Polyamide-imide
Encyclopedia
Polyamide-imides are thermoplastic amorphous polymer
s that have exceptional mechanical, thermal and chemical resistant properties. These properties put polyamide-imides at the top of the price and performance pyramid. Polyamide-imides are produced by Solvay Advanced Polymers under the trademark Torlon. Other high-performance polymers in this same realm are polyetheretherketones and polyimide
s.
Polyamide-imides hold, as the name suggests, a positive synergy of properties from both polyamide
s and polyimides, such as high strength, melt processibility, exceptional high heat capability, and broad chemical resistance. Polyamide-imide polymers can be processed into a wide variety of forms – from injection or compression molded parts and ingots – to coatings, films, fibers and adhesives. Generally these articles reach their maximum properties with a subsequent thermal cure process.
(NMP), dimethylacetamide
(DMAC), dimethylformamide
(DMF), or dimethylsulfoxide (DMSO) at temperatures between 20-60°C. The byproduct HCl must be neutralized in situ or removed by washing it from the precipitated polymer. Further thermal treatment of the polyamideimide polymer increases molecular weight and causes the amic acid groups to form imides with the evolution of water.
methylenediphenyldiisocyanate (MDI), is reacted with trimellitic anhydride (TMA). The product achieved at the end of this process is a high molecular weight, fully imidized polymer solution with no condensation byproducts, since the carbon dioxide gas byproduct is easily removed. This form is convenient for the manufacture of wire enamel or coatings. The solution viscosity is controlled by stoichiometry, monofunctional reagents, and polymer solids. The typical polymer solids level is 35-45% and it may be diluted further by the supplier or user with diluents.
The PAI enamel is very thermally stable as well as abrasion and chemical resistant. PAI is often used over polyester wire enamels to achieve higher thermal ratings.
PAI is also used in decorative, corrosion resistant coatings for industrial uses, often in conjunction with fluoropolymers. The PAI aids in adhering the fluoropolymer to the metal substrate. They also find usage in non-stick cookware coatings. While solvents can be used, some water-borne systems are used. These are possible because the amide-imide contains acid functionality.
dryer capable of maintaining a dew point of -40°F (-40°C) is recommended. If drying is done in pans or trays, put the resin in layers no more than 2 to 3 inches (5 to 8 cm) deep in drying trays. Dry for 24 hours at 250°F, or 16 hours at 300°F, or 8 hours at 350°F. If drying at 350°F (177°C), limit drying time to 16 hours. For the injection molding press,a desiccant hopper dryer is recommended. The circulating air suction pipe should be at the base of the hopper, as near the feed throat as possible. During extended runs, keep the resin covered and re-dry if necessary.
The mold temperature should be in the range of 325°F to 425°F (163°C to 218°C).
Polymer
A polymer is a large molecule composed of repeating structural units. These subunits are typically connected by covalent chemical bonds...
s that have exceptional mechanical, thermal and chemical resistant properties. These properties put polyamide-imides at the top of the price and performance pyramid. Polyamide-imides are produced by Solvay Advanced Polymers under the trademark Torlon. Other high-performance polymers in this same realm are polyetheretherketones and polyimide
Polyimide
Polyimide is a polymer of imide monomers. The structure of imide is as shown. Polyimides have been in mass production since 1955...
s.
Polyamide-imides hold, as the name suggests, a positive synergy of properties from both polyamide
Polyamide
A polyamide is a polymer containing monomers of amides joined by peptide bonds. They can occur both naturally and artificially, examples being proteins, such as wool and silk, and can be made artificially through step-growth polymerization or solid-phase synthesis, examples being nylons, aramids,...
s and polyimides, such as high strength, melt processibility, exceptional high heat capability, and broad chemical resistance. Polyamide-imide polymers can be processed into a wide variety of forms – from injection or compression molded parts and ingots – to coatings, films, fibers and adhesives. Generally these articles reach their maximum properties with a subsequent thermal cure process.
Chemistry
The currently popular commercial methods to synthesize polyamide-imides are the acid chloride route and the isocyanate route.Acid chloride route
The earliest route to polyamide-imides is the condensation of an aromatic diamine, such as methylene dianiline (MDA) and trimellitic acid chloride (TMAC). Reaction of the anhydride with the diamine produces an intermediate amic acid. The acid chloride functionality reacts with the aromatic amine to give the amide bond and hydrochloric acid (HCl) as a by-product. In the commercial preparation of polyamideimides, the polymerization is carried out in a dipolar, aprotic solvent such as N-methylpyrrolidoneMethylpyrrolidone
N-Methyl-2-pyrrolidone is a chemical compound with 5-membered lactam structure. It is a clear to slightly yellow liquid miscible with water and solvents like ethyl acetate, chloroform, benzene and lower alcohols or ketones. It also belongs to the class of dipolar aprotic solvents which includes...
(NMP), dimethylacetamide
Dimethylacetamide
Dimethylacetamide is the organic compound with the formula CH3CN2. This colorless, water miscible, high boiling liquid is commonly used as a polar solvent in organic chemistry. DMAc is miscible with most other solvents, although it is poorly soluble in aliphatic hydrocarbons.The chemical reactions...
(DMAC), dimethylformamide
Dimethylformamide
Dimethylformamide is an organic compound with the formula 2NCH. Commonly abbreviated as DMF , this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions...
(DMF), or dimethylsulfoxide (DMSO) at temperatures between 20-60°C. The byproduct HCl must be neutralized in situ or removed by washing it from the precipitated polymer. Further thermal treatment of the polyamideimide polymer increases molecular weight and causes the amic acid groups to form imides with the evolution of water.
Diisocyanate Route
This is the primary route to polyamide-imides which are used as wire enamels. A diisocyanate, often 4,4’-methylenediphenyldiisocyanate (MDI), is reacted with trimellitic anhydride (TMA). The product achieved at the end of this process is a high molecular weight, fully imidized polymer solution with no condensation byproducts, since the carbon dioxide gas byproduct is easily removed. This form is convenient for the manufacture of wire enamel or coatings. The solution viscosity is controlled by stoichiometry, monofunctional reagents, and polymer solids. The typical polymer solids level is 35-45% and it may be diluted further by the supplier or user with diluents.
Coatings
The product used mainly for coatings is sold in a powdered form and is roughly 50% imidized. One of the major uses is as a magnet wire enamel. The magnet wire enamel is made by dissolving the PAI powder in a strong, aprotic solvent such as N-methyl pyrrolidone. Diluents and other additives can be added to provide the correct viscosity for application to the copper or aluminum conductor. Application is typically done by drawing the conductor through a bath of enamel and then through a die to control coating thickness. The wire is then passed through an oven to drive off the solvent and cure the coating. The wire usually is passed through the process several times to achieve the desired coating thickness.The PAI enamel is very thermally stable as well as abrasion and chemical resistant. PAI is often used over polyester wire enamels to achieve higher thermal ratings.
PAI is also used in decorative, corrosion resistant coatings for industrial uses, often in conjunction with fluoropolymers. The PAI aids in adhering the fluoropolymer to the metal substrate. They also find usage in non-stick cookware coatings. While solvents can be used, some water-borne systems are used. These are possible because the amide-imide contains acid functionality.
Molded or Machined Articles
The polyamide-imides used for molded articles are also based on aromatic diamines and trimellitic acid chloride, but the diamines are different from those used in the products used for coatings and the polymer is more fully imidized prior to compounding and pellitizing. Resins for injection molding include unreinforced, glass-fiber reinforced, carbon fiber reinforced, and wear resistant grades. These resins are sold at a relatively low molecular weight so they can be melt processed by extrusion or injection-molding. The molded articles are then thermally treated for several days at temperatures up to 260°C (500°F). During this treatment, commonly referred to a postcure, the molecular weight increases through change extension and the polymer get much stronger and more chemically resistant. Prior to postcure, parts can be reground and reprocessed. After postcure, reprocessing is not practical.High-strength Grades
Property | Test Method | units | neat PAI | 30% GF PAI | 30% CF PAI |
---|---|---|---|---|---|
Tensile Strength | ASTM D 638 | MPa (kpsi) | 152 (22.0) | 221 (32.1) | 221 (32.0) |
Tensile Modulus | ASTM D 638 | GPa (kpsi) | 4.5 (650) | 14.5 (2,110) | 16.5 (2,400) |
Tensile Elongation | ASTM D 638 | % | 7.6 | 2.3 | 1.5 |
Flexural Strength | ASTM D 790 | MPa (kpsi) | 241 (34.9) | 333 (48.3) | 350 (50.7) |
Flexural Modulus | ASTM D 638 | GPa (kpsi) | 5.0 (730) | 11.7 (1,700) | 16.5 (2,400) |
Compressive Strength | ASTM D 695 | MPa (kpsi) | 221 (32.1) | 264 (38.3) | 254 (36.9) |
Shear Strength | ASTM D 732 | MPa (kpsi) | 128 (18.5) | 139 (20.1) | 119 (17.3) |
Izod Impact Strength | ASTM D 256 | J/m (ftlb/in) | 144 (2.7) | 80 (1.5) | 48 (0.9) |
Izod Impact Strength-Unnotched | ASTM D 4812 | J/m (ftlb/in) | 1070 (20) | 530 (10) | 320 (6) |
Heat Deflection Temperature @ 264 psi | ASTM D 648 | °C (°F) | 278 (532) | 282 (540) | 282 (540) |
Coefficient Linear Thermal Expansion | ASTM D 696 | ppm/°C (ppm/°F) | 31 (17) | 16 (9) | 9 (5) |
Volume Resistivity | ASTM D 257 | ohm-cm | 2e17 | 2e17 | |
Specific Gravity | ASTM D 792 | 1.42 | 1.61 | 1.48 | |
Water Absorption, 24 hr | ASTM D 570 | % | 0.33 | 0.24 | 0.26 |
Wear-Resistant PAI Grades
Property | Test Method | units | 4275 | 4301 | 4435 | 4630 | 4645 |
---|---|---|---|---|---|---|---|
Tensile Strength | ASTM D 638 | MPa (kpsi) | 117 (16.9) | 113 (16.4) | 94 (13.6) | 81 (11.8) | 114 (16.6) |
Tensile Modulus | ASTM D 638 | GPa (kpsi) | 8.8 (1,280) | 6.8 (990) | 14.5 (2,100) | 7.4 (1,080) | 18.6 (2,700) |
Tensile Elongation | ASTM D 638 | % | 2.6 | 3.3 | 1.0 | 1.9 | 0.8 |
Flexural Strength | ASTM D 790 | MPa (kpsi) | 208 (30.2) | 215 (31.2) | 152 (22.0) | 131 (19.0) | 154 (22.4) |
Flexural Modulus | ASTM D 790 | GPa (kpsi) | 7.3 (1.060) | 6.9 (1,000) | 14.8 (2,150) | 6.8 (990) | 12.4 (1,800) |
Compressive Strength | ASTM D 695 | MPa (kpsi) | 123 (17.8) | 166 (24.1) | 138 (20.0) | 99 (14.4) | 157 (22.8) |
Izod Impact Strength, Notched | ASTM D 256 | J/m (ft-lb/in) | 85 (1.6) | 64 (1.2) | 43 (0.8) | 48 (0.9) | 37 (0.7) |
Izod Impact Strength, Unnotched | ASTM D 4812 | J/m (ft-lb/in) | 270 (5) | 430 (8) | 210 (4) | 160 (3) | 110 (2) |
Heat Deflection Temperature at 264 psi | ASTM D 648 | °C (°F) | 280 (536) | 279 (534) | 278 (532) | 280 (536) | 281 (538) |
Coefficient Linear Thermal Expansion | ASTM D 696 | ppm/°C (ppm/°F) | 25 (14) | 25 (14) | 14 (8) | 16 (9) | 9 (3) |
Pre-drying the resin
PAI resin is hygroscopic, and will pick up ambient moisture. Before processing PAI resin, drying is required to avoid brittle parts, foaming, and other molding problems. The resin must be dried to a moisture content of 500 ppm or less. A desiccantDesiccant
A desiccant is a hygroscopic substance that induces or sustains a state of dryness in its local vicinity in a moderately well-sealed container....
dryer capable of maintaining a dew point of -40°F (-40°C) is recommended. If drying is done in pans or trays, put the resin in layers no more than 2 to 3 inches (5 to 8 cm) deep in drying trays. Dry for 24 hours at 250°F, or 16 hours at 300°F, or 8 hours at 350°F. If drying at 350°F (177°C), limit drying time to 16 hours. For the injection molding press,a desiccant hopper dryer is recommended. The circulating air suction pipe should be at the base of the hopper, as near the feed throat as possible. During extended runs, keep the resin covered and re-dry if necessary.
Injection molding equipment
In general, modern reciprocating-screw injection molding presses with microprocessor controls capable of closed-loop control are recommended for molding PAI. The press should be fitted with a low compression ratio, constant taper screw. The compression ratio should be between 1.1 and 1.5 to 1, and no check device should be used.Starting point temperatures
Zone | Temp, °F | Temp, °C |
---|---|---|
Feed Zone | 580 | 304 |
Middle Zone | 620 | 327 |
Front Zone | 650 | 343 |
Nozzle | 700 | 371 |
The mold temperature should be in the range of 325°F to 425°F (163°C to 218°C).