Shape memory polymers and textiles

Student: Maria Madalina Iancu

Content: How it started? Polymers

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1. 2.

3. 4. 5. 6. 7. 8.

How shape memory alloys work? Shape memory effect Applications of shape memory Shape memory materials Conclusion Biography

1.How it started?
The first reported steps towards the discovery of the shape memory effect were taken in the 1930s. The basic phenomenon of the memory effect governed by the
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thermoelastic behavior of the martensite phase was widely reported a decade later by Kurdjumov and Khandros (1949) and also by Chang and Read (1951). The nickel-titanium alloys were first developed in 19621963 by the United States Naval Ordnance Laboratory and commercialized under the trade name Nitinol (an acronym for Nickel Titanium Naval Ordnance Laboratories). Their remarkable properties were discovered by accident. A sample that was bent out of shape many times was presented at a laboratory management meeting. One of the associate technical directors, Dr. David S. Muzzey, decided to see what would happen if the sample was subjected to heat and held his pipe lighter underneath it. To everyone's amazement the sample stretched back to its original shape. There is another type of SMA, called a ferromagnetic shape memory alloy (FSMA), that changes shape under strong magnetic fields. These materials are of particular interest as the magnetic response tends to be faster and more efficient than temperature-induced responses. Metal alloys are not the only thermally-responsive materials; shape memory polymers have also been developed, and became commercially available in the late 1990s.

2. Polymers

The word polymer literally means "many parts." A polymeric solid material may be considered to be one that contains many chemically bonded parts or units which themselves are bonded

together to form a solid. Two industrially important polymeric materials are plastics and elastomers. Plastics are a large and varied group of synthetic materials which are processed by forming or molding into shape. Plastics can be divided into two classes, thermoplastics and thermosetting plastics, depending on how they are structurally and chemically bonded. Elastomers or rubbers can be elastically deformed a large amount when a force is applied to them and can return to their original shape (or almost) when the force is released. Effect of Temperatures on Polymers Solids on heating eventually melt to form a liquid. With polymers it is not so simple. Rubber on cooling (in liquid nitrogen) becomes brittle or glassy. Many polymers have a mixture of ordered (crystalline) regions and random (amorphous) regions. In the glassy state the tangled chains in the amorphous region are frozen so movement of chains is not possible. The polymer is brittle. If the glassy material is heated, the chains reach a temperature at which they can move. This temperature is called the glass transition temperature Tg. Above this temperature the polymer is flexible. At the melting point, the crystalline regions break down and the polymer becomes a viscous liquid. The glass transition temperature of a polymer can be changed by two different ways: 1. Copolymerisation - Ethene can be polymerised with propene to give a new polymer with different properties. 2. Plasticisers - PVC is quite brittle. Tg can be lowered, making it less brittle, by introducing a substance between the polymer chains, allowing the chains to slide over each other more easily. Such a substance is called a plasticiser. Synthetic fabrics are man-made copies of natural fabrics. Synthetic fibers do not occur in nature as themselves but are usually derivatives of petroleum products. Examples of common synthetic fabrics are polyester, spandex, rayon, and velcro. The image is of Velcro (hook side). A plant in nature gave the inventor of Velcro the idea for the product. Velcro is in the class of materials called polymers. We are all familiar with liquid crystal display (LCD) devices.Do you realize liquid crystals are polymeric materials? A liquid crystal is, as the name suggests, a state of matter intermediate between a 'normal' liquid and a solid. Liquid crystal phases are formed from geometrically anisotropic molecules - usually this means they are cigar shaped, though other shapes are possible. In a liquid crystal phase, the polymer molecules have a certain degree of order. This effect can be achieved because of the given flexibility of the polymer chains. When the importance of polymeric materials in our daily life is taken into
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consideration, we find a very broad, additional spectrum of possible applications for intelligent polymers that covers an area from minimally invasive surgery, through high-performance textiles, up to self repairing plastic components in every kind of transportation vehicles.

3.

How

Shape memory alloy works?

A shape memory alloy (SMA, smart metal, memory metal, memory alloy, muscle wire, smart alloy) is an alloy that "remembers" its original, coldforged shape: returning the pre-deformed shape by heating. This material is a lightweight, solid-state alternative to conventional actuators such as hydraulic, pneumatic, and motor-based systems. Shape memory alloys have applications in industries including medical and aerospace. Shape-memory materials are stimuli-responsive materials. They have the capability of changing their shape upon application of an external stimulus. A change in shape caused by a change in temperature is called a thermally induced shape-memory effect. The main focus is on thermo responsive shape-memory polymers. The shape memory effect is not related to a specific material property of single polymers; it rather results from a combination of the polymer structure and the polymer morphology together with the applied processing and programming technology. Shape memory behavior can be observed for several polymers that may differ significantly in their chemical composition. The process of programming and recovery of a shape is shown schematically in Figure 1. First, the polymer is conventionally processed to receive its permanent shape. Afterwards, the polymer is deformed and the intended temporary shape is fixed. This process is called programming. The programming process either consists of heating up the sample, deforming, and cooling the sample, or drawing the shape-memory effect.

The permanent shape is transferred to the temporary shape by the programming process. Heating the sample to a temperature above the switching transition T trans results in the recovery of the permanent shape. sample at a low temperature (so called cold drawing). The permanent shape is now stored while the sample shows the temporary shape. Heating up the shape-memory polymer above a transition temperature Trans induces the shape memory effect. As a consequence, the recovery of the store permanent shape can be observed. Cooling down the polymer below the transition temperature leads to solidification of the material, however, no recovery of the temporary shape can be observed. The effect described is named as a oneway shape memory effect. By further programming, including mechanical deformation, the work piece can be brought into a temporary shape again. This new temporary shape does not necessarily match the first temporary shape. Figure 2 demonstrates the performance of shape-memory polymers. The permanent shape of the polymers formed from 1 and 2 is that of a rod which has been deformed to a spiral (temporary shape) during the programming process. Under the influence of hot air having a temperature of 70 o C the permanent shape is recovered as soon as the switching temperature T tran is reached. The permanent shape is recovered with a precision of more than 99 % with appropriately optimized programming conditions. This precision makes these materials suitable for highly demanding applications. These elastic materials show at least two separated phases:
The phase showing the highest thermal transition T

acts as the physical cross-link and is responsible for the permanent shape. Above this temperature the polymer melts and can be processed by conventional processing techniques such as extrusion or injection molding.
perm

A second phase serves as a molecular switch and enables the fixation of the

temporary shape. The transition temperature for the fixation of the switching segments can either be a glass transition (Tg ) or a melting temperature (Tm). After forming the material above the switching temperature, but below T perm, the temporary shape can be fixed by cooling the polymer below the switching temperature. Heating up the material above T trans again cleaves the physical cross-links in the switching phase. The three main types of shape memory alloys are :
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copper-zinc-aluminium-nickel copper-aluminium-nickel nickel-titanium (NiTi) alloys but SMAs can also be created by alloying zinc copper, gold and iron

NiTi alloys are generally more expensive and change from austenite to martensite upon cooling; Mf is the temperature at which the transition to martensite completes upon cooling. Accordingly, during heating As and Af are the temperatures at which the transformation from martensite to austenite starts and finishes. Repeated use of the shape memory effect may lead to a shift of the characteristic transformation temperatures (this effect is known as functional fatigue, as it is closely related with a change of microstructural and functional properties of the material) The transition from the martensite phase to the austenite phase is only dependent on temperature and stress, not time, as most phase changes are, as there is no diffusion involved. Similarly, the austenite structure receives its name from steel alloys of a similar structure. It is the reversible diffusionless transition between these two phases that results in special properties. While martensite can be formed from austenite by rapidly cooling carbon-steel, this process is not reversible, so steel does not have shape memory properties. In this figure, (T) represents the martensite fraction. The difference between the heating transition and the cooling transition gives rise to hysteresis where some of the mechanical energy is lost in the process. The shape of the curve depends on the material properties of the shape memory alloy, such as the alloying and work hardening.
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4. Shape Memory Effect

Figure 4: Microscopic Diagram of the Shape Memory Effect

The shape memory effect is observed when the temperature of a piece of shape memory alloy is cooled to below the temperature Mf. At this stage the alloy is completely composed of Martensite which can be easily deformed. After distorting the SMA the original shape can be recovered simply by heating the wire above the temperature Af. The heat transferred to the wire is the power driving the molecular rearrangement of the alloy, similar to heat melting ice into water, but the alloy remains solid. The deformed Martensite is now transformed to the cubic Austenite phase, which is configured in the original shape of the wire. The Shape memory effect is currently being implemented in:

Coffepots The space shuttle Thermostats Vascular Stents Hydraulic Fittings (for Airplanes)

One way vs. two way shape memory

Shape memory alloys have different shape memory effects. Two common effects are one-way and two-way shape memory. A schematic of the effects is shown below. The procedures are very similar: starting from martensite (a), adding a reversible deformation for the one-way effect or severe deformation with an irreversible amount for the two-way (b), heating the sample (c) and cooling it again (d).

One-way memory effect: When a shape memory alloy is in its cold state (below As), the metal can be bent or stretched and will hold those shapes until heated above the transition temperature. Upon heating, the shape changes to its original. When the metal cools again it will remain in the hot shape, until deformed again. With the one-way effect, cooling from high temperatures does not cause a macroscopic shape change. A deformation is necessary to create the lowtemperature shape. On heating, transformation starts at As and is completed at Af (typically 2 to 20 C or hotter, depending on the alloy or the loading conditions). As is determined by the alloy type and composition and can vary between 150 C and 200 C
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Two-way memory effect:

is the effect that the material remembers two different shapes: one at low

temperatures, and one at the high-temperature shape. A material that shows a shape memory effect during both heating and cooling is called two-way shape memory. can also be obtained without the application of an external force (intrinsic twoway effect). The reason the material behaves so differently in these situations lies in training.
training implies that a shape memory can "learn" to behave in a certain way.

Under normal circumstances, a shape memory alloy "remembers" its hightemperature shape, but upon heating to recover the high-temperature shape, immediately "forgets" the low-temperature shape. Pseudo- elasticity One of the commercial uses of shape memory alloy exploits the pseudo-elastic properties of the metal during the hightemperature (austenitic) phase. The frames of reading glasses have been made of shape memory alloy as they can undergo large deformations in their high-temperature state and then instantly revert back to their original shape when the stress is removed. This is the result of pseudo elasticity; the martensitic phase is generated by stressing the metal in the austenitic state and this martensite phase is capable of large strains. Pseudo-elasticity occurs in shape memory alloys when the alloy is completely composed of Austenite (temperature is greater than Af). Unlike the shape memory effect, pseudo-elasticity occurs without a change in temperature. The load on the shape memory alloy is increased until the Austenite becomes transformed into Martensite simply due to the loading; this process is shown in Figure 5. The loading is absorbed by the softer Martensite, but as soon as the loading is decreased the Martensite begins to transform back to Austenite since the temperature of the wire is still above Af, and the wire springs back to its original shape. Some examples of applications in which pseudo-elasticity is used are:

Eyeglass Frames Bra Underwires Medical Tools

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Cellular Phone Antennae Orthodontic Arches

With the removal of the load, the martensite transforms back into the austenite phase and resumes its original shape. This allows the metal to be bent, twisted and pulled, before reforming its shape when released. This means the frames of shape memory alloy glasses are claimed to be "nearly indestructible" because it appears no amount of bending results in permanent plastic deformation.The martensite temperature of shape memory alloys is dependent on a number of factors including alloy chemistry. Crystal structures Many metals have several different crystal structures at the same composition, but most metals do not show this shape memory effect. The special property that allows shape memory alloys to revert to their original shape after heating is that their crystal transformation is fully reversible. In most crystal transformations, the atoms in the structure will travel through the metal by diffusion, changing the composition locally, even though the metal as a whole is made of the same atoms. A reversible transformation does not involve this diffusion of atoms, instead all the atoms shift at the same time to form a new structure, much in the way a parallelogram can be made out of a square by pushing on two opposing sides. At different temperatures, different structures are preferred and when the structure is cooled through the transition temperature, the martensitic structure forms from the austenitic phase. Manufacture Shape memory alloys are typically made by casting, using vacuum arc melting or induction melting. These are specialist techniques used to keep impurities in the alloy to a minimum and ensure the metals are well mixed. The ingot is then hot rolled into longer sections and then drawn to turn it into wire. The way in which the alloys are "trained" depends on the properties wanted. The "training" dictates the shape that the alloy will remember when it is heated. This occurs by heating the alloy so that the dislocations re-order into stable positions, but not so hot that the material recrystallizes. They are heated to between 400 C and 500 C for 30 minutes. Typical variables for some alloys are 500 C and for more than 5 minutes.

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They are then shaped while hot and are cooled rapidly by quenching in water or by cooling with air. Properties The copper-based and NiTi-based shape memory alloys are considered to be engineering materials. These compositions can be manufactured to almost any shape and size. The yield strength of shape memory alloys is lower than that of conventional steel, but some compositions have a higher yield strength than plastic or aluminum. The yield stress for Ni Ti can reach 500 MPa.(megapascal). As a result, these materials are used in applications where the super elastic properties or the shape memory effect can be exploited. One of the advantages to using shape memory alloys is the high level of recoverable plastic strain that can be induced. The maximum recoverable strain these materials can hold without permanent damage is up to 8% for some alloys. This compares with a maximum strain0.5% for conventional steels.

5. Applications

Agriculture and Agribusiness

Polymeric materials are used in and on soil to improve aeration, provide mulch, and promote plant growth and health. Medicine

Many biomaterials, especially heart valve replacements and blood vessels, are made of polymers like Dacron, Teflon and polyurethane. Shape memory alloys are applied in medicine, for example, as fixation devices for osteotomies in orthopaedic surgery, in dental braces to exert constant tooth-moving forces on the teeth.
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Optometry: Eyeglass frames made from titanium-containing SMAs are marketed under the trademarks Flexon and TITANflex. These frames are usually made out of shape memory alloys that have their transition temperature set below the expected room temperature Dentistry :The range of applications for SMAs has grown over the years, a major area of development being dentistry. One example is the prevalence ofdental braces using SMA technology to exert constant tooth-moving forces on the teeth; Consumer Science

Plastic containers of all shapes and sizes are light weight and economically less expensive than the more traditional containers. Clothing, floor coverings, garbage disposal bags, and packaging are other polymer applications. Industry

Automobile parts, windshields for fighter planes, pipes, tanks, packing materials, insulation, wood substitutes, adhesives, matrix for composites, and elastomers are all polymer applications used in the industrial market. Sports

Playground equipment, various balls, golf clubs, swimming pools, and protective helmets are often produced from polymers.

Advantages and Disadvantages of Shape Memory Alloys Some of the main advantages of shape memory alloys include:

Bio-compatibility Diverse Fields of Application Good Mechanical Properties (strong, corrosion resistant)

There are still some difficulties with shape memory alloys that must be overcome before they can live up to their full potential. These alloys are still relatively expensive to manufacture and machine compared to other materials such as steel and aluminum. Most SMA's have poor fatigue properties; this means that while under the same loading conditions (i.e. twisting, bending, compressing) a steel component may survive for more than one hundred times more cycles than an SMA element

6. Shape memory materials

These types of materials are those that can revert from the current shape to a previously held shape, usually due to the action of heat. This technology has been
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extensively pioneered by the UK Defence Clothing and Textiles Agency. When these shape memory materials are activated in garments, the air gaps between adjacent layers of clothing are increased, in order to give better insulation. Shape memory alloys, such as nickel-titanium, have been developed to provide increased protection against sources of heat, even extreme heat. A shape memory alloy possesses different properties below and above the temperature at which it is activated. Below this temperature, the alloy is easily deformed. At the activation temperature, the alloy exerts a force to return to a previously adopted shape and becomes much stiffer. The temperature of activation can be chosen by altering the ratio of nickel to titanium in the alloy. Cuprous-zinc alloys are capable of a two-way activation and therefore can produce the reversible variation needed for protection from changeable weather conditions. They will also react to temperature changes brought about by variations in physical activity levels.In practice , a shape memory alloy is usually in the shape of a spring .The spring is flat below the activation temperature but becomes extend above it. Shape Memory polymers have the same effect as the Ni ti but , being polymers, they will potentially be more compatible with textiles. They could also be employed as flame but as they are the thermoplastic polyurethanes they melt at a much lower temperature than the alloys and this limits their use to threats such as hot liquid. The shape memory effect is observed when a plastic conforme to one shape returns at a particular temperature to a previously adopted shape. For clothing application the desirabiles temperatures for the shape memory effect to be tiggred will be near body temperature.

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Conclusions

Shape memory materials are fascinating materials, with potential for application as smart materials and also as new functional materials. Starting from the basic principles of the martensitic transformation, on which the shape memory effect and the superelasticity of alloys are based, the mechanisms of the two phenomena are clearly described , with possible applications. The many uses and applications of shape memory alloys ensure a bright future for these metals. Research is currently carried out at many robotics departments and materials science departments. With the innovative ideas for applications of SMAs and the number of products on the market using SMAs continually growing, advances in the field of shape memory alloys for use in many different fields of study seems very promising.
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References
http://books.google.com/ Shape Memory Materials http://Shape Memory Alloy Shape

http://www.eng.buffalo.edu http://www-2.unipv.it http://webdocs.cs.ualberta.ca

http://smart.tamu.edu

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