Toughening of dicyandiamide-cured DGEBA-based epoxy resins by CTBN liquid rubber

Toughening of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin with liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer has been investigated. For this purpose six blend samples were prepared by mixing DGEBA with different concentrations of CTBN from 0 to 25 phr with an increment of 5 phr. The samples were cured with dicyandiamide curing agent accelerated by Monuron. The reactions between oxirane groups of DGEBA and carboxyl groups of CTBN were followed by Fourier-transform infrared (FTIR) spectroscopy. Tensile, impact, fracture toughness and dynamic mechanical analysis of neat as well as the modified epoxies have been studied to observe the effect of CTBN modification. The tensile strength of the blend systems increased by 26 % when 5 phr CTBN was added, and it remained almost unchanged up to 15 phr of CTBN. The elongation-at-break and Izod notched impact strength increased significantly, whereas tensile modulus decreased gradually upon the addition of CTBN. The maximum toughness of the prepared samples was achieved at optimum concentration of 15 phr of CTBN, whereas the fracture toughness (K _IC) remained stable for all blend compositions of more than 10 phr of CTBN. The glass transition temperature (T _g) of the epoxy resin significantly increased (11.3 °C) upon the inclusion of 25 phr of CTBN. Fractured surfaces of tensile test samples have been studied by scanning electron microscopic analysis. This latter test showed a two-phase morphology where the rubber particles were distributed in the epoxy resin with a tendency towards co-continuous phase upon the inclusion of 25 phr of CTBN.     

Mechanical,thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system

The present study focuses on the preparation of a novel hybrid epoxy nanocomposite with glycidyl polyhedral oligomeric silsesquioxane (POSS) as nanofiller, carboxyl terminated poly(acrylonitrile‐co‐butadiene) (CTBN) as modifying agent and diglycidyl ether of bisphenol A (DGEBA) as matrix polymer. The reaction between DGEBA, CTBN, and glycidyl POSS was carefully monitored and interpreted by using Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC). An exclusive mechanism of the reaction between the modifier, nanofiller, and the matrix is proposed herein, which attempts to explains the chemistry behind the formation of an intricate network between POSS, CTBN, and DGEBA. The mechanical properties, such as tensile strength, and fracture toughness, were also carefully examined. The fracture toughness increases for epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems with respect to neat epoxy, but for hybrid composites toughening capability of soft rubber particles is lost by the presence of POSS. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. The viscoelastic properties of epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems were analyzed using dynamic mechanical thermal analysis (DMTA). The storage modulus shows a complex behavior for the epoxy/POSS composites due to the existence of lower and higher crosslink density sites. However, the storage modulus of the epoxy phase decreases with the addition of soft CTBN phase. The T_g corresponding to epoxy‐rich phase was evident from the dynamic mechanical spectrum. For hybrid systems, the T_g is intermediate between the epoxy/rubber and epoxy/POSS systems. Finally, TGA (thermo gravimetric analysis) studies were employed to evaluate the thermal stability of prepared blends and composites. POLYM. COMPOS., 37:2109–2120, 2016. © 2015 Society of Plastics Engineers     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

Synergistic toughening of epoxy resin by CTBN and CM-β-CD

Carboxymethyl-β-cyclodextrin (CM-β-CD) and carboxyl terminated liquid nitrile rubber (CTBN) were used as binary component fillers in toughening the epoxy resin (E-54). For a single component filler system, the addition of CTBN resulted in significantly improved fracture toughness but reduction of glass transition temperature (T_g) and modulus of epoxy resin. On the other hand, the addition of CM-β-CD resulted in a modest increase in modulus and T_g, and significant improvement in toughness. This work provides a promising route of nanocomposites with excellent toughness. Besides the mechanism of synergistic toughening in this project was explained, and the major toughening mechanisms were attributed to interfacial micro-cracks, energy dissipation of CM-β- CD. This work gives us a further understanding of the modification effect of β- CD.     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Miscibility and mechanical properties of tetrafunctional epoxy resin/phenolphthalein poly(ether ether ketone) blends

Phenolphthalein poly(ether ether ketone) (PEK‐C) was found to be miscible with uncured tetraglycidyl 4,4′‐diaminodiphenylmethane (TGDDM), which is a type of tetrafunctional epoxy resin (ER), as shown by the existence of a single glass transition temperature (T_g) within the whole composition range. The miscibility between PEK‐C and TGDDM is considered to be due mainly to entropy contribution. Furthermore, blends of PEK‐C and TGDDM cured with 4,4′‐diaminodiphenylmethane (DDM) were studied using dynamic mechanical analysis (DMA), Fourier‐transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). DMA studies show that the DDM‐cured TGDDM/PEK‐C blends have only one T_g. SEM observation also confirmed that the blends were homogeneous. FTIR studies showed that the curing reaction is incomplete due to the high viscosity of PEK‐C. As the PEK‐C content increased, the tensile properties of the blends decreased slightly and the fracture toughness factor also showed a slight decreasing tendency, presumably due to the reduced crosslink density of the epoxy network. SEM observation of the fracture surfaces of fracture toughness test specimens showed the brittle nature of the fracture for the pure ER and its blends with PEK‐C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 598–607, 2001     

Synthesis and characterization of bis(4‐cyanato 3,5‐dimethylphenyl) naphthyl methane/epoxy/glass fiber composites

Bis(4‐cyanato 3,5‐dimethylphenyl) naphthylmethane was prepared by treating CNBr with bis(4‐hydroxy 3,5‐dimethylphenyl) naphthylmethane in the presence of triethylamine at −5 to 5°C. The dicyanate was characterized by FT‐IR and NMR techniques. The prepared dicyanate was blended with commercial epoxy resin in different ratios and cured at 120°C for 1 hr, 180°C for 1 hr, and post cured at 220°C for 1 hr using diamino diphenyl methane (DDM) as curing agent. Castings of neat resin and blends were prepared and characterized by FT‐IR technique. The morphology of the blends was evaluated by SEM analysis. The composite laminates were also fabricated from the same composition using glass fiber. The mechanical properties like tensile strength, flexural strength, and fracture toughness were measured as per ASTMD 3039, D 790, and D 5528, respectively. The tensile strength increased with increase in cyanate content (3, 6, and 9%) from 322 to 355 MPa. The fracture toughness values also increased from 0.7671 kJ/m² for neat epoxy resin to 0.8615 kJ/m² for 9% cyanate ester epoxy modified system. The thermal properties were also studied. The 10% weight loss temperature of pure epoxy is 358°C and it increased to 398°C with incorporation of cyanate ester resin. The incorporation of cyanate ester up to 9% loading level does not affect the T_g to a very great extent. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane/epoxy/glass fiber composites

Bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane was prepared by treating CNBr with bis(4‐hydroxy‐3,5‐dimethylphenyl)anisylmethane and blended with commercial epoxy resin in different ratios and cured at 120°C for 2 h, 180°C for 1 h, and postcured at 220°C for 1 h using diamino diphenyl methane as curing agent. Castings of neat resin and blends were prepared and characterized. The composite laminates were also fabricated with glass fiber using the same composition. The tensile strength of the composites increased with increase in cyanate content (3, 6, and 9%) from 322 to 355 MPa. The fracture toughness values also increased from 0.7671 kJ/m², for neat epoxy resin, to 0.8615 kJ/m², for 9% cyanate ester‐modified epoxy system. The 10% weight loss temperature of pure epoxy (358°C) was increased to 390°C by the incorporation of cyanate ester resin. The incorporation of cyanate ester up to 9% in the epoxy resin increases the T_g from 143 to 147°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fracture testing and toughening of epoxy resins

The tapered cantilever cleavage and the single-edge-notch tension fracture toughness tests have been shown to give similar results for several cured epoxy resin systems. Methods for the calculation of fracture energy and critical stress intensity factors are described and discussed. These tests have been used to study the influence of rubber modifiers (“Hycar” CTBN and “Blendex” 311) on the toughness of a conventional epoxy resin (“Epikote” 828) reacted with anhydride curing agents. The modifiers used increase fracture energies and stress intensity factors by factors of approximately 5 and 2 respectively.     

Studies on the curing behavior,thermal, and mechanical properties of epoxy resin-co-amine-functionalized lead phthalocyanine

A high performance copolymer was prepared by using epoxy (EP) resin as matrix and 3,10,17,24-tetra-aminoethoxy lead phthalocyanine (APbPc) as additive with dicyandiamide as curing agent. Fourier-transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetric analysis (DSC), and thermogravimetric analysis (TGA) were used to study the curing behavior, curing kinetics, dynamic mechanical properties, impact and tensile strength, and thermal stability of EP/APbPc blends. The experimental results show that APbPc, as a synergistic curing agent, can effectively reduce the curing temperature of epoxy resin. The curing kinetics of the copolymer was investigated by non-isothermal DSC to determine kinetic data and measurement of the activation energy. DMA, impact, and tensile strength tests proved that phthalocyanine can significantly improve the toughness and stiffness of epoxy resin. Highest values were seen on the 20 wt% loading of APbPc in the copolymers, energy storage modulus, and impact strength increased respectively 388.46 MPa and 3.6 kJ/m², T_g decreased 19.46°C. TGA curves indicated that the cured copolymers also exhibit excellent thermal properties.     

Toughening of epoxy systems by brominated epoxy

Blends of brominated epoxy (BE) and conventional epoxy resins were studied following curing with aliphatic triethylenetetramine (TETA), etheric (polyether diamine‐ PEA4), and aromatic (3,3′‐diamino diphenyl sulfone [DDS]) hardeners. The addition of BE resulted in an increase in T_g in all tested blends. Blends with 50 wt% BE cured with TETA demonstrated an increase in flexural modulus and flexural strength, while preserving the elongation. Blends with 40 wt% BE cured with PEA4 and 50 wt% BE cured with DDS resulted in a significant enhanced tensile elongation. The shear strength of all cured systems decreased moderately with the addition of BE exhibiting a mixed mode failure. Analysis of the fracture morphology using electron microscopy supported the increase of toughness levels as a result of incorporating BE to conventional epoxy. A unique nodular and rough fracture morphology was obtained, which is related to a toughening mechanism caused by the addition of BE. It was concluded that blends of BE and conventional epoxy could be used as structural adhesives having high T_g, enhanced mechanical properties and increased toughness. POLYM. ENG. SCI., 59:206–215, 2019. © 2018 Society of Plastics Engineers     

Studies of thermal,mechanical properties,and kinetic cure reaction of carboxyl-terminated polybutadiene acrylonitrile liquid rubber with diepoxy octane

Epoxy resins, despite their unique properties, have limitations in many applications due to their low fracture toughness. One of the most effective methods to overcome this limitation is to use toughening agents, such as carboxyl terminated poly butadiene-acrylonitrile (CTBN) in the epoxy matrix. CTBN can react with various compounds, such as epoxies. In this study, we investigated the severity of CTBN sedimentation with di epoxy octane (DEO) in the presence basis catalysts. The studied of the physical properties of the synthesized copolymer in the presence of pyridine compared to other catalysts increases mechanical properties (248.43% elongation, 0.63 MPa strength, and 32 hardness with Shore A) and decreases the glass transition temperature (−45.1) of the copolymer. Investigated the cure kinetics of the CTBN-DEO reaction was in the presence of pyridine using a nonisothermal technique of differential scanning calorimetry, and the curing kinetic parameters, such as activation energy (E_a), pre-exponential factor (A), and rate constant (k), were calculated by different kinetic methods. The obtained curing kinetic values with different kinetic methods are well-matched, the E_a values are in the range of 91.3–97.1 kJ.mol⁻¹ and the A values are in the range of 0.48 × 10¹¹–1.51 × 10¹¹ S⁻¹.     

Influence of the Stoichiometric Ratio on the Curing Kinetics and Mechanical Properties of Epoxy Resin Cured with a Rosin-Based Anhydride

Bio-based alternatives for petroleum-based epoxy resin curing agents, such as maleopimaric acid (MPA), are indispensable for sustainable fiber reinforced polymer composites with thermosetting matrices. However, previous investigations disregarded the importance of choosing the right stoichiometric ratio R between the anhydride groups in the rosin-based curing agent and the epoxy groups in the resin. Therefore, the influence of R on the curing kinetics and mechanical properties of an epoxy resin cured with a rosin-based anhydride is studied. Here, Fourier-transform infrared spectroscopy (FT–IR) indicates that for R ⩾ 0.9 unreacted anhydride groups are present in the thermoset. Consequently, the network density decreases and the glass transition temperature T_g drops by about 40 °C. On the other hand, the steric hindrance of unreacted functional groups for R ⩾ 0.9, increases the flexural modulus and the reduced network density improves fracture toughness. The results indicate that the best R for overall high mechanical performance and good processability is preferably low (R ⩽ 0.7). Here, a low R results in a high T_g and good processability due to a low viscosity. However, the latency of the mixtures is low and therefore, the mixtures are not fit for processing via prepreg technology.     

The effect of urea bond on structure and properties of toughened epoxy resins

In this article, modified poly(oxypropylene) diamines were synthesized and used as a new flexible curing agent for epoxy resins. The purpose of modification is to introduce urea group into epoxy resins. The reaction rate, mechanical properties, glass transition temperature (T_g), and fracture surface morphology of these toughened epoxy resins were investigated. Because of urea groups, the reactivity between poly(oxypropylene) diamines and epoxy resins was significantly enhanced. At the same time, the urea groups resulted in strong intersegmental hydrogen bonding between modified poly(oxypropylene) chain, which reduced the compatibility of poly(oxypropylene) with epoxy resins and resulted in higher T_g of toughened epoxy. The modified sample had tensile strength of 15.8 MPa and ultimate elongation of 118% at room temperature, whereas the unmodified sample only had 6.2 MPa and 70%. The scanning electron microscope analysis showed that the modified system displayed tough fracture feature, whereas the unmodified system showed typical brittle fracture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyester hot-melt adhesives. I. Factors affecting adhesion to epoxy resin coatings

The peel strength and tensile shear strength of polyester hot-melt adhesives on metals coated with epoxy resins are affected by four characteristics of the polyester: (1) inherent viscosity, (2) glass transition temperature (T_g), (3) degree of crystallinity, and (4) melting point. The inherent viscosity affects the strength, toughness, and crystallinity of the adhesive. The T_g and degree of crystallinity affect the low-temperature adhesive properties; the peel strength is relatively low when the T_g is appreciably above the use temperature. The T_g, degree of crystallinity, and melting point affect the high-temperature adhesive properties. A hot-melt adhesive with high peel and tensile shear strengths from 0° to 120°C is the polyester of 1,4-butanediol and trans-1,4-cyclohexanedicarboxylic acid.     

Study of morphological and mechanical performance of amine‐cured glassy epoxy–clay nanocomposites

The effect of three different alkylammonium‐modified montmorillonite on morphological and mechanical properties of glassy epoxy‐amine nanocomposites is reported. Small amounts of clays <10 phr (part per hundred of resin) were used in each system of nanocomposite. The morphology of the prepared nanocomposites was performed by means of X‐ray diffraction and transmission electron microscopy. Differential scanning calorimetry (DSC) was used to investigate the glass transition temperatures (T_g). Mechanical properties were based on tensile characteristics (Young's modulus), impact strength, and fracture toughness. The measured moduli were compared to theoretical predictions. Scanning electron microscopy was used to study the morphological structure of the fracture surfaces of impacted specimens. It was found that at a low content of 2 phr (1.2 wt %) of nanoclays, the impact strength and the fracture toughness were improved by 77 and 90% respectively, comparatively to the neat epoxy, whereas DSC revealed a reduction of the T_g of nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal Properties,Fracture Toughness and Water Absorption of Epoxy-Palm Oil Blends

Epoxidized palm oil (EPO) was blended with cycloaliphatic epoxide, epoxy novolac and diglycidyl ethers of bisphenol-A. The fracture toughness and thermal properties of epoxy/EPO blends were characterized using single-edge notched bending tests and differential scanning calorimetry. Increased EPO loading improved the fracture toughness (K _IC ) of the epoxy blends. The epoxy blends with higher EPO loading exhibited higher degree of conversion. The glass transition temperature (T _g ) of the epoxy blends shifted to higher temperature as the increasing of DSC heating rate. Water absorption caused T _g reduction of epoxy blends but it was determined that the water molecules absorbed were totally reversible.     

Toughening of semi-IPN structured epoxy using a new PEEK-type polymer via in situ azide–alkyne click polymerization

A new poly(ether ether ketone)-type polymer prepared from 1,4-bis(azidomethyl)benzene (p-BAB), 4,4′-bis(2-propynyloxy)benzophenone (PBP) or 4,4′-sulfonylbis(propynyloxy)-benzene (SBP) via azide–alkyne click polymerization was used as a toughening agent to improve the fracture toughness, thermal stability of the toughened epoxy and reduce its viscosity during processing. The epoxy was toughened by the polymer [poly(p-BAB/PBP)] via in situ polymerization during the curing process, which largely decreased viscosity during the epoxy mixing process compared to that of a neat epoxy. The fracture toughness of 5 wt % poly(p-BAB/PBP) toughened epoxy is two times higher than that of the neat epoxy, and even higher than that of the polyethersulfone-type [poly(p-BAB/SBP)] toughened epoxy using the same amount of toughening agents. In addition, the T _g of this toughened epoxy is higher than that of engineering plastic, which could be regarded as the evidence for the excellent thermal resistance. These phenomena might be attributed to the formation of semi-interpenetrating polymer networks composed by the epoxy network and the linear poly(p-BAB/PBP). In situ poly(p-BAB/PBP) has unique advantages such as decreased viscosity and improved thermal stability in comparison with in situ poly(p-BAB/SBP). These features are significant for the development of carbon-fiber-reinforced plastics as alternate materials to metals. Therefore, in situ poly(p-BAB/PBP) is a promising toughener for epoxy systems. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48178.     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Investigation of readily processable thermoplastic-toughened thermosets. III. Toughening BMIs and epoxy with a comb-shaped imide oligomer

This is the third in a five-part series describing the preparation of tough, high-performance thermosets from low viscosity, autoclave-processable prepolymers. The first 2 articles described toughening of bismaleimides (BMI) and epoxy with linear imide thermoplastics of ∼ 1000 g/mol. Highly processable prepolymers were obtained, which resulted in increases in fracture toughness for BMI of ∼ 75–100%, while the fracture toughness of epoxy was increased by up to 220%. This article describes the preparation of a low-molecular-weight comb-shaped imide oligomer (∼ 4100 g/mol) and the effect of the oligomer architecture and end-group on BMI and epoxy prepolymer viscosity and fracture toughness. When an unreactive comb-shaped oligomer was incorporated in a BMI prepolymer (10% thermoplastic loading in the thermoset), the fracture toughness increased by 67% over that of an untoughed control, while a reactive oligomer increased the fracture toughness by 150% over an untoughened control. At 55°C, the viscosity of the solution of the reactive comb-shaped imide in B was only 6.2 Pa · S. When the oligomer was dissolved in epoxy resin, the viscosity was less than 0.2 Pa · S at 90°C, and the fracture toughness increased by 110 and 133% (at ∼ 13% loading in the thermoset), relative to an untoughened control, depending on the reactivity of the end group. The T_g and high-temperature modulus of BMI and epoxy remained approximately the same relative to the untoughened controls. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 943–951, 1998