CF_Industry_Overview_20090225碳纤维发展综述

A Brief History of the Composites Industry

The first known FRP (Fiber Reinforced Composites) product was a boat hull manufactured in the mid 1930s. FRP composites applications have revolutionized the aerospace, sporting goods, marine, electrical, corrosion-resistance, and transportation industries. FRP composite materials date back to the early 1940s in the defense industry, particularly for use in aerospace and naval applications. The U.S. Air Force and Navy capitalized on FRP composites’ high strength-to-weight ratio and inherent resistance to weather and the corrosive effects of salt air and sea. The rapid development and use of composite materials beginning in the 1940s had three main driving forces.

https://www.360docs.net/doc/7b911277.html,itary vehicles, such as airplanes, helicopters, and rockets, placed a premium on high-

strength, lightweight materials.

2.The emergence of new, lightweight polymers offered solutions for a variety of uses,

provided something could be done to increase the mechanical properties of plastics.

3.The extremely high theoretical strength of certain materials, such as glass fibers, was

being discovered to solve the problems posed by the military's demands.

By 1945, over 7 million pounds of fiberglass were being used in military applications. The benefits of FRP composites, especially their corrosion resistance capabilities, were communicated to the public sector. Fiberglass pipe was first introduced in 1948, its widest areas of use being within the corrosion market and the oil industry. FRP composites proved to be a worthy alternative to other traditional materials even in the high-pressure, large diameter situations of chemical processing. The 1950s brought new revolutionary applications for FRP composites. The same technology that produced the reinforced plastic for the Manhattan Project in World War II spawned the development of high performance composite materials carbon fiber for solid rocket motor cases and tanks in 1960s and 1970s. Now, high-performance race cars are the proving ground for technology transfer to passenger vehicles. High performance composite materials have been demonstrated in advanced technology aircraft such as the F-117, F-18, V22 and F35 Stealth Fighters, and the B-2 Bomber. Currently, FRP composites are being used for space applications and are involved in several NASA test initiatives

There were three principal driving forces that led to the interest and investment in composite materials in the United States in the mid-1950s and 1960s.

1.The demand for lower weight and higher rigidity for aerospace structures, electronics,

sports equipment, and other applications;

2.the solid-state theory's predictions of extremely high potential crystal strengths, more

than 1 million psi tensile strengths, and elastic moduli of more than 100 million psi; and

3.the flourishing U.S. economy.

From the late 1960s to late 1970s, cyclical global recessions and the oil crisis slowed the growth of the composites industry. Many businesses collapsed during this period and many raw material producers either withdrew from the market or consolidated their business. Nowadays the composites industry has settled into a mature phase as new market sectors for composites continue to appear, such as sporting goods, wind turbine blades, and the automotive industry. These emerging applications demand the development of materials and manufacturing processes

with low cost, high throughput, and high consistency. As these applications continue to mature, composites are being transformed from exotic materials into commonly used industrial materials. Therefore, the next 50 years could be even more eventful than the last 50 years for the composites industry.

A Brief History of the Carbon Fiber Industry

The earliest known commercial use of carbon fibers was the carbonization of cotton and bamboo fibers for incandescent lamp filaments in the late 1800s. Practical commercial uses of carbon fibers for reinforcement began in the 1960s. Union Carbide Corporation during World War II investigated the carbonization of rayon and PAN (polyacrylonitrile). In 1959 and 1962, two processes for manufacturing high strength and high modulus carbon fibers from rayon and PAN precursor fibers were invented simultaneously. In 1963, high modulus carbon fibers made from pitch were invented. The following precursor materials were considered for producing carbon fibers: rayon, PAN, pitch, polyesters, polyamides, polyvinyl alcohol, polyvinylidene, poly-p-phenylene, and phenolic resins. Of these materials, rayon, PAN and pitch have been found to offer the greatest mechanical properties.

Early carbon fibers were made from rayon. Today more than 90% of the commercially marketed carbon fibers are made from PAN. PAN-based carbon fibers possess higher strength-modulus and failure strain with high yield compared to fibers made from pitch or rayon. Rayon-based carbon fibers have very low yield (10%-30% depending on the precursor) and are difficult to process compared to PAN-based carbon fibers. Today no carbon fiber is produced in the United States from rayon. Pitch-based carbon fibers provide properties not readily obtained with PAN-based fibers such as higher modulus, and good thermal and electrical properties. Pitch-based carbon fiber is used in specialty applications. The current technologies for producing carbon fiber use the thermal decomposition of precursor fiber materials.

The successful commercial production of carbon fiber started in 1960 with the aerospace and defense industries’ requirements of high performances of high stiffness and strength for lightweight materials. After years of boom-and-bust cycles, the global carbon fiber industry has recently experienced a significant resurgence due to increasing demand for the technology in a wide range of applications. This resurgence is driven largely by demand for carbon fiber and advanced composite materials from the industrial, aerospace, sporting goods, and, increasingly, wind energy industries. The competitors in the marketplace continue to maneuver strategically to take advantage of the current supply constraints and establish long-term relationships with selected customers, often at pre-set prices.

The market for carbon fiber has experienced excellent growth in recent years. The growth rate for the last 23 years averaged about 12%. The global carbon fiber industry is slated to grow to $0.9 billion by the year 2010, with the market for finished carbon fiber reinforced composites parts set to grow to $9.9 billion in the same period. The rapid increase in demand for carbon fiber for new applications (wind energy and industrial applications) and the shortage of PAN precursor fiber supply created significant price increases recently. The composite materials industry requires large, capital-intensive equipment with long product development and qualification cycles. The world's carbon fiber producers are attempting to forecast demand

through 2014 and beyond. They are increasing production capacities by simultaneously considering the addition and geographic placement of new production facilities.

Prior to 1991, the carbon fiber industry was driven by the Department of Defense and defense industries. These high performance carbon fibers are produced in small tows ranging from 1,000 (1K) filaments to 12,000 (12K) filaments per tow. After the end of the cold war and with the collapse of the USSR, the demand for carbon fiber dropped sharply and the carbon fiber industry experienced its share of consolidation and restructuring through various acquisitions, similar to contractions in the defense industries. Cytec purchased Amoco’s carbon fiber business that was purchased from BASF’s manufacturing plant and equipment in Rock Hill, South Carolina, in 1993. Hexcel acquired Hercules PAN and carbon fiber business in Decatur, Alabama, and Salt Lake City, Utah, in 1993. Zoltek bought equipment from Stackpole, Courtaulds, and Cydeca, Mexico. RK Carbon was sold to Sigri Great Lakes Carbon (SGL). The impacts of the drop in demand for carbon fiber in 1995 through 2000 were:

1.all carbon fiber producers were operating below their capacity (less than 60%);

2.the price of carbon fiber was reduced;

3.dependence on defense and aerospace markets was reduced; and

4.the market for carbon fiber expanded into commercial aerospace, industrial, sporting

equipment, energy and automotive applications.

By 2002, this resulted in increasing the demand for carbon fiber and the need for carbon fiber at affordable prices to meet the competitive requirement in these new market segments. The result of these changes in the market demand created the needs for low cost carbon fibers and the large expansion of carbon producers manufacturing capacities.

Splittable PAN fiber large tow, based on textile industry tow of more than 320K filaments, provided the precursor for producing commercial grade carbon fiber that met the industrial applications of carbon fiber at affordable and competitive prices. The tow sizes for aerospace grade carbon fiber range from 1K - 12K filaments, and their prices could be as high as $200/lb depending on the carbon fiber class (high modulus). Composites manufacturing technologies during the last 50 years were developed and implemented for these small tow sizes. The commercial large tow sizes are 50K – 84K and their current prices are around $8/lb - $12/lb depending on the volume. Large tow carbon fibers are manufactured in the standard modulus type (approximately 30 – 35 Msi tensile modulus). Also, large tow carbon fiber has been successfully used in many industrial applications, such as automotive, sporting equipment, and wind energy. There are some difficulties and issues in the manufacturing of composite structures and components made from large tow carbon fiber tows using technologies for the small carbon fiber tows. These issues are being addressed and researched to take advantage of the large carbon fiber tow competitive prices. In the last five years, many carbon fiber producers are marketing carbon fiber in 24K, 36K, and 50K tow sizes. These intermediate size tows have been successfully used in weaving and filament winding processing technologies to overcome the large tow processing difficulties. The PAN-based carbon fiber commercial grade large tow producers are Zoltek, SGL Carbon, TohoTenax (at the former Fortafil location), and Mitsubishi/Grafil. It is estimated that current uses of large tow represent approximately 25% - 30% of the carbon fiber market; it is expected to increase to approximately 40% by 2012.

The price of carbon fiber and carbon fiber products has hindered the expansion and utilization of carbon fiber materials into new and emerging markets. Also, carbon fiber price and the market volume have kept carbon fiber materials from becoming commodity materials. The current business models, adopted by composites product producers and end users of carbon fiber materials, demand high quality materials at stable, affordable prices. The demands of reducing material costs, improving quality, and reducing inventories have pushed the carbon fiber material suppliers to integrate and consolidate their manufacturing and business operations. The following approaches have been adopted by the carbon fiber industry:

1.Integration of precursor production facilities and carbon fiber conversion facilities. The

Japanese companies have the advantage in these areas. Most of the Japanese carbon fiber producers have a long history in textile and PAN precursor production. Also, Japanese carbon manufacturers are in close business cooperation with end users to create markets for their carbon fiber material products.

2.Acquisition of textile manufacturing facilities and conversion of these facilities to

produce precursor for carbon fiber (Zoltek).

3.Integration of carbon manufacturing facilities with other post materials processing

operations to provide ready-to-use raw materials for the manufacturing of composites products and structures (weaving, braiding, prepregging, resin development and impregnation). This integration adds value to the supplied material product forms and reduces the user’s effort in developing the required material forms (resin selection, material types, control of the incoming material quality, manufacturing costs, and focusing of the composite product production).

4.Development of market applications for carbon fiber material by cooperative efforts

between the material suppliers and the end users for new and emerging market applications (such as wind energy, offshore oil exploration and production, energy and automotive).

In the half-century since PAN-based carbon fiber was invented, Asian, U.S. and European companies have successfully manufactured and commercialized PAN-based and pitch-based carbon fibers. Presently, the carbon fiber industry consists of three Japanese companies, four European and U.S. companies, and one Taiwanese company. The three Japanese companies have 65% -70 % of the carbon fiber market share. Other countries such as Russia, India, Korea, and China are entering the carbon fiber manufacturing industry. Demand is growing steadily, particularly in civil aircraft, energy, automotive, and general industry. The forecasted demand for carbon fiber is approximately 40,000 metric tonnes in 2010. The world's leading carbon fiber producers currently are:

1.Cytec Industries

2.Hexcel Corporation

3.Mitsubishi Rayon Co., Ltd.

4.SGL Group

5.TohoTenax (Teijin Limited)

6.Toray Industries

7.Zoltek Companies