PMMA, ALTERNATIVE TO

GLASS?
By Akhil (PES1201801945) and Mayur (PES1201801990)

APRIL 20, 2019

PES UNIVERSITY
 CONTENTS
1. History
2. Processing
 1. INTRODUCTION

Poly(methyl methacrylate) (PMMA), also known as acrylic, acrylic glass,

or plexiglass as well as by the trade names Crylux, Plexiglas, Acrylite, Lucite,
and Perspex among several others (see below), is a transparent thermoplastic often
used in sheet form as a lightweight or shatter-resistant alternative to glass. The
same material can be used as a casting resin, in inks and coatings, and has many
other uses.
Although not a type of familiar silica-based glass, the substance, like many
thermoplastics, is often technically classified as a type of glass (in that it is a non-
crystalline vitreous substance) hence its occasional historical designation as acrylic
glass. Chemically, it is the synthetic polymer of methyl methacrylate. The material
was developed in 1928 in several different laboratories by many chemists, such as
William Chalmers, Otto Röhm, and Walter Bauer, and was first brought to market in
1933 by German Röhm & Haas AG (as of January 2019 part of Evonik Industries)
and its partner and former U.S. affiliate Rohm and Haas Company under
the trademark Plexiglas.[5]
PMMA is an economical alternative to polycarbonate (PC) when tensile
strength, flexural strength, transparency, polishability, and UV tolerance are more
important than impact strength, chemical resistance and heat
resistance.[6] Additionally, PMMA does not contain the potentially harmful bisphenol-
A subunits found in polycarbonate. It is often preferred because of its moderate
properties, easy handling and processing, and low cost. Non-modified PMMA
behaves in a brittle manner when under load, especially under an impact force, and
is more prone to scratching than conventional inorganic glass, but modified PMMA is
sometimes able to achieve high scratch and impact resistance.

2. HISTORY
The first acrylic acid was created in 1843. Methacrylic acid, derived from acrylic acid,
was formulated in 1865. The reaction between methacrylic acid and methanolresults
in the ester methyl methacrylate. Polymethyl methacrylate was discovered in the
early 1930s by British chemists Rowland Hill and John Crawford at Imperial
Chemical Industries (ICI) in England. ICI registered the product under the trademark
Perspex. About the same time, chemist and industrialist Otto Röhm of Rohm and
Haas AG in Germany attempted to produce safety glass by polymerizing methyl
methacrylate between two layers of glass. The polymer separated from the glass as
a clear plastic sheet, which Röhm gave the trademarked name Plexiglas in 1933.
Both Perspex and Plexiglas were commercialized in the late 1930s. In the United
States, E.I. du Pont de Nemours & Company (now DuPont Company) subsequently
introduced its own product under the trademark Lucite. In 1936 ICI Acrylics (now
Lucite International) began the first commercially viable production of acrylic safety
glass. During World War II both Allied and Axis forces used acrylic glass for
submarine periscopes and aircraft windshields, canopies, and gun turrets. Airplane
pilots whose eyes were damaged by flying shards of PMMA fared much better than
those injured by standard glass, demonstrating better compatibility between human
tissue and PMMA than glass.[7] Civilian applications followed after the war.[8
6. PROPERTIES
PMMA is a strong, tough, and lightweight material. It has a density of 1.17–
1.20 g/cm3,[1][21] which is less than half that of glass.[1] It also has good impact
strength, higher than both glass and polystyrene; however, PMMA's impact strength
is still significantly lower than polycarbonate and some engineered polymers. PMMA
ignites at 460 °C (860 °F) and burns, forming carbon dioxide, water, carbon
monoxide and low-molecular-weight compounds, including formaldehyde.[22]
PMMA transmits up to 92% of visible light (3 mm thickness), and gives a reflection of
about 4% from each of its surfaces due to its refractive index (1.4905 at
589.3 nm).[3] It filters ultraviolet (UV) light at wavelengths below about 300nm (similar
to ordinary window glass). Some manufacturers [23] add coatings or additives to
PMMA to improve absorption in the 300–400 nm range. PMMA passes infrared light
of up to 2,800 nm and blocks IR of longer wavelengths up to 25,000 nm. Colored
PMMA varieties allow specific IR wavelengths to pass while blocking visible
light (for remote control or heat sensor applications, for example).
PMMA swells and dissolves in many organic solvents; it also has poor resistance to
many other chemicals due to its easily hydrolysed ester groups. Nevertheless, its
environmental stability is superior to most other plastics such as polystyrene and
polyethylene, and PMMA is therefore often the material of choice for outdoor
applications.[24]
PMMA has a maximum water absorption ratio of 0.3–0.4% by weight.[21] Tensile
strength decreases with increased water absorption.[25] Its coefficient of thermal
expansion is relatively high at (5–10) ×10−5 °C−1.[26]

 Skeletal structure of methyl methacrylate, the constituent monomer of PMMA

 7. USES

1. Daylight redirection

 Laser cut acrylic panels have been used to redirect sunlight into a light pipe or
tubular skylight and, from there, to spread it into a room.[31]
 Attenuation being quite strong for distances over one meter (more than 90%
intensity loss for a 3000 K source [34 ] ), acrylic broadband light guides are then
dedicated mostly to decorative uses.
 Pairs of acrylic sheets with a layer of micro-replicated prisms between the sheets
can have reflective and refractive properties that let them redirect part of
incoming sunlight in dependence on its angle of incidence. Such panels act as
miniature light shelves. Such panels have been commercialized for purposes
of day-lighting, to be used as a window or a canopy such that sunlight
descending from the sky is directed to the ceiling or into the room rather than to
the floor. This can lead to a higher illumination of the back part of a room, in
particular when combined with a white ceiling, while having a slight impact on the
view to the outside compared to normal glazing.[35][36]

2. Medical technologies and implants

 PMMA has a good degree of compatibility with human tissue, and it is used in the
manufacture of rigid intraocular lenses which are implanted in the eye when the
original lens has been removed in the treatment of cataracts. This compatibility
was discovered by the English ophthalmologist Sir Harold Ridley in WWII RAF
pilots, whose eyes had been riddled with PMMA splinters coming from the side
windows of their Super-marine Spitfire fighters – the plastic scarcely caused any
rejection, compared to glass splinters coming from aircraft such as the Hawker
Hurricane.[37]
In particular, acrylic-type contact lenses are useful for cataract surgery in patients
that have recurrent ocular inflammation (uveitis), as acrylic material induces less
inflammation.

 Eyeglass lenses are commonly made from PMMA.

 Historically, hard contact lenses were frequently made of this material. Soft
contact lenses are often made of a related polymer, where acrylate monomers
containing one or more hydroxyl groups make them hydrophilic.
 In orthopaedic surgery, PMMA bone cement is used to affix implants and to
remodel lost bone. It is supplied as a powder with liquid methyl methacrylate
(MMA). Although PMMA is biologically compatible, MMA is considered to be an
irritant and a possible carcinogen. PMMA has also been linked
to cardiopulmonary events in the operating room due to hypotension.[39] Bone
 cement acts like a grout and not so much like a glue in arthroplasty. Although
sticky, it does not bond to either the bone or the implant, it primarily fills the
spaces between the prosthesis and the bone preventing motion. A disadvantage
of this bone cement is that it heats up to 82.5 °C (180.5 °F) while setting that may
cause thermal necrosis of neighbouring tissue. A careful balance of initiators and
monomers is needed to reduce the rate of polymerization, and thus the heat
generated.
 In cosmetic surgery, tiny PMMA microspheres suspended in some biological fluid
are injected as a soft tissue filler under the skin to reduce wrinkles or scars
permanently.[40] PMMA as a soft tissue filler was widely used in the beginning of
the century to restore volume in patients with HIV-related facial wasting. PMMA
is used illegally to shape muscles by some bodybuilders.
 Plombage is an outdated treatment of tuberculosis where the pleural space
around an infected lung was filled with PMMA balls, in order to compress and
collapse the affected lung.
 Emerging biotechnology and Biomedical research uses PMMA to
create microfluidic lab-on-a-chip devices, which require 100 micrometre-wide
geometries for routing liquids. These small geometries are amenable to using
PMMA in a biochip fabrication process and offers moderate biocompatibility.
 Bioprocess chromatography columns use cast acrylic tubes as an alternative to
glass and stainless steel. These are pressure rated and satisfy stringent
requirements of materials for biocompatibility, toxicity and extractables.

3. Uses in dentistry
Due to its aforementioned biocompatibility, Poly (methyl methacrylate) is a
commonly used material in modern dentistry, particularly in the fabrication of dental
prosthetics, artificial teeth, and orthodontic appliances.

 Acrylic Prosthetic Construction: Pre-polymerized, powdered PMMA spheres

are mixed with a Methyl Methacrylate liquid monomer, Benzoyl Peroxide
(initiator), and NN-Dimethyl-P-Toluidine (accelerator), and placed under heat and
pressure to produce a hardened polymerized PMMA structure. Through the use
of injection molding techniques, wax based designs with artificial teeth set in
predetermined positions built on gypsum stone models of patients' mouths can
be converted into functional prosthetics used to replace missing dentition. PMMA
polymer and methyl methacrylate monomer mix is then injected into a flask
containing a gypsum mould of the previously designed prosthesis, and placed
under heat to initiate polymerization process. Pressure is used during the curing
process to minimize polymerization shrinkage, ensuring an accurate fit of the
prosthesis. Though other methods of polymerizing PMMA for prosthetic
fabrication exist, such as chemical and microwave resin activation, the previously
described heat-activated resin polymerization technique is the most commonly
used due to its cost effectiveness and minimal polymerization shrinkage.
 Artificial Teeth: While denture teeth can be made of several different materials,
PMMA is a material of choice for the manufacturing of artificial teeth used in
dental prosthetics. Mechanical properties of the material allow for heightened
control of aesthetics, easy surface adjustments, decreased risk of fracture when
in function in the oral cavity, and minimal wear against opposing teeth.
 Additionally, since the bases of dental prosthetics are often constructed using
PMMA, adherence of PMMA denture teeth to PMMA denture bases is
unparalleled, leading to the construction of a strong and durable prosthetic.[41]

4. Artistic and aesthetic uses

Lexus Perspex car sculpture.

Plexiglas art by Manfred Kielnhofer

Kawai acrylic grand piano

 Acrylic paint essentially consists of PMMA suspended in water; however since

PMMA is hydrophobic, a substance with both hydrophobic and hydrophilic
groups needs to be added to facilitate the suspension.
 Modern furniture makers, especially in the 1960s and 1970s, seeking to give their
products a space age aesthetic, incorporated Lucite and other PMMA products
into their designs, especially office chairs. Many other products (for example,
 guitars) are sometimes made with acrylic glass to make the commonly opaque
objects translucent.
 Perspex has been used as a surface to paint on
 In the 1950s and 1960s, Lucite was an extremely popular material for jewellery,
with several companies specialized in creating high-quality pieces from this
material. Lucite beads and ornaments are still sold by jewellery suppliers
 Acrylic Sheets are produced in dozens of standard colours.

5. Other uses

 PMMA, in the commercial form is used vastly in the medical field. It is used for
plastic histology, electron micropsy, as well as many more uses.
 PMMA has been used to create ultra-white opaque membranes that are
flexible and switch appearance to transparent when wet.[44]
 Acrylic is used in tanning beds as the transparent surface that separates the
occupant from the tanning bulbs while tanning. The type of acrylic used in
tanning beds is most often formulated from a special type of polymethyl
methacrylate, a compound that allows the passage of ultraviolet rays
 Sheets of PMMA are commonly used in the sign industry to make flat cut out
letters in thicknesses typically varying from 3 to 25 millimetres (0.1 to 1.0 in).
These letters may be used alone to represent a company's name and/or logo,
or they may be a component of illuminated channel letters. Acrylic is also
used extensively throughout the sign industry as a component of wall signs
where it may be a backplate, painted on the surface or the backside, a
faceplate with additional raised lettering or even photographic images printed
directly to it, or a spacer to separate sign components.
 PMMA was used in Laserdisc optical media.[45] (CDs and DVDs use both
acrylic and polycarbonate for impact resistance.)
 It is used as a light guide for the backlights in TFT-LCDs.
 Plastic optical fiber used for short distance communication is made from
PMMA, and perfluorinated PMMA, clad with fluorinated PMMA, in situations
where its flexibility and cheaper installation costs outweigh its poor heat
tolerance and higher attenuation over glass fiber.
 PMMA, in a purified form, is used as the matrix in laser dye-doped organic
solid-state gain media for tunable solid state dye lasers.[46]
 In semiconductor research and industry, PMMA aids as a resist in the electron
beam lithography process. A solution consisting of the polymer in a solvent is
used to spin coat silicon and other semiconducting and semi-insulating wafers
with a thin film. Patterns on this can be made by an electron beam (using
an electron microscope), deep UV light (shorter wavelength than the
standard photolithography process), or X-rays. Exposure to these creates
chain scission or (de-cross-linking) within the PMMA, allowing for the selective
removal of exposed areas by a chemical developer, making it a positive
photoresist. PMMA's advantage is that it allows for extremely high resolution
patterns to be made. Smooth PMMA surface can be easily nanostructured by
treatment in oxygen radio-frequency plasma47] and nanostructured PMMA
surface can be easily smoothed by vacuum ultraviolet (VUV) irradiation.[47]
  PMMA is used as a shield to stop beta radiation emitted from radioisotopes.
 Small strips of PMMA are used as dosimeter devices during
the Gamma Irradiation process. The optical properties of PMMA change as
the gamma dose increases, and can be measured with a spectrophotometer.
 A backlight-reactive tattoo ink using PMMA microcapsules has been
developed.[48]
 PMMA can be used as a dispersant for ceramic powders to stabilize colloidal
suspensions in non-aqueous media.] Due to its high viscosity upon
dissolution, it can also be used as binder material for solution deposition
processes, e.g. printing of solar cells.[49]
 Artificial nails in the "acrylic" type often include PMMA powder.[51]
 Some modern briar, and occasionally meerschaum, tobacco pipes sport
stems made of Lucite.
 PMMA technology is utilized in roofing and waterproofing applications. By
incorporating a polyester fleece sandwiched between two layers of catalyst-
activated PMMA resin, a fully reinforced liquid membrane is created in situ.
 PMMA is a widely used material to create deal toys and financial tombstones.

8. PMMA, SUBSTITUTE FOR GLASS

 Weight
Acrylic glass has a lower density, which can range from 1150-1190 kg/m³.
This is less than half the density of glass which ranges from 2400 to 2800
kg/m³. Transportation and assembly of acrylic building materials is
consequently easier and cheaper.
 Impact resistance
Acrylic is many times stronger than glass and thus more resistant to strokes
(10-20 times). Acrylic has a higher impact strength than glass and does not
shatter when exposed to high strains. Shattering into small, blunt chunks is
desirable for applications in which tempered glass is used, e.g. in
automobiles.
However, shattering is not desired for the use of glazing underwater. The
crack resistance is especially valuable, when large underwater windows are
craned into their location. The installation of large and heavy glazing bears a
certain risk for the installation company when using laminated safety glass.
Point loads while hanging on the crane or due to uneven seating might lead to
material failure. Acrylic is more tolerant to these forces and rather flexes then
breaks. Acrylic's high impact strength, durability and applicability make it the
ideal material even when human lives are at stake. Therefore acrylic is used
in deep sea submarine windows. When acrylic shatter, it is, in contrast to
glass, in large pieces with relative blunt edges. At the same time contribute
the low weight to make acrylic much safer.
 Insulation
Acrylic insulates better than glass, and is used heavily in skylights and doors
to coolers
The thermal conductivity of acrylic is lower than that of laminated glass. In
other words the thermal insulation of acrylic is better than of laminated glass.

Material Insulation

Air 0.03W/mK

Acrylic 0.19 /mK

Water 0.57W/mK

Glass 0.79W/mK

 Manufacturing
Molding and extrusion of glass items are more expensive and requires much
more energy.
 Machining
Glass cannot be easily processed by sawing, milling and bending. Moreover,
it is a lot more difficult be form after heating
 Optical transmittance
Acrylic transmits more light than glass. Up to 92% of visible light is transmitted
through acrylic. Mineral glass transmits 80-90%, depending on the type of
glass and manufacturer. This is especially relevant, when comparing load
bearing transparent materials with the same depth. These windows are
usually several centimeters thick, which makes differences in the optical
transmittance particularly noticeable. Bullet proof glass is a well-known type of
load-bearing glass and transmits, similarly to other types of mineral glass, a
white- to green-type of light. This phenomenon is not observable with Acrylic.
 Gloss
Acrylic provides a softer reflection of light. Station glass and acrylic opposite
each other and one is seldom in doubt about what is what. Acrylic with glass
look is acrylic added a bit of colour so that it even more looks like glass.
 UV Resistance
Using acrylic outdoors exposes the material to potentially high amounts of
ultraviolet radiation (UV). It is a common misconception that UV rays lead to
the yellowing of acrylic glazing. This might be true for low quality
acrylic. Plexiglas and other well-known brands are immune even against high
UV radiation. Up to 30 years are guaranteed by the manufacturer.
 Safety glass consists of multiple layers of mineral glazing, separated by
plastic laminate. Normal plastic laminates are not resistant against UV and
are especially sensitive to humidity.
 Chemical Resistance
Acrylics are unaffected by aqueous solutions of most laboratory chemicals, by
detergents, cleaners, dilute inorganic acids, alkalis, and aliphatic
hydrocarbons. However, acrylics are NOT recommended for use with
chlorinated or aromatic hydrocarbons, esters, or ketones.

9. LIMITATIONS
 Poor scratch resistance
 Limited heat resistance (80°C)
 Limited chemical resistance, prone to attack by organic solvents
 Poor wear and abrasion resistance
 Cracking under load possible