CN105619931B

CN105619931B - A kind of laminated metal Cu/Mo/Cu coiled strip and continuous process

Info

Publication number: CN105619931B
Application number: CN201511003030.9A
Authority: CN
Inventors: 胡传凯
Original assignee: Chongqing Jin Rong Pioneer Metals Corp
Current assignee: Chongqing Jin Rong Pioneer Metals Corporation
Priority date: 2015-12-28
Filing date: 2015-12-28
Publication date: 2019-08-02
Anticipated expiration: 2035-12-28
Also published as: CN105619931A

Abstract

The invention discloses a kind of laminated metal Cu/Mo/Cu coiled strip and continuous process, including the cleaning of surface clean, method hot rolling, surface of semi-finished, semi-finished product rolling, continuous bright annealing, 8 finished product rolling, finishing and slitting steps.Tens of rice or even hundred meters can achieve using the laminated metal the Cu/Mo/Cu coiled strip finished product length that this method manufactures; be conducive to improve production efficiency, reduce production cost, guarantees product quality consistency; it is suitble to scale continuous production, there is preferable production application value.

Description

A kind of laminated metal Cu/Mo/Cu coiled strip and continuous process

Technical field

The invention patent relates to laminated metal coiled strip manufacture fields, and in particular to a kind of high thermal conductivity, low-expansion coefficient The laminated metal CMC coiled strip and continuous process.

Background technique

The laminated metal Cu/Mo/Cu (CMC) is a kind of novel high thermal conductivity, low-expansion electronic package material, is had excellent Good heating conduction and adjustable thermal expansion coefficient, be domestic and international high-power electronic component first choice electronic package material and Heat sink heat sink material is widely used in microwave, communication, radio frequency, aerospace, power electronics, high power semiconductor lasers, medical treatment Etc. industries.For example, the BGA package of prevalence just largely uses the material as substrate in the world now.In addition, in microwave packaging and Radio frequency package field is also largely done using the material heat sink.In Military Electronic Equipment, it is usually adopted to high reliability circuit The basis material of plate.

CMC and the laminated metal novel C u/MoCu/Cu are also key mating necessary to many high-tech areas in China Material, the basis of high-end electronic product development and production, for example, modern microwave communication emitter, power electronic devices, height The products such as performance integrated circuit.

Compared to traditional tungsten copper (WuCu), molybdenum copper (MoCu) metallic composite, the laminated metal copper-molybdenum copper (Cu/Mo/Cu) Thermal conductivity is higher, and copper/molybdenum copper/copper laminated metal (Cu/MoCu/Cu) is led because of copper net distribution in molybdenum in molybdenum-copper Heating rate is higher.

Common preparation method, which has, welds compound, composite electroplated, Explosion composite etc., such as publication number CN1843691A and CN1850436A, publication date are on October 11st, 2006 and on October 25th, 2006, and the engagement of plate copper cladding plate shape molybdenum forms compound Plate is unable to continuous production, needs by annealing, rolling repeatedly, and technique is cumbersome, and discontinuous large-scale production, production efficiency is low, Quality conformance is not easy to control.

A kind of patent of invention " preparation method of copper-molybdenum copper laminar composite material " of Zhu Yubin et al., publication number CN102527747.A, cleans the surface of copper sheet and molybdenum plate, and size is cut into onesize, alternately superposition load briquetting, and layered laminate pushes away Enter in hydrogen furnace, keep the temperature (60-100) minute, complete three metal diffusion bondings, production efficiency is low, is not suitable for large-scale production.

The patent of invention " manufacturing method of copper-molybdenum-copper three layer composite plate " of Wang Zhifa et al., such as publication number: Electrolytic copper plate is placed, heating makes copper sheet fusing and molybdenum plate blank using founding solid-liquid combination principle in molybdenum ingot two sides by CN1408485 Solid-liquid combination, then hot rolling, anneal, be rolled down to finished product, the combined process is complicated, and the control of the thickness proportion of molybdenum layer and layers of copper by Limit is unable to satisfy product quality requirement.

A kind of patent of invention " high bond strength high-precision copper-molybdenum-copper laminated composite materials preparation side of Wang Dezhi et al. Method ", application number: 201210433614.X, using the principle of three-layer metal piece stacking diffusion brazing, soldering is combined into composite plate Piece, then rolled thickness reduction, since molybdenum is easier to aoxidize, the bond strength of the technique is not easy to control, and product is also stratiform gold Belong to sheet material, production efficiency is low.

Zhang Jiayu et al. patent of invention " a kind of preparation method of copper-molybdenum copper laminar composite material ", the patent No.: It is complex to obtain composite plate method by Explosion composite twice by CN102371719A, and production process has risk, and cost It is higher, be not suitable for large-scale production.

United States Patent (USP) (US4950554, US4988392, US4957823) prepares copper-molybdenum copper material using welding milling method Material, higher to welding equipment requirement, product realizes that difficulty is larger, is easy to appear local welding loosely defect, while preparation cost Also higher.

Summary of the invention

Present invention aims at for discontinuous existing for existing Cu/Mo/Cu (CMC) laminar composite manufacturing process Property, a kind of simple process is provided, convenient for continuous large-scale production the compound coiled strip in laminated metal used for electronic packaging and it is continuous plus Work method.

The technical solution for the continuous process that the present invention uses to achieve the goals above is as follows: Cu/Mo/Cu layers a kind of The continuous process of shape metal coiled strip, including the cleaning of surface clean, method hot rolling, surface of semi-finished, semi-finished product roll, even Continue bright annealing, 8 finished product rolling, finishing and slitting steps, device therefor all has winding and unreels function in this method.Tool Steps are as follows for body:

(1) surface clean: copper (Cu) winding of 0.1-3.0mm thickness unreels, and on-line continuous deoils, pickling (5-20% Dilute sulfuric acid), polishing (round scouring pad polished silicon wafer), rinse (pure water), batch as web-like；By the molybdenum of 0.1-3.0mm thickness (Mo) winding unreels, and on-line continuous deoils, pickling, polishing (round wire brush wheel), rinses (pure water), batches as web-like.

(2) it method hot rolling: copper winding and molybdenum winding cleaned in step (1), is rolled up according to copper winding, molybdenum winding, copper The upper, middle and lower sequence of band, unreels, respectively enters heating furnace and heat warm area accordingly, under a shielding gas, while entering two rollings Three-layer metal rolling bonding is laminated metal band and batched as web-like by machine；

(3) semi-finished product clean: step (2) laminated metal coiled strip unreels, it is clean through persulfuric acid continuous acid-washing, circle hundred The polishing of cloth polishing piece, pure water rinse, and batch as web-like.

(4) semi-finished product roll: the metal coiled strip after step (3) cleaning unreels, on φ 170*250 two-roller mill Calendering, extends along its length, spreads in the width direction negligible, and deflection 10-30% batches as web-like.

(5) continuous bright annealing: the laminated metal coiled strip after step (4) rolling unreels, by continuous bright annealing Furnace is made annealing treatment under a shielding gas, is batched as web-like.

(6) finished product rolls: through step (5) treated laminated metal coiled strip, unreeling, in tetra- rolling of φ 90/260*300 Roll on machine, extend along its length, spread in the width direction negligible, deflection 3-30% batches as web-like.

(7) finishing: the laminated metal coiled strip rolled using multiple roll evener to step (6) is unreeled, leveling, winding, instead This process is repeated again, until laminated metal band leveling.

(8) slitting: unreeling, and cuts extra edge, batches as web-like, obtains the Cu/Mo/Cu for meeting thickness ratio requirement Laminated metal coiled strip.

In a specific embodiment of the present invention, the copper winding is pure copper material, and molybdenum winding is selected from pure molybdenum or molybdenum-copper Material.Molybdenum-copper is Mo₇₀Cu、Mo₆₀Cu or Mo₅₀Cu。

Specifically, step (2) is described enters heating furnace specifically: copper winding enters 600-900 DEG C of heating warm area, molybdenum winding Into 800-1200 DEG C of heating warm area, when as identical with molybdenum winding heating temperature such as copper winding, into same heating warm area, in 3- 20m³Under the protection of/h ammonolysis craft gas or hydrogen, while entering 45-150 tons of two-roller mills, deflection 30-70%, with 1- Three-layer metal rolling bonding is laminated metal band and batched as web-like by 10m/min mill speed.

Further, it is made annealing treatment described in step (5) are as follows: 600-900 DEG C of furnace temperature of annealing is passed through 5-10m³/ h ammonolysis craft Gas or hydrogen shield, tape running speed 3-10m/min.

Use the laminated metal Cu/Mo/Cu coiled strip intermediate core layer made from above method for pure Mo or MoCu alloy (such as Mo₇₀Cu、Mo₆₀Cu、Mo₅₀Cu etc.), top and bottom are pure Cu layers, and upper layer and lower layer copper layer thickness difference is less than 0.03mm.The Cu/ The Cu:Mo:Cu thickness degree proportion of the laminated metal Mo/Cu coiled strip is 1:1:1~1:6:1.

Compared to traditional tungsten copper (WuCu), molybdenum copper (MoCu) metallic composite, the laminated metal copper-molybdenum copper (Cu/Mo/Cu) Thermal conductivity is higher, and copper/molybdenum copper/laminated metal copper (Cu/MoCu/Cu) is led because of copper net distribution in molybdenum in molybdenum-copper Heating rate is higher.

Mo or MoCu layers has a lower thermal expansion coefficient, and Cu layer have preferable thermal conductivity, good electric conductivity and lower The excellent performance such as contact resistance, the expansion system of Cu/Mo/Cu or Cu/MoCu/Cu lamellar composite coiled strip and thermal conductivity can be with It is adjusted according to the threeply degree ratio of design.Usual thickness ratio 1:1:1,1:2:1,1:3:1,1:4:1,13:74:13.

Raw material Cu winding, Mo or MoCu winding, Cu winding itself have certain length, and by rolling reductions, thickness is thinned, Under the action of batching power, coiled strip alongst extends, and spreading in the width direction is smaller.So Cu winding, Mo or After MoCu winding, Cu winding are combined by continuously hot rolling, finished product length can achieve the three-layer metal of tens of rice or even hundred meters Compound coiled strip.

Product prepared according to the methods of the invention is conducive to improve production efficiency, reduces production cost, guarantees product quality Consistency is suitble to scale continuous production, and the blank of such long ribbon shape material can not be provided by compensating for the country, has preferable raw Produce application value.

Detailed description of the invention

Fig. 1 is manufacturing process flow diagram of the invention；

Fig. 2 is surface clean schematic diagram；

Fig. 3 is method hot rolling schematic diagram；

Fig. 4 is that surface of semi-finished cleans schematic diagram；

Fig. 5 is that semi-finished product roll schematic diagram；

Fig. 6 is continuous bright annealing schematic diagram；

Fig. 7 is that finished product rolls schematic diagram；

Fig. 8 is finishing schematic diagram；

Fig. 9 is slitting schematic diagram.

Specific embodiment

Device therefor all has winding and unreels function in following instance.Flow chart of the invention is referring to Fig. 1, in embodiment Each step schematic diagram arrive Fig. 9 referring to fig. 2.

Embodiment 1

1, surface clean: copper (Cu) winding of 1.0mm thickness is unreeled in the equipment with retractable volume function, online It continuously deoils, 10% dilute sulfuric acid pickling, round scouring pad polished silicon wafer polishing, pure water flushing；The molybdenum (Mo) of 1.8mm thickness is rolled up Band unreels in the equipment with retractable volume function, on-line continuous deoils, 20% acid solution pickling, the polishing of round wire brush wheel, Pure water rinses.

2, it method hot rolling: (Cu, Mo, Cu) three metal coiled strip after cleaning, unreels, respectively enters the corresponding of heating furnace Heating warm area, Cu enters 750 DEG C of heating warm areas, and Mo is into 950 DEG C of heating warm areas, in 10m³/ h ammonolysis craft gas or hydrogen Under protection, while entering 100 tons of milling trains, deflection 33% is rolled down to thickness 2.0mm, completes three gold medals with 8m/min mill speed Belong to rolling bonding to be laminated metal band and batch as web-like.

3, semi-finished product clean: laminated metal coiled strip unreels, by 10% sulfuric acid continuous acid-washing, round scouring pad polishing Piece polishing, pure water rinse, and batch as web-like.

4, semi-finished product roll: laminated metal coiled strip unreels, and extends along its length on φ 170*250 two-roller mill, Spread in the width direction negligible, thickness 1.6mm is arrived in calendering, and deflection 20% batches as web-like.

5, continuous bright annealing: laminated metal coiled strip unreels, and by 700 DEG C of continuous bright annealing furnace, is passed through 6m³/h Ammonolysis craft gas or hydrogen shield, tape running speed 3m/min batch as web-like.

6, finished product rolls: laminated metal coiled strip unreels, and 1.52mm is arrived in calendering on φ 90/260*300 four-high mill, Deflection 5% batches as web-like.

7, finishing: the multiple roll evener of 7 rollers leveling repeatedly.

8, slitting: cutting extra edge, obtains Cu/Mo/Cu (CMC) coiled strip of 1:3:1 ratio requirement.

Embodiment 2

1, surface clean: copper (Cu) winding of 0.7mm thickness unreels, in the equipment with retractable volume function, continuously It deoils, 15% dilute sulfuric acid pickling, round scouring pad polished silicon wafer polishing, pure water flushing；By the molybdenum (Mo of 1.0mm thickness₇₀Cu it) rolls up Band unreels, in the equipment with retractable volume function, continuously deoil, 20% acid solution pickling, round wire brush wheel polishing, it is pure Water rinses.

2, method hot rolling: (Cu, Mo of cleaning₇₀Cu, Cu) three metal coiled strips unreel, respectively enter the corresponding of heating furnace Heating warm area, Cu enter 700 DEG C of heating warm areas, Mo₇₀Cu enters 900 DEG C of heating warm areas, in 10m³/ h ammonolysis craft gas or hydrogen Under the protection of gas, while entering 100 tons of milling trains, deflection 42% is rolled down to thickness 1.4mm, with the completion of 8m/min mill speed Three metal rolled be combined into laminated metal band and batch as web-like.

3, semi-finished product clean: laminated metal coiled strip unreels, by 10% dilute sulfuric acid pickling, round scouring pad polished silicon wafer Polishing, pure water rinse, and batch as web-like.

4, semi-finished product roll: laminated metal coiled strip unreels, extends along its length on two-roller mill, along width side Negligible to spreading, thickness 1.15mm is arrived in calendering, and deflection 17.0% batches as web-like.

6, finished product rolls: laminated metal coiled strip unreels, and 1.02mm is arrived in calendering on φ 90/260*300 four-high mill, Deflection 11% batches as web-like.

7, finishing: the multiple roll evener of 9 rollers leveling repeatedly.

8, slitting: cutting extra edge, obtains the Cu/Mo of 1:2:1 ratio requirement₇₀Cu/Cu coiled strip.

Embodiment 3

1, surface clean: copper (Cu) winding of 0.1mm thickness unreels, in the equipment with retractable volume function, continuously It deoils, 15% dilute sulfuric acid pickling, round scouring pad polished silicon wafer polishing, pure water flushing；By the molybdenum (Mo of 0.4mm thickness₆₀Cu it) rolls up Band unreels, in the equipment with retractable volume function, continuously deoil, 20% acid solution pickling, round wire brush wheel polishing, it is pure Water rinses.

2, method hot rolling: (Cu, Mo of cleaning₆₀Cu, Cu) three metal coiled strips unreel, respectively enter the corresponding of heating furnace Heating warm area, Cu enter 600 DEG C of heating warm areas, Mo₆₀Cu enters 800 DEG C of heating warm areas, in 3m³/ h ammonolysis craft gas or hydrogen Protection under, while entering 45 tons of milling trains, deflection 30% is rolled down to thickness 0.4mm, with 10m/min mill speed, completes three It is metal rolled to be combined into laminated metal band and batch as web-like.

3, semi-finished product clean: laminated metal coiled strip unreels, by 15% dilute sulfuric acid pickling, round scouring pad polished silicon wafer Polishing, pure water rinse, and batch as web-like.

4, semi-finished product roll: laminated metal coiled strip unreels, extends along its length on two-roller mill, along width side It is negligible to spreading, it is rolled down to thickness 0.36mm, deflection 10% batches as web-like.

5, continuous bright annealing: laminated metal coiled strip unreels, and by 600 DEG C of continuous bright annealing furnace, is passed through 5m³/h Ammonolysis craft gas or hydrogen shield, tape running speed 10m/min batch as web-like.

6, finished product rolls: laminated metal coiled strip unreels, and rolls on φ 90/260*300 four-high mill, is rolled down to thickness 0.35mm is spent, deflection 3% batches as web-like.

7, finishing: the multiple roll evener of 19 rollers leveling repeatedly.

8, slitting: cutting extra edge, obtains Cu/Mo₆₀Cu/Cu coiled strip.

Embodiment 4

1, it surface clean: by copper (Cu) winding of 3mm thickness, unreels, in the equipment with retractable volume function, continuously goes Oil, 20% dilute sulfuric acid pickling, round scouring pad polished silicon wafer polishing, pure water rinse；By the molybdenum (Mo of 2mm thickness₅₀Cu) winding is put Volume continuously deoils, 20% acid solution pickling, the polishing of round wire brush wheel, pure water punching in the equipment with retractable volume function It washes.

2, method hot rolling: (Cu, Mo of cleaning₅₀Cu, Cu) three metal coiled strips unreel, respectively enter the corresponding of heating furnace Heating warm area, Cu enter 900 DEG C of heating warm areas, Mo₅₀Cu enters 1200 DEG C of heating warm areas, in 20m³/ h ammonolysis craft gas or hydrogen Under the protection of gas, while entering 150 tons of milling trains, deflection 30% is rolled down to thickness 5.6mm, with the completion of 1m/min mill speed Three metal rolled be combined into laminated metal band and batch as web-like.

3, semi-finished product clean: laminated metal coiled strip unreels, by 20% dilute sulfuric acid pickling, round scouring pad polished silicon wafer Polishing, pure water rinse, and batch as web-like.

4, semi-finished product roll: laminated metal coiled strip unreels, extends along its length on two-roller mill, along width side It is negligible to spreading, it is rolled down to thickness 3.9mm, deflection 30% batches as web-like.

5, continuous bright annealing: laminated metal coiled strip unreels, and by 600 DEG C of continuous bright annealing furnace, is passed through 5m³/h Ammonolysis craft gas or hydrogen shield, tape running speed 3m/min batch as web-like.

6, finished product rolls: laminated metal coiled strip unreels, and rolls on φ 90/260*300 four-high mill, is rolled down to thickness 3.2mm deflection 20% is spent, is batched as web-like.

7, finishing: the multiple roll evener of 7 rollers leveling repeatedly.

8, slitting: cutting extra edge, obtains the Cu/Mo of 1:1:1₅₀Cu/Cu coiled strip.

Claims

1. a kind of continuous process of laminated metal Cu/Mo/Cu coiled strip, it is characterised in that: multiple including surface clean, hot rolling Conjunction, surface of semi-finished cleaning, semi-finished product rolling, continuous bright annealing, 8 finished product rolling, finishing and slitting steps, specific steps It is as follows:

(1) surface clean: by copper winding on having winding and the equipment for unreeling function, unreeling, on-line continuous deoils, pickling, Polishing is rinsed, and is batched as web-like；By molybdenum winding on there is winding and the equipment for unreeling function, unreel, on-line continuous deoils, Pickling, polishing, flushing are batched as web-like；

(2) method hot rolling: copper winding and molybdenum winding cleaned in step (1), according to copper winding, molybdenum winding, copper winding Upper, middle and lower sequence, unreels, into heating furnace, wherein copper winding enters 600-900 DEG C of heating warm area, and molybdenum winding enters 800-1200 DEG C heating warm area, and molybdenum volume heating temperature at least than copper volume heating temperature it is 200 DEG C high, under a shielding gas, enter simultaneously Three-layer metal rolling bonding is laminated metal band and batched as web-like by two-roller mill, deflection 30-70%；

(3) semi-finished product clean: step (2) laminated metal coiled strip unreeling, throws through persulfuric acid continuous acid-washing, round scouring pad Mating plate polishing, pure water rinse, and batch as web-like；

(4) semi-finished product roll: the laminated metal coiled strip after step (3) cleaning unreels, on φ 170*250 two-roller mill Calendering, deflection 10-30% batch as web-like；

(5) continuous bright annealing: the laminated metal coiled strip after step (4) rolling unreels, by continuous bright annealing furnace, It is made annealing treatment, is batched as web-like under a shielding gas；

(6) finished product rolls: the laminated metal coiled strip after step (5) annealing unreels, in tetra- rolling of φ 90/260*300 Roll on machine, deflection 3-30% batches as web-like；

(7) finishing: using multiple roll evener to step (6) rolled metal coiled strip, unreeling, leveling, winds, is iteratively repeated this Process, until band is smooth；

(8) slitting: unreeling, and cuts extra edge, batches as web-like, obtains the Cu/Mo/Cu stratiform for meeting thickness ratio requirement The upper layer and lower layer copper layer thickness difference of metal coiled strip, the laminated metal Cu/Mo/Cu coiled strip is less than 0.03mm.

2. the continuous process of a kind of laminated metal Cu/Mo/Cu coiled strip according to claim 1, it is characterised in that: institute Stating copper winding is pure copper material, and with a thickness of 0.1-3.0mm, molybdenum winding is selected from pure molybdenum or molybdenum-copper material, with a thickness of 0.1- 3.0mm。

3. the continuous process of a kind of laminated metal Cu/Mo/Cu coiled strip according to claim 2, it is characterised in that: institute Stating molybdenum-copper is Mo₇₀Cu、Mo₆₀Cu or Mo₅₀Cu。

4. special according to claim 1 to a kind of continuous process of any one of 3 laminated metal Cu/Mo/Cu coiled strips Sign is: step (2) is described to enter heating furnace specifically: copper winding enters 600-900 DEG C of heating warm area, and molybdenum winding enters 800- 1200 DEG C of heating warm areas, in 3-20m³Under the protection of/h ammonolysis craft gas or hydrogen, while entering 45-150 tons of two-roller mills, becomes Shape amount is that three-layer metal rolling bonding is laminated metal band and is batched as web-like by 30-70% with 1-10m/min mill speed.

5. special according to claim 1 to a kind of continuous process of any one of 3 laminated metal Cu/Mo/Cu coiled strips Sign is: making annealing treatment described in step (5) are as follows: 600-900 DEG C of furnace temperature of annealing is passed through 5-10m³/ h ammonolysis craft gas or hydrogen Gas shielded, tape running speed 3-10m/min.

6. special according to claim 1 to a kind of continuous process of any one of 3 laminated metal Cu/Mo/Cu coiled strips Sign is: the thickness degree proportion of the laminated metal Cu/Mo/Cu coiled strip is 1:1:1~1:6:1.

7. a kind of laminated metal Cu/Mo/Cu coiled strip, it is characterised in that: the laminated metal Cu/Mo/Cu coiled strip is by weighing Benefit requires 1 to 6 any methods to manufacture.