Polycarbonate

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Polycarbonate
Lexan.png
Repeating chemical structure unit of
Polycarbonate made from bisphenol A

Near to Short-wave Infrared Transmittance Spectrum

Polycarbonate IR transmission.png
IR transmittance of polycarbonate. Also, polycarbonate is almost completely transparent throughout the entire visible region until 400 nm, blocking UV light
Physical Properties
Density (ρ) 1.20–1.22 g/cm3
Abbe number (V) 34.0
Refractive index (n) 1.584–1.586
Flammability V0-V2
Limiting oxygen index 25–27%
Water absorptionEquilibrium (ASTM) 0.16–0.35%
Water absorption – over 24 hours 0.1%
Radiation resistance Fair
Ultraviolet (1-380nm) resistance Fair
Mechanical Properties
Young's modulus (E) 2.0–2.4 GPa
Tensile strengtht) 55–75 MPa
Elongation (ε) at break 80–150%
Compressive strength (σc) >80 MPa
Poisson's ratio (ν) 0.37
HardnessRockwell M70
Izod impact strength 600–850 J/m
Notch test 20–35 kJ/m2
Abrasive resistance – ASTM D1044 10–15 mg/1000 cycles
Coefficient of friction (μ) 0.31
Speed of sound 2270 m/s
Thermal Properties
Melting temperature (Tm) 155 °C (311 °F)[1]
Glass transition temperature (Tg) 147 °C (297 °F)
Heat deflection temperature
  • 0.45 MPa: 140 °C (284 °F)
  • 1.8 MPa: 128–138 °C (262–280 °F)
Vicat softening point at 10 kN 145 °C (293 °F)[citation needed]
Upper working temperature 115–130 °C (239–266 °F)
Lower working temperature −40 °C (−40 °F)[2]
Thermal conductivity (k) at 23 °C 0.19–0.22 W/(m·K)
Thermal diffusivity (a) at 25 °C 0.144 mm²/s[3]
Linear thermal expansion coefficient (α) 65–70 × 10−6/K
Specific heat capacity (c) 1.2–1.3 kJ/(kg·K)
Electrical Properties
Dielectric constant (εr) at 1 MHz 2.9
Permittivity (ε) 2.568 × 10−11 F/m
Relative permeability (μr) at 1 MHz 0.866(2)
Permeability (μ) at 1 MHz 1.089(2) μN/A2
Dissipation factor at 1 MHz 0.01
Surface resistivity 1015 Ω/sq
Volume resistivity (ρ) 1012–1014 Ω·m
Chemical Resistance
Acidsconcentrated Poor
Acidsdilute Good
Alcohols Good
Alkalis Good-Poor
Aromatic hydrocarbons Poor
Greases & Oils Good-fair
Halogenated Hydrocarbons Good-poor
Halogens Poor
Ketones Poor
Gas permeation at 20 °C
Nitrogen 10 – 25 cm3·mm/(m2·day·Bar)
Oxygen 70 – 130 cm3·mm/(m2·day·Bar)
Carbon dioxide 400 – 800 cm3·mm/(m2·day·Bar)
Water vapour 1–2 gram·mm/(m2·day) @ 85%–0% RH gradient
Economics
Price 2.6 – 2.8 /kg[4]

Polycarbonates (PC), known by the trademarked names Lexan, Makrolon, Makroclear, arcoPlus® and others, are a particular group of thermoplastic polymers. They are easily worked, molded, and thermoformed. Because of these properties, polycarbonates find many applications. Polycarbonates do not have a unique resin identification code and are identified as Other, 7. Items made from polycarbonate can contain the precursor monomer bisphenol A (BPA).

Structure[edit]

Polycarbonates received their name because they are polymers containing carbonate groups (–O–(C=O)–O–). Most polycarbonates of commercial interest are derived from rigid monomers. A balance of useful features including temperature resistance, impact resistance and optical properties position polycarbonates between commodity plastics and engineering plastics.

Production[edit]

The main polycarbonate material is produced by the reaction of bisphenol A (BPA) and phosgene COCl
2
. The overall reaction can be written as follows:

Polycarbonatsynthese.svg

The first step of the synthesis involves treatment of bisphenol A with sodium hydroxide, which deprotonates the hydroxyl groups of the bisphenol A.[5]

(HOC6H4)2CMe2 + 2 NaOH → Na2(OC6H4)2CMe2 + 2 H2O

The diphenoxide (Na2(OC6H4)2CMe2) reacts with phosgene to give a chloroformate, which subsequently is attacked by another phenoxide. The net reaction from the diphenoxide is:

Na2(OC6H4)2CMe2 + COCl2 → 1/n [OC(OC6H4)2CMe2]n + 2 NaCl

In this way, approximately one billion kilograms of polycarbonate is produced annually. Many other diols have been tested in place of bisphenol A, e.g. 1,1-bis(4-hydroxyphenyl)cyclohexane and dihydroxybenzophenone. The cyclohexane is used as a comonomer to suppress crystallisation tendency of the BPA-derived product. Tetrabromobisphenol A is used to enhance fire resistance. Tetramethylcyclobutanediol has been developed as a replacement for BPA.[5]

An alternative route to polycarbonates entails transesterification from BPA and diphenyl carbonate:

(HOC6H4)2CMe2 + (C6H5O)2CO → 1/n [OC(OC6H4)2CMe2]n + 2 C6H5OH

The diphenyl carbonate was derived in part from carbon monoxide, this route being greener than the phosgene method.[5]

Properties and processing[edit]

Polycarbonate is a durable material. Although it has high impact-resistance, it has low scratch-resistance and so a hard coating is applied to polycarbonate eyewear lenses and polycarbonate exterior automotive components. The characteristics of polycarbonate are quite like those of polymethyl methacrylate (PMMA, acrylic), but polycarbonate is stronger and usable over a greater temperature range. Polycarbonate is highly transparent to visible light, with better light transmission than many kinds of glass.

Polycarbonate has a glass transition temperature of about 147 °C (297 °F),[6] so it softens gradually above this point and flows above about 155 °C (311 °F).[1] Tools must be held at high temperatures, generally above 80 °C (176 °F) to make strain- and stress-free products. Low molecular mass grades are easier to mold than higher grades, but their strength is lower as a result. The toughest grades have the highest molecular mass, but are much more difficult to process.

Unlike most thermoplastics, polycarbonate can undergo large plastic deformations without cracking or breaking. As a result, it can be processed and formed at room temperature using sheet metal techniques, such as bending on a brake. Even for sharp angle bends with a tight radius, heating may not be necessary. This makes it valuable in prototyping applications where transparent or electrically non-conductive parts are needed, which cannot be made from sheet metal. Note that PMMA/Plexiglas, which is similar in appearance to polycarbonate, is brittle and cannot be bent at room temperature.

Main transformation techniques for polycarbonate resins:

  • extrusion into tubes, rods and other profiles including multiwall
  • extrusion with cylinders (calenders) into sheets (0.5–20 mm (0.020–0.787 in)) and films (below 1 mm (0.039 in)), which can be used directly or manufactured into other shapes using thermoforming or secondary fabrication techniques, such as bending, drilling, routing, laser cutting etc.
  • injection molding into ready articles
A bottle made from polycarbonate

Applications[edit]

Electronic components[edit]

Polycarbonate is mainly used for electronic applications that capitalize on its collective safety features. Being a good electrical insulator and having heat-resistant and flame-retardant properties, it is used in various products associated with electrical and telecommunications hardware. It can also serve as a dielectric in high-stability capacitors.[5] However, commercial manufacture of polycarbonate capacitors mostly stopped after sole manufacturer Bayer AG stopped making capacitor-grade polycarbonate film at the end of year 2000.[7][8]

Construction materials[edit]

Polycarbonate sheeting in a greenhouse

The second largest consumer of polycarbonates is the construction industry, e.g. for domelights, flat or curved glazing, and sound walls.

Data storage[edit]

CDs and DVDs

A major application of polycarbonate is the production of Compact Discs, DVDs, and Blu-ray Discs. These discs are produced by injection molding polycarbonate into a mold cavity that has on one side a metal stamper containing a negative image of the disc data, while the other mold side is a mirrored surface. Typical products of sheet/film production include applications in advertisement (signs, displays, poster protection).[5]

Automotive, aircraft, and security components[edit]

In the automotive industry, injection-molded polycarbonate can produce very smooth surfaces that make it well-suited for sputter deposition or evaporation deposition of aluminium without the need for a base-coat. Decorative bezels and optical reflectors are commonly made of polycarbonate. Due to its low weight and high impact resistance, polycarbonate is the dominant material for making automotive headlamp lenses. However, automotive headlamps require outer surface coatings because of its low scratch resistance and susceptibility to ultra violet degradation (yellowing). The use of polycarbonate in automotive applications is limited to low stress applications. Stress from fasteners, plastic welding and molding render polycarbonate susceptible to stress corrosion cracking when it comes in contact with certain accelerants such as salt water and plastisol.

It can be laminated to make bullet-proof "glass", although "bullet-resistant" is more accurate for the thinner windows, such as are used in bullet-resistant windows in automobiles. The thicker barriers of transparent plastic used in teller's windows and barriers in banks are also polycarbonate.

So-called "theft-proof" large plastic packaging for smaller items, which cannot be opened by hand, is uniformly made from polycarbonate.

F-22 cockpit canopy

The cockpit canopy of the F-22 Raptor jet fighter is made from a piece of high optical quality polycarbonate, and is the largest piece of its type formed in the world.[9][10]

South African security companies have launched the 'transparent burglar bar' under a variety of retail names, made from polycarbonate.[11]

Niche applications[edit]

Polycarbonate, being a versatile material with attractive processing and physical properties, has attracted myriad smaller applications. The use of injection molded drinking bottles, glasses and food containers is common, but the use of BPA in the manufacture of polycarbonate has stirred serious controversy (see Potential hazards in food contact applications), leading to development and use of "BPA-free" plastics in various formulations.

Laboratory safety goggles

Polycarbonate is commonly used in eye protection, as well as in other projectile-resistant viewing and lighting applications that would normally indicate the use of glass, but require much higher impact-resistance. Polycarbonate lenses also protect the eye from UV light. Many kinds of lenses are manufactured from polycarbonate, including automotive headlamp lenses, lighting lenses, sunglass/eyeglass lenses, swimming goggles and SCUBA masks, and safety glasses/goggles/visors including visors in sporting helmets/masks and police riot gear. Windscreens in small motorized vehicles are commonly made of polycarbonate, such as for motorcycles, ATVs, golf carts, and small planes and helicopters.

The light weight of polycarbonate as opposed to glass has led to development of electronic display screens that replace glass with polycarbonate, for use in mobile and portable devices. Such displays include newer e-ink and some LCD screens, though CRT, plasma screen and other LCD technologies generally still require glass for its higher melting temperature and its ability to be etched in finer detail.

As more and more governments are restricting the use of glass in pubs and clubs[12] due to the increased incidence of glassings, polycarbonate glasses[13] are becoming popular for serving alcohol because of their strength, durability, and glass-like feel.

Other miscellaneous items include durable, lightweight luggage, MP3/digital audio player cases, ocarinas, computer cases, riot shields, instrument panels, tealight candle containers and blender jars. Many toys and hobby items are made from polycarbonate parts, e.g. fins, gyro mounts, and flybar locks for use with radio-controlled helicopters.[14]

Standard Polycarbonate resins are not suitable for long term exposure to UV radiation. To overcome this the primary resin can have UV Stabilisers added. These grades are sold as UV Stabilised Polycarbonate to Injection Moulding and Extrusion companies. Other applications including Polycarbonate sheet may have the anti-UV layer added as a special coating or a coextrusion for enhanced weathering resistance.

Polycarbonate is also used as a printing substrate for nameplate and other forms of industrial grade under printed products. The polycarbonate provides a barrier to wear, the elements, and fading.

Medical applications[edit]

Many polycarbonate grades are used in medical applications and comply with both ISO 10993-1 and USP Class VI standards (occasionally referred to as PC-ISO). Class VI is the most stringent of the six USP ratings. These grades can be sterilized using steam at 120 °C, gamma radiation, or by the ethylene oxide (EtO) method.[15] However, scientific research indicates possible problems with biocompatibility. Dow Chemical strictly limits all its plastics with regard to medical applications.[16][17]

Phones[edit]

Some major smartphone manufacturers use polycarbonate. Nokia has used polycarbonate in their phones starting with the N9's unibody case in 2011. This practice continues with various phones in the Lumia series. Samsung has started using polycarbonate with Galaxy S III's battery cover in 2012. This practice continues with various phones in the Galaxy series. Apple has started using polycarbonate with iPhone 5c's unibody case in 2013.

Primary resin manufacturers and brands[edit]

Manufacturer Brand Manufacturer Brand
Sabic Lexan Bayer Makrolon
Teijin Panlite LG Lupoy
Mitsubishi Iupilon Idemitsu Tarflon
Chi Mei Wonderlite Honam Hopelex
Cheil/Samsung Infino Styron Calibre
Samyang Trirex Kazanorgsintez Mapka
PCCI (KZPC) Unigel Durolon

Semi-finished products produced from polycarbonate[edit]

Manufacturer Brand
SABIC, Innovative Plastics Lexan Sheets and Lexan Films
Power Chem Plast Ltd. Durotuff Sheets
VMI Plastic Pvt. Ltd. Sunlite Sheets
Arla Plast AB Makroclear Sheets

History[edit]

Polycarbonates were first discovered in 1898 by Alfred Einhorn, a German scientist working at the University of Munich.[18] However, after 30 years of laboratory research, this class of materials was abandoned without commercialization. Research resumed in 1953, when Hermann Schnell at Bayer in Uerdingen, Germany patented the first linear polycarbonate. The brand name "Makrolon" was registered in 1955.

Also in 1953, and one week after the invention at Bayer, Daniel Fox at GE in Schenectady, New York, independently synthesized a branched polycarbonate. Both companies filed for U.S. patents in 1955, and agreed that the company lacking priority would be granted a license to the technology.[19][20]

Once patent priority was resolved, in Bayer's favor, Bayer began commercial production under the trade name Makrolon in 1958 and GE began production under the name Lexan in 1960.

After 1970, the brownish original polycarbonate tint was improved to "glass-clear".

Potential hazards in food contact applications[edit]

Main articles: Bisphenol A and Endocrine disruptor

The use of polycarbonate containers for the purpose of food storage is controversial. The basis of this controversy is their hydrolysis (degradation by water, often referred to as leaching) occurring at high temperature, releases bisphenol A:

1/n [OC(OC6H4)2CMe2]n + H2O → (HOC6H4)2CMe2 + CO2

More than 100 studies have explored the bioactivity of bisphenol A derived from polycarbonates. Bisphenol A appeared to be released from polycarbonate animal cages into water at room temperature and it may have been responsible for enlargement of the reproductive organs of female mice.[21] However, the animal cages used in the research were fabricated from industrial grade polycarbonate, rather than FDA food grade polycarbonate.

An analysis of the literature on bisphenol A leachate low-dose effects by vom Saal and Hughes published in August 2005 seems to have found a suggestive correlation between the source of funding and the conclusion drawn. Industry-funded studies tend to find no significant effects whereas government-funded studies tend to find significant effects.[22]

Sodium hypochlorite bleach and other alkali cleaners catalyze the release of the bisphenol A from polycarbonate containers.[23][24] A chemical compatibility chart shows that polycarbonate is incompatible with ammonia and acetone because it dissolves in their presence.[25] Alcohol is one recommended organic solvent for cleaning grease and oils from polycarbonate.

Bioremediation[edit]

A species of fungus found in Belize, Geotrichum candidum, has been found to consume the polycarbonate found in CDs.[26]

See also[edit]

References[edit]

  1. ^ a b "Polycarbonate". city plastics. Retrieved 2013-12-18. 
  2. ^ M. Parvin and J. G. Williams (1975). "The effect of temperature on the fracture of polycarbonate". Journal of Materials Science 10 (11): 1883. doi:10.1007/BF00754478. 
  3. ^ J. Blumm, A. Lindemann (2003/2007). "Characterization of the thermophysical properties of molten polymers and liquids using the flash technique". High Temperatures-High Pressures. 35/36 (6): 627. doi:10.1068/htjr144.  Check date values in: |date= (help)
  4. ^ CES Edupack 2010, Polycarbonate (PC) specs sheet
  5. ^ a b c d e Volker Serini "Polycarbonates" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000. doi:10.1002/14356007.a21_207
  6. ^ Answers to Common Questions about Bayer Polycarbonate Resins
  7. ^ Film Capacitors
  8. ^ Wima (capacitor manufacturer) on discontinuation of polycarbonate capacitors and recommended substitutes.
  9. ^ Egress technicians keep raptor pilots covered. Pacaf.af.mil. Retrieved on 2011-02-26.
  10. ^ F-22 Cockpit. Globalsecurity.org (2008-01-21). Retrieved on 2011-02-26.
  11. ^ [1]. Retrieved on 2012-06-28.
  12. ^ http://www.olgr.nsw.gov.au/alcohol_restrictions_for_violent_venues.asp, http://www.olgr.qld.gov.au/industry/liquor_compliance/glass_bans/index.shtml
  13. ^ http://polysafe.com.au/
  14. ^ Hobby Applications of Polycarbonate
  15. ^ Medical Applications of Polycarbonate
  16. ^ "Dow Plastics Medical Application Policy". 
  17. ^ "Makrolon Polycarbonate Biocompatibility Grades". 
  18. ^ "Polycarbonate (PC)". UL Prospector. Retrieved 5 May 2014. 
  19. ^ "Polycarbonate is Polyfunctional". Chemical Institute of Canada. Retrieved 5 May 2014. 
  20. ^ Jerome T. Coe (27 August 2010). "Lexan Polycarbonate: 1953-1968". Unlikely Victory: How General Electric Succeeded in the Chemical Industry. John Wiley & Sons. pp. 71–77. ISBN 978-0-470-93547-7. 
  21. ^ Howdeshell, KL; Peterman PH; Judy BM; Taylor JA; Orazio CE; Ruhlen RL; Vom Saal FS; Welshons WV (2003). "Bisphenol A is released from used polycarbonate animal cages into water at room temperature". Environmental Health Perspectives 111 (9): 1180–7. doi:10.1289/ehp.5993. PMC 1241572. PMID 12842771. Retrieved 2006-06-07. 
  22. ^ vom Saal FS, Hughes C (2005). "An extensive new literature concerning low-dose effects of bisphenol A shows the need for a new risk assessment". Environ. Health Perspect. 113 (8): 926–33. doi:10.1289/ehp.7713. PMC 1280330. PMID 16079060. 
  23. ^ Hunt, PA; Kara E. Koehler, Martha Susiarjo, Craig A. Hodges, Arlene Ilagan, Robert C. Voigt, Sally Thomas, Brian F. Thomas and Terry J. Hassold (2003). "Bisphenol A Exposure Causes Meiotic Aneuploidy in the Female Mouse". Current Biology 13 (7): 546–553. doi:10.1016/S0960-9822(03)00189-1. PMID 12676084. 
  24. ^ Koehler, KE; Robert C. Voigt; Sally Thomas; Bruce Lamb; Cheryl Urban; Terry Hassold; Patricia A. Hunt (2003). "When disaster strikes: rethinking caging materials". Lab Animal 32 (4): 24–27. doi:10.1038/laban0403-24. PMID 19753748. 
  25. ^ Premium Twinwall and Triplewall Polycarbonate Sheet by Verolite
  26. ^ "Fungus eats CD". Nature. 2001. 

External links[edit]