/or the carrier layer is carrier copper or carrier aluminum or organic film.
15. such as the described in any item composite metallic materials of claim 1-11, which is characterized in that the carrier layer is close to the metal
The roughness Rz of the one side of layers of foil is less than or equal to 5 μm；And/or one side of the metal foil layer far from the carrier layer
Roughness Rz is less than or equal to 3.0 μm.
16. such as the described in any item composite metallic materials of claim 1-11, which is characterized in that the carrier layer is close to the barrier
The side of layer is equipped with the first antioxidation coating；And/or the metal foil layer is equipped with second far from the side of the barrier layer and prevents
Oxide layer.
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| CN113036086A (en) * | 2019-12-24 | 2021-06-25 | 广州方邦电子股份有限公司 | Preparation method of battery pole piece, battery pole piece and lithium battery |
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