SILK
Introduction
Silk is a natural protein fiber primarily obtained from the larvae of Bombyx mori, a species of
moth. Other types of silk are produced by Antheraea pernyi (Chinese Tussah moth) and
Antheraea mylitta (Indian Tussah moth).
Life Cycle of Bombyx mori (50 days):
Feeding: Larvae exclusively feed on mulberry leaves for 30 days, increasing their mass by ~100
times.
Cocoon Formation: Spinning begins when silk glands are filled.
Movement: Head moves in a figure-eight pattern to form a cocoon over 3–6 days.
Filaments: Two fibroin filaments bound by sericin (15–25 µm for Bombyx mori, ~65 µm for
Tussah silk).
The length of silk filament per cocoon: 1–2 km.
Without intervention, the moth emerges by softening the cocoon using an enzyme, which
damages the silk. To prevent this, cocoons are stifled with hot air (~110°C) for several hours.
Post-Processing:
Drying: Removes moisture.
Degumming: Removes sericin using soap solutions, proteolytic enzymes, or dilute alkalis/acids.
Bleaching: Conducted using hydrogen peroxide.
Chemical Composition of Silk
Silk fibroin is a protein composed primarily of amino acids, such as glycine, alanine, and serine
(over 80% of total residues).
Key Structural Features:
High glycine content (~50 mol%) in Bombyx mori. Tussah silk contains more alanine than
glycine.
Repetitive glycine–alanine segments enable β-pleated sheet crystallinity (~70%).
Fibroin structure:
H-chain (350,000 relative molar mass)
L-chain (25,000 relative molar mass)
Linked by disulfide bridges.
Bleaching of Silk
Purpose: Removes residual pigments causing a yellowish tint.
Agents:
Oxidative: Hydrogen peroxide (pH 8–9), sodium perborate, sodium persulfate.
Reductive: Sodium dithionite (neutral to mildly acidic pH).
Chemical Reactions of Silk
1. Acid and Alkali Treatments:
Hydrolysis of fibroin chains, especially at pH extremes.
Moderate hydrolysis in the pH range of 4–8.
Dilute organic acids (e.g., citric acid) enhance the "scroop" effect.
2. Oxidation:
Peptide bond cleavage and tyrosine oxidation using agents like hydrogen peroxide.
Cross-linking forms between amino groups and oxidized tyrosine residues.
3. Cross-Linking:
Agents like methanal or diepoxides enhance properties like crease resistance.
Alkali-induced lysinoalanine cross-links improve washability.
4. Reactive Dyes:
Applied via nucleophilic substitution or addition reactions on hydroxyl and amine groups.
5. Action of Light:
Photochemical degradation leads to yellowing and mechanical property loss.
Silk Weighting
Weight loss (up to 25%) occurs during degumming.
Traditional weighting (tin salts) is now replaced by grafting methacrylic acid or methyl
methacrylate for environmental and mechanical benefits.
3.4.6 Properties of Bombyx mori Silk
Mechanical Properties:
Tenacity: 38 cN tex⁻¹ (reduced by 20% when wet).
Elongation: ~23% (dry), up to 38% (wet).
Elastic Recovery: ~50% from 10% stretch.
Resilience: High.
Abrasion Resistance: Moderate.
Moisture Regain: 10–11%.
Launderability: Requires gentle washing.
Applications:
Luxury textiles (e.g., haute couture, scarves, ties).
Medical uses (e.g., sutures, wound dressings).
SPIDER SILK
Introduction
Spider silk is a protein filament secreted by spiders for web construction.
Properties and Applications:
Combination of high tenacity and extensibility (e.g., bulletproof vests).
Dragline silk: Strong and tough for structural web components.
Viscid silk: Highly extensible, used in spiral web formation.
Aciniform silk: Wraps prey.
Challenges in Production:
Spiders are solitary, predatory, and produce less silk than silkworms.
Alternatives: Genetically engineered silkworms, bacteria, or goats producing spider silk proteins.
Chemical Composition of Spider Silk
Composed of spidroin 1 and spidroin 2 proteins (relative molar mass: 280,000–300,000).
High glycine and alanine content; minimal cystine.
Proline content varies: Higher in viscid silks for extensibility.
Structural Properties:
Crystals of β-sheets form from alanine segments.
Proline segments are amorphous, contributing to flexibility.
Mechanical Properties
Spider silk exhibits remarkable mechanical properties, which vary depending on the type of silk:
Dragline Silk:
Tenacity: 40–220 cN tex⁻¹
Elongation: 10–40%
Initial Modulus: 800–2200 cN tex⁻¹
Viscid Silk:
Tenacity: 10–40 cN tex⁻¹
Elongation: Up to 200%
Initial Modulus: ≤100 cN tex⁻¹
Aciniform Silk:
Tenacity: 25–100 cN tex⁻¹
Elongation: 40–50%
Initial Modulus: 40–45 cN tex⁻¹
Comparison with p-Aramid (e.g., Kevlar®):
Tenacity: 190–240 cN tex⁻¹
Elongation: 1–4%
Initial Modulus: 3800–7800 cN tex⁻¹
Summary:
Dragline silk rivals synthetic fibers like Kevlar® in tenacity but offers significantly higher
extensibility, making it an outstanding natural material.