session 3 - speaker 2 yang xiao(en)€¦ · magnesium alloy:study on corrosion behavior and...

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Mg alloys production and research of Aluminum Corporation of China Limited

Yang Xiao Zhengzhou Light Metals Research Institute

Zhengzhou Light Alloys Technology Co., Ltd.

2017-5

Singapore

Preface

l History According to the former Soviet Union's industrial system in the fifth plan built Fushun aluminum plant (3,000 tons of electrolytic magnesium) and the Northeast light alloy processing plant (magnesium plate, belt, tube, rod, type)；In 1965, the magnesium plate with the workshop into the Luoyang copper processing plant magnesium plate workshop. At the same year, the establishment of Zhengzhou Light Metal Research Institute. The above four units are China's magnesium industry technology, talent, product source and development basis.

l  Development The production and research of Aluminium Corp magnesium alloy mainly involves three subordinate units of Zhengzhou Light Metal Research Institute, China Aluminum Luoyang Copper Limited Company and Northeast Light Alloy Limited Company.

Number Institute Production and Research 侧重⽅方向 Application

1 Zhengzhou Light Metals Research Institute

Ø  Ultra-light Mg-Li alloy Ø  High strength and heat resistant magnesium-rare

earth alloy Ø  MB15（ZK61M）Deformed Magnesium Alloy Ø  No flux smelting process

Tube, rod, profile

Aerospace National Defense

2 Luoyang Copper Co., Ltd

Ø  AZ31、ZK60and Rare-earth magnesium alloy (ME20) and so on

Ø  Double Roller Continuous Casting Process Plate National Defense

3 Northeast Light Alloy Co., Ltd

Ø  Magnesium alloy products(MB2、MB8、MB15) Ø  Magnesium alloy R & D (fire, high strength, high

damping, high thermal conductivity)

Study on Ultra - light Mg - Li Alloy Basis

Aerospace

Contents

Zhengzhou Light Metal Research Institute

Luoyang Copper Limited Company

Northeast Light Alloy Limited Company

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Luoyang Copper Limited Company

Northeast Light Alloy Limited Company

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1.Zhengzhou Light Metal Research Institute

Zhengzhou Light Metal Research Institute is the unique large-scale research institutes in China's light metal field. It is a research center of CHALCO, making a great contribution to the rapid development of China's aluminum and magnesium industry. Its research and development of silicon thermal reduction magnesium method ensure China primacy for decades.

l  China's light metal professional field only large-scale scientific research institutions

l  China Light Metal Academic Committee Secretary - General unit l  International Magnesium Standards Association (IMA) Secretary

General l  National Light Metal Quality Supervision and Inspection Center l  National Aluminum Smelting Engineering Technology Research

Center l  China Aluminum Industry Co., Ltd. Postdoctoral Research Station l  International Organization for Standardization (ISO) in China technical

standards focal point l  Non - ferrous metal standard sample of fixed - point development

units

1.Production and Research of Magnesium Alloys of Zhengzhou Light Metal Research Institute


Ultra-light Mg-Li alloy 1

High strength heat resistant magnesium rare earth alloy 2

MB15 (ZK61M) Deformed Magnesium Alloy 3

No flux smelting process 4

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1.1 Ultra-light Mg-Li alloy

Advantages of Mg-Li alloys

l Ultra light, high specific strength, high

specific modulus

l Excellent rigidity

l Conductive, heat conduction

l High damping capacity

l Excellent electromagnetic shielding

performance

l Can be welded, good machining and

cold formability

The same weight of typical metal

Density Decreases Density g/cm

3


Research l  Casting Low vacuum induction smelting and gas protection

smelting

l  Alloying Aluminum, zinc, rare earth elements (including mixed

rare earth, Y, Ce, La, etc.) ,alkali metals (Ca, Sr, etc.) and

Sn, Pb, etc.

l  Deformation Extrusion, Rolling, Forging

l  Heat treatment Annealing, Solid solution, Homogenization

l  Surface treatment Micro-arc oxidation, anodizing, spray

plating

l  Security Flammable and explosive, lithium toxicity protection

1.1Ultra-light Mg-Li alloy

Effect of Cold Rolling and Annealing on Microstructure and Properties of LA91

a. 挤压态 b. ε=60% c. ε=75% d. ε=95% Diff

eren

t col

d ro

lling

de

form

atio

n E

ffect

of D

iffer

ent A

nnea

ling

Tem

pera

ture

on

Mic

rost

ruct

ure

of

Col

d R

olle

d ε=60

%

ε=95

%


ε=75%of cold rolled sheet at different annealing temperatures

（ a）2 0 0℃×1 h a n n e a l i n g（b）2 5 0℃×1 h annealing

（ c）3 0 0℃×1 h a n n e a l i n g（d）3 5 0℃×1 h annealing

Mechanical Properties of LA91 Alloy Plate with Different Cold Rolling Deformation before and after Annealing

a. tensile strength b. Elongation

Stress - Strain Curve of LA91 Alloy Plate with Different Deformation

Effect of Cold Rolling and Annealing on Microstructure and Properties of LA91

1.1 Ultra-light Mg-Li alloy Effect of Heat Treatment on Microstructures and Properties of LA141

Microstructure of LA141 Plate after Rolling and Heat Treatment a-Rolling，b-225℃×2h，c- 175℃×1h The composition of LA141 plate after rolling and heat treatment

Effect of Heat Treatment on Tensile Mechanical Properties of LA141 Plate

1.1 Ultra-light Mg-Li alloy Corrosion and protection Study on Surface Corrosion and Protection of

Magnesium Alloy:Study on Corrosion Behavior and Mechanism of Alloy，Magnesium alloy passivation, anodic oxidation, microarc oxidation, electrophoresis, electroless plating, plasma spraying, painting, magne t ron spu t te r ing and o the r t rea tmen t process.Through the corrosion behavior of the alloy to choose anti-corrosion process, through the salt spray, friction and wear test to test the coating performance, according to the coating failure to adjust the process, and constantly optimize and improve the alloy protective performance.

Cooperative development of corrosion resistant magnesium alloy results in the famous magazine Nature Materials (IF: 38.891) published： A high-specific-strength and corrosion-resistant magnesium alloy, 2015, 14(12).Through the specific composition and thermal processing technology, the alloy from the corrosion potential is significantly shifted to form a self-repair function, similar to the stainless steel Li2CO3 film.

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Grade Density g/cm3

Hardness HB

Tensile Strength

MPa

Yield Strength MPa

Elongation %

LA91 1.45 45-75 180-240 120-190 10-30

LA141 1.35 40-70 160-230 100-170 20-40

LZ91 1.48 45-75 180-240 140-180 15-35

MA21 1.6 50-80 200-260 150-220 6-25

MA18 1.48 45-65 140-210 90-180 10-30

1.1 Ultra-light Mg-Li alloy Production (research and development) of the Mg-Li alloy grades and performance

Including the standard grade alloy and special composition of Mg-Li alloy, its mechanical properties meet or better than the United States or the former Soviet Union production of magnesium alloy.


Serial number Part Name Application areas Customer

category

1 Single combat with communications radar Communication Military

2 UAV parts Aviation Military、Civil 3 Fighter antenna bearing Aviation Military

4 Satellite grating shell Aviation Military、Civil

5 Aeronautical equipment housing parts Aviation Military

6 Waveguide Communication Military 7 Other Transportation、3C Civil

Zhengzhou Light Metal Research Institute produces high-quality large-scale magnesium alloys ingots. The ingots would be forged, extruded or rolled, to produce magnesium alloys forging slabs, bars and sheets or plates. It has developed a variety of Mg-Li alloys parts, including many military and civilian customers, widely used in aerospace, transportation and 3C products.

Typical products and applications

At present, a large size of Mg-Li alloy ingot has been successfully

produced. The diameter of ingot can reach 350mm. In addition, a 200 * 800

mm flat ingot mold is made, and the trial is preparing.

Mg-Li alloy ingot with a diameter of 350mm Mg-Li alloy ingot with a diameter of 240mm

1）Ingot casting


The successful production of Mg-Li alloy sheet and foil, the product size is accurate, good shape, smooth surface, excellent performance, has completed the supply of spare parts for aerospace parts.

Mg-Li alloy rolled sheet Mg-Li alloy rolled foil

Mg-Li alloy（Rolling） Thickness/mm Width/mm Length Plate 0.5~45 ≤1000 ≤2000

Foil 0.05~0.5 ≤300 L

2）Plate (foil)


3）Forging Slab and Bar Mg-Li alloy forged slab

Slab thickness of up to 110mm, width

up to 350mm, length up to 400mm, weight

up to 50kg.

Mg-Li alloy forged bar Forging bar diameter 30 ~ 150mm,

length 1000 ~2000mm, weight up to 30kg.


4）communications radar

Aluminum Alloy

60Kg

Mg-Li Alloy

35Kg �

Weight

41.5% loss

A total of hundreds of parts, all the use of Mg-Li and made of surface corrosion treatment, played a significant weight loss effect.


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5）UAV Parts

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6）Fighter Antenna Bearing

Mg-Li alloy aircraft antenna bearing

A Mg-Li alloy was prepared by vacuum melting furnace and processed to prepare high performance magnesium and lithium alloy material and processed into the base of the fighter antenna.

Original 2024 Aluminum alloy

415g

Mg-Li Alloy 220g

Weight 47% loss


7）Satellite Grating Shell

Satellite grating cover housing parts


8）Aeronautical Equipment Shell Parts

Avionics equipment shell parts (micro-arc oxidation treatment)


9）Waveguide

Mg-Li alloy waveguide


10）Some other Applications

Sound vibration film、Bike frame and Notebook shell


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1.2 High strength and heat resistant magnesium rare earth alloy

Application Temperature /℃

High Temperature Performance and Application of High Strength- Heat resistant- Mg-RE Alloy

Armored vehicle body

Tank load wheel Satellite stent Car body Missile

cabin Car wheels Tank engine cylinder Car engine cylinder

Tensile Strength /MPa

1.2 High strength and heat resistant Mg-RE alloys

(a) casting ingots ；(b) extrusion ingots ；(c) rolling slab ；(d)和(e) extruded rod ； (f) rolling sheet

(e)

(a) (b (c)

(d) (f)

High strength and heat resistant Mg-RE alloy products


Properties of high strength and heat resistant Mg-RE alloy products

Alloys Properties Tensile Temperature/℃


The tensile properties of Mg-Gd-Y-Zr alloy at different temperatures

图 4- 4 Mg-9Gd-4Y-0.6Zr合金挤压 T5态在不同温度下的拉伸性能

Super plasticity of coarse-grain

Low Temperature Super plasticity

Elon

gatio

n /%

Tens

ile st

reng

th

Tensile Temperature/℃

The extrusion temperature of Mg-Gd-Y-Zr alloy decreased from 500℃ to 400℃： Ø  Grain size decreased from 126 µm

to 7.4 µm； Ø  Tensile strength increased from

200MPa to 312MPa， improved 112MPa, an increase of 56%

Ø  Elongation increased from 2.9% to 5.6%

Gain refinement of magnesium alloy has the following characteristics ： ①Effective；② Do not reduce the plasticity of the material ；③ There are many ways to refine grains and easy to implement in production

Mg-Gd-Y-Zr alloy bars fine-grain strengthening

1.2High strength and heat resistant Mg-RE alloys

Progress in study on fine-grain strengthening of Mg-Gd-Y-Zr alloy Extrusion Temperature/℃

Grain Size/um

Vickers Hardness/ HV 98N

dda


Progress in study on precipitation strengthening of Mg-Gd-Y-Zr alloy

lamellar morphology

High strength(UTS:400MPa) Mg

alloys was fabricated in

2004 peak-aging

much precipitated

phases

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1.3 The wrought magnesium alloy of MB15（ZK61M）

MB15（ZK61M）wrought magnesium alloy

Isothermal Forging : Developing a high uniformity of microstructure, high

performance and low anisotropy of MB15 forged magnesium alloy.

Microstructure uniform increased more than 30% ， tensile strength and yield

strength increased more than 30MPa， inclusion and porosity decreased more

than 5%， the property of anisotropy decreased more than 30Mpa。

To improve the microstructure uniformity and explore the potential of mechanical

properties of MB15, we carried out four aspects in the study ：

①MB15 Quality control of casting ingot ；

②MB15 Processing Map ；

③MB15 Finite Element Simulation and Analysis of the forging process ；

④MB15 Isothermal Forging （ In progress ）.

1.4 Fluxless melting

The development of fluxless melting In order to obtain good toughness and improve the fatigue property of

magnesium alloy, it is necessary to reduce the content of metal impurity elements and the amount of nonmetallic inclusions by the appropriate casting process. Impurity elements have a very negative effect on corrosion resistance and toughness of magnesium alloy. Non-metallic inclusions would also reduce the toughness of magnesium alloys .

The biggest problem with the existence of magnesium alloy production in China is that the original magnesium quality is unstable, high content of impurities and the amount of inclusions. Smelting process behind, the use of flux, low level of workers and other reasons caused by the performance of domestic magnesium alloy products are not up to standard.

Zhengzhou Light Metal Research Institute selected the best high-purity magnesium alloy raw materials, as well as military grade low sodium and low potassium high purity lithium ingots. Magnesium-lithium alloy produced by melt-free vacuum casting process is characterized by high plasticity and good corrosion resistance compared with ordinary magnesium alloy.

Content

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1. Luoyang copper Co. Ltd.

Luoyang Copper Co. Ltd. is China's first production of magnesium alloy sheet business and started to produce of magnesium alloy sheet in 1962.It has made great contribution to National Defense and National Economy Equipments:1600mm reversible hot milling roll ，800mm cold rolling mill ， annual production capacity of 500 tons ,cumulative production of 10000 tons . l  The earliest and highest yield enterprises specializing in the production

of magnesium alloy sheet l  National Enterprise Technical Center l  National heavy nonferrous metal testing and testing center

Plate Sheet Strip

2. The magnesium alloys production and research of Luoyang copper Co. Ltd.

Luoyang copper Co., Ltd.

AZ31、ZK60 and ME20 1

Twin-roll casting process 2

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2.1 AZ31、ZK60 and ME20

Products

Type specifications State Standard Application

M2M(MB1) AZ40M(MB2) AZ41M(MB3) ME20M(MB8)

AZ31B、ZK61M

thickness width length

H112

GB/T5153-2003

GB/T5154-2003

Aerospace, aviation,

shipbuilding and other defense

industries; textile, chemical

machinery

8-110 800-1300 1000-3000

Note thickness＞30㎜ or length＞1800㎜

Type specifications State Standard Application

M2M(MB1) AZ40M(MB2) AZ41M(MB3) ME20M(MB8)

AZ31B、ZK61M

Thickness Width Length

H18、H24、O

GB/T5153-2003

GB/T5154-2003

Aerospace, aviation,

shipbuilding and other defense

industries; textile,

chemical machinery

2.0-8.0 800-1200 ≤3500

0.6-1.0 100-250 ≤2000

Note （1）sheet length more than 500㎜

Hot rolling alloy type and specifications

Cold rolling alloy type and specifications

2.1 AZ31、ZK60 and ME20

Properties of products

Type State Thickness /mm

Rm/（N/mm2） Rp0.2/（N/mm2） Elongation /%

not less than A50mm

ZK61M

H112 8.00〜～12.50 285 180 — 7 T5 295 190 4

H112 >12.50〜～20.00

280 200 7 — T5 290 210 4 H112 >20.00〜～

32.00 270 200 6 — T5 285 215 4

H112 >32.00〜～70.00

265 210 6 — T5 280 215 4

ZK61M sheet mechanical properties (RT)

2.2 Twin-roll continuous casting and rolling process

Development Magnesium alloy continuous casting and rolling technology was used as early as 1980 by the United States House Chemical Company Hinte Engineering Compan for the first time, followed by Germany, France, Australia, South Korea, China and other research. The process simplifies the sheet production process, shortening the production cycle, equipment investment is also reduced . l  Luoyang Copper Co. Ltd. used this technology in 2005 and produced 6mm×600mmAZ31B magnesium alloy casting and rolling roll . l  The newly established Luoyang Tongqi Magnesium company continues the experimental

study of the technology. From equipment research and development to process testing, trying to break through the bottleneck of industrial production, after several years of testing, and achieved initial results ， successfully produced specifications for 6.7mm×620mm、6.7mm×1000mmAZ31B、AZ41M magnesium alloy casting and rolling roll, the maximum weight is 500Kg。

l  Luoyang Copper Co. Ltd. and Taiyuan University of Science and Technology to strengthen cooperation in the magnesium casting equipment, intelligent upgrade, the temperature, flow, level, speed and other technical parameters to build "cycle feedback correction, closed-loop program control" the whole process of man-machine dialogue intelligence Control System ，and strive to achieve from the smelting, liquid, liquid level control, release, molding and fault return and other full precise quantitative control, to achieve the copper-copper alloy casting process from qualitative to quantitative, from experience to intellectual control of the change.


Performance comparison of twin-roll continuous casting and rolling and conventional rolling

l  The mechanical properties of

the AZ31B cast sheet are

close to that of the ingot,

which is lower than that of

the hot rolled sheet.

Respectively, using cast

sheet and hot-rolled sheet for

cold-temperature rolling, its

performance has reached the

requirements of GB /

T5154-2010.

l  The use of twin-roll

continuous casting process to

produce AZ31B magnesium

alloy sheet can achieve the

national standard .

Type Thickness /mm State Note

Cast -rolled slab

Semi-continuous ingot casting

Hot -rolled

sheet

Casting and rolling billet

Hot -rolled billet


Twin-roll continuous casting and rolling products

6.7mm×600mm rolled coil 6.7mm×1000mm rolled coil

Production Workshop 6.7mm×1000mm sheet

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3. Northeast Light Alloy Co. Ltd

Northeast Light Alloy Co. Ltd is China's first company to produce wrought magnesium alloy. It cast China's first qualified wrought magnesium alloy ingot in 1958 and then began to produce magnesium alloy sheet . The company ont only provided much-needed magnesium alloy tube, rods, profiles, but also provided the production of small-size squeeze plate, strip for the national defense and military departments in past 50 years.

l  National Enterprise Technology Center l  The National high Technology Enterprise l  National Innovation Enterprise l  National Enterprises and Institutions of Intellectual Property pilot units

3. The production and research of Northeast Light Alloy Co. Ltd

Northeast Light Alloy Co. Ltd

Products(MB2、MB8、MB15) 1

Research(flame-retardant 、 high-strength 、 high- damping 、 high-heat conductivity) 2

3.1 Products of magnesium alloy

Products and Applications

Number Type Type State Application specification

1 Alloy Profiles

MB2（AZ40M） MB8（ME20M）MB15（ZK61M）

R、F aircraft 20

2 Alloy Bar MB2（AZ40M） MB8（ME20M）MB15（ZK61M）

R aircraft （ forging stock） Ф60～300mm

3 Alloy Forgings

MB2（AZ40M）MB15（ZK61M） R、F engine

die forging : 5 open die

forging:20

Northeast Light Alloy Co. Ltd products

In addition, Northeast Light Alloy Co. Ltd also carried out a

small amount of magnesium alloy ingot production and trial

production. The company adopted advanced the semi-continuous

casting method and successfully prepared ultra-high toughness Mg-

Gd-Y-Zn-Zr alloy ingot(diameter of 500mm) .It is the largest size of

rare earth magnesium alloy ingots in the recent roports at home and

abroad.

3.2 Research of magnesium alloy

Research and development of magnesium alloy for traffic

2、Development of magnesium alloys for traffic u  Low cost and ultra high strength flame retardant magnesium alloy u  Low cost and can be high-speed forming high toughness wrought magnesium alloy u  Low cost and high damping high strength magnesium alloy

u  Low cost and high thermal conductivity easy to form magnesium alloy

1、Significance l  The use of new materials with higher strength and lower weight is the

constant pursuit of rail transit design . l  Heavy weight loss of rail transport not only lead to higher performance,

but also reduce the energy consumption of vehicle operation . l  Now a large number of aluminum alloy body has reached a limit,

lightweight high strength magnesium alloy in the field of high speed rail vehicle has a wide range of applications.


A. Low cost and ultra high strength flame retardant magnesium alloy

Alloy condition YS (MPa)

UTS (MPa)

ε (%)

Mg-Al-Ca-1 As-extruded 423 440 4.6

Mg-Al-Ca-2 As-extruded 350 350 15

Mg-Zn-Ca As-extruded 325 340 16

Tensile properties at room temperature

Aiming at the civil transportation tools, the company developed a low-cost ultra-high strength flame retardant and corrosion resistant magnesium alloy without rare earth .Its yield strength is similar to that of ultra - high strength rare earth magnesium alloy with a large amount of expensive rare earth. It has a wide range of application prospect in the rail transport.

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B. High damping and high strength magnesium alloy

Alloys condition Testing T YS

(MPa) UTS

(MPa) ε (%) Q-1

Mg-Cu-Mn-X As-extruded RT 220 250 13 > 0.01

Mg-Si-Sr-X As-extruded RT 250 320 8 > 0.01

Mg-Zn-Ca-X As-extruded RT 270 340 9 > 0.01

Mg-Mn-X As-extruded RT 200 280 20 > 0.01

Based on the deep research on the damping mechanism of magnesium

alloy, different series of high damping high strength magnesium alloys were

developed. Tensile and damping properties of

high damping and high strength magnesium alloy at room temperature


C. New type of high thermal conductivity of magnesium alloys u Suitable for die - casting of high thermal conductivity and high strength magnesium alloy u Good die-casting performance (Comparable to AZ91) ）

l thermal conductivity （>100W/mk) l strength (Better than AZ91 ） l low cost

u  Easy forming of high conductivity high - strength magnesium alloys

l High-speed extrusion, low temperature extrusion, stamping l thermal conductivity （>125W/mk) l strength （ Comparable to ZK60) l Corrosion resistance l low cost

u Mg-Zn-X u Mg-Al-X u Mg-La-X

u Mg-Zn-X u Mg-Al-X

Thanks！

Zhengzhou Light Metals Research Institute Zhengzhou Light Alloys Technology Co., Ltd.

Website: http://almgcu.com Contact : Yang Xiao E-mail : [email protected] Tel : 13783670172

session 3 - speaker 2 yang xiao(en)€¦ · magnesium alloy:study on corrosion behavior and...

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