Morphology and properties of nylon6 and high density polyethylene blends in absence and presence of nanoclay

The morphology and properties of nylon6/HDPE blends without and with nanoclay has been reported. Scanning electron microscopy study of the (70/30 w/w) nylon6/HDPE blends with small amount (0.1 phr) of nanoclay indicated a reduction in the average domain sizes (D) of dispersed HDPE phase and hence better extent of mixing compared to the blend without any nanoclay. X‐ray diffraction study and transmission electron microscopy revealed that nanoclay layers were mostly located in nylon6 matrix of the (70/30 w/w) nylon6/HDPE blend. However, the same effect of nanoclay on the morphology was not observed in (30/70 w/w) nylon6/HDPE blend where HDPE became the matrix. In (30/70 w/w) nylon6/HDPE blend, addition of nanoclay increased the D of dispersed nylon6 domains by preferential location of the clays in side the nylon6 domains. Thus, the clay platelets in the matrix phase acted as barrier that restricted the coalescence of dispersed domains during melt‐mixing. Addition of PE‐g‐MA in both the compositions of nylon6/HDPE blend effectively reduced the D of dispersed phases. Storage modulus and thermal stability of the blend were improved in presence of small amount of clay, whereas addition of PE‐g‐MA lowered the mechanical and thermal properties of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of clay modification on the morphology and the mechanical/physical properties of ABS/PMMA blends

The effect of three types of organoclays on the morphology and mechanical properties of lower critical solution temperature‐type poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. Polymers were melt‐compounded with 2 and 4 wt % of clays using a twin‐screw extruder. X‐ray scattering and transmission electron microscopy revealed that the intercalation of the nanoclay in the hybrid nanocomposite was more affected by the polarity of the organoclay. Although the morphology of the blends varied by PMMA content, scanning electron microscopy showed smaller PMMA domains for the hybrid systems containing clay particles. Although good dispersion of the nanoclay through the ABS matrix and at the blend interface led to enhancement of tensile strength, the increment of the stiffness was more noticeable for nanocomposites including less polar organoclay. Well‐dispersed clay platelets increased the glass transition temperature. In addition, nanoscratching analysis illustrated an improvement in scratch resistance of ABS because of the presence of PMMA and organoclay. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A study on weld line morphology and mechanical strength of injection molded polystyrene/poly(methyl methacrylate) blends

In this work, the mechanical strength and weld line morphology of injection molded polystyrene/poly(methyl methacrylate) (PS/PMMA) blends were investigated by scanning electron microscopy (SEM) and mechanical property test. The experimental results show that the tensile strength of PS/PMMA blends get greatly decreased due to the presence of the weld line. Although the tensile strength without the weld line of PS/PMMA (70/30) is much higher than that of the PS/PMMA (30/70) blend, their tensile strength with weld line shows reversed change. The viscosity ratio of dispersed phase over matrix is a very important parameter for control of weld‐line morphology of the immiscible polymer blend. In PS/PMMA (70/30) blend, the PMMA dispersed domains at the core of the weld line are spherically shaped, which is the same as bulk. While in the PS/PMMA (30/70) blend, the viscosity of the dispersed PS phase is lower than that of the PMMA matrix, the PS phase is absent at the weld line, and PS particles are highly oriented parallel to the weld line, which is a stress concentrator. This is why weld line strength of PS/PMMA (30/70) is lower than that of PS/PMMA (70/30) blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1856–1865, 2002; DOI 10.1002/app.10450     

Cocontinuous phase morphology of asymmetric compositions of polypropylene/high‐density polyethylene blend by the addition of clay

A novel method of developing cocontinuous morphology in 75/25 and 80/20 w/w polypropylene/high density polyethylene (PP/HDPE) blends in the presence of small amount (0.5 phr) of organoclay has been reported. SEM study indicated a reduction in average domain sizes (D) of disperse HDPE when PP, HDPE, and the organoclay were melt‐blended simultaneously at 200°C. However, when the two‐sequential heating protocol was employed, (that is, the organoclay was first intercalated by HDPE chains at 150°C, followed by melt blending of PP at 200°C), very interestingly a cocontinuous morphology was found even for very asymmetric blend compositions. WAXD study revealed the intercalation of both PP and HDPE chains inside the clay galleries, when PP/HDPE and clay were melt‐mixed together at 200°C. However, when the two‐sequential heating protocol was used the organoclay platelets were selectively intercalated by the HDPE chains. Addition of SEPS in the blend decreased the D of HDPE domains in both the blending methods. Thus, the observed cocontinuous morphology in asymmetric composition of PP/HDPE blend in presence of clay is because of the barrier effect of the clay platelets in the HDPE phase that restrict the phase inversion into the domain/matrix morphology. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of PE-g-MA-Compatibilizer on the Morphology and Mechanical Properties of 70/30 HDPE/ENR Blends

The effects of PE-g-MA as a compatibilizer in binary blends of 70/30 high-density polyethylene/epoxidized natural rubber (HDPE/ENR) have been investigated by means of mechanical analysis and scanning electron microscopy. The special emphasis was given to the role of PE-g-MA in inducing interactions between HDPE and ENR. It has been observed that increasing the amount of PE-g-MA in the blend increases the tensile strength, elongation at break, and impact strength. It is believed that the degree of cross-link increased, which led to improve the interaction between the HDPE and ENR. The optimum stress values are shown in the blend containing 6% PE-g-MA. Scanning electron micrographs (SEM) of the samples also indicated that the addition of compatibilizer decreases the domain size of the dispersed phase. Well-dispersed plastic particles in a rubber matrix were strongly indicated in these samples. The results obtained reveal that the addition of PE-g-MA in HDPE/ENR blend led to an increase in the homogeneity of the blends.     

Compatibilization Mechanism of Nanoclay in Immiscible PS/PMMA Blend Using Unmodified Nanoclay

Organically modified nanoclays have been reported to play the role of a compatibilizer for immiscible polymer blends. However, the mechanism of compatibilization by nanoclay has been reported differently. In this work, we investigated the exact mechanism of compatibilization of nanoclay in immiscible polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend in the presence of sodium-montmorillonite (Na-MMT) through selective dispersion of clay in the matrix phase. Through a detailed investigation of the morphology of PS/PMMA/Na-MMT blend nanocomposites, the plausible mechanism behind the compatibilization effect of clay in immiscible blends has been proposed.     

Effects of dynamic vulcanization on the physical,mechanical, and morphological properties of high‐density polyethylene/(natural rubber)/(thermoplastic tapioca starch) blends

Blending of high density polyethylene (HDPE), natural rubber (NR), and thermoplastic tapioca starch (TPS) have been studied. Two series of samples having 5–30 wt% of TPS were prepared: (a) unvulcanized blends (control) and (b) dynamically vulcanized HDPE/NR/TPS blends. The composition of the HDPE/NR was constant and fixed at a blend ratio of 70/30. Morphology studies by SEM showed that the TPS particles were homogeneously dispersed and well‐embedded in vulcanized HDPE/NR matrix. The SEM micrographs showed agreement with the tensile strength and elongation at break values. Tensile strength improved significanly when the HDPE/NR/TPS blends were vulcanized by using sulfur curative system. The enhancement in tensile properties is attributed to the crosslinking reaction within the NR phase. J. VINYL ADDIT. TECHNOL., 18:192–197, 2012. © 2012 Society of Plastics Engineers     

Effect of organoclays on the rheological and morphological properties of poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate)/ clay nanocomposites

Using the rheological measurements, the effect of three types of organoclays on the morphology and nanoclay dispersion in the poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. For this purpose, polymers were melt blended with 2 and 4 wt% of organoclays in a twin‐screw extruder. Structural analysis of the blends and nanocomposites through the rheometery, theoretical approach, X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy revealed that the clay content and interaction level between clays and the polymers dominated the morphology. While the morphology of the blends varied by PMMA content, smaller PMMA domains were observed for blends containing clay particles. Better‐interacted and intercalated nanoclays were mainly located within the interface at lower content. While, at higher content, they tended to migrate into the dispersed phase. Theoretical calculations of interfacial tensions and wetting coefficients confirmed this kind of migration. POLYM. COMPOS., 33:1893–1902, 2012. © 2012 Society of Plastics Engineers     

Blends of high density polyethylene and ethylene/1‐octene copolymers: Structure and properties

The morphology formation in the blends comprising a high density polyethylene (HDPE) and selected ethylene/1‐octene copolymers (EOCs) was studied with variation of blend compositions using atomic force microscopy (AFM). The binary HDPE/EOC blends studied showed well phase‐separated structures (macrophase separation) in consistence with individual melting and crystallization behavior of the blend components. For the blends comprising low 1‐octene content copolymers, the lamellar stacks of one of the phases were found to exist side by side with that of the another phase giving rise to leaflet vein‐like appearance. The formation of large HDPE lamellae particularly longer than in the pure state has been explained by considering the different melting points of the blend components. The study of strain induced structural changes in an HDPE/EOC blend revealed that at large strains, the extensive stretching of the soft EOC phase is accompanied by buckling of HDPE lamellar stack along the strain axis and subsequent microfibrils formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1887–1893, 2007     

Dynamic mechanical behavior of high‐density polyethylene/ethylene vinyl acetate copolymer blends: The effects of the blend ratio,reactive compatibilization,and dynamic vulcanization

The effects of the blend ratio, reactive compatibilization, and dynamic vulcanization on the dynamic mechanical properties of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends have been analyzed at different temperatures. The storage modulus of the blend decreases with an increase in the EVA content. The loss factor curve shows two peaks, corresponding to the transitions of HDPE and EVA, indicating the incompatibility of the blend system. Attempts have been made to correlate the observed viscoelastic properties of the blends with the blend morphology. Various composite models have been used to predict the dynamic mechanical data. The experimental values are close to those of the Halpin–Tsai model above 50 wt % EVA and close to those of the Coran model up to 50 wt % EVA in the blend. For the Takayanagi model, the theoretical value is in good agreement with the experimental value for a 70/30 HDPE/EVA blend. The area under the loss modulus/temperature curve (LA) has been analyzed with the integration method from the experimental curve and has been compared with that obtained from group contribution analysis. The LA values calculated with group contribution analysis are lower than those calculated with the integration method. The addition of a maleic‐modified polyethylene compatibilizer increases the storage modulus, loss modulus, and loss factor values of the system, and this is due to the finer dispersion of the EVA domains in the HDPE matrix upon compatibilization. For 70/30 and 50/50 blends, the addition of a maleic‐modified polyethylene compatibilizer shifts the relaxation temperature of both HDPE and EVA to a lower temperature, and this indicates increased interdiffusion of the two phases at the interface upon compatibilization. However, for a 30/70 HDPE/EVA blend, the addition of a compatibilizer does not change the relaxation temperature, and this may be due to the cocontinuous morphology of the blends. The dynamic vulcanization of the EVA phase with dicumyl peroxide results in an increase in both the storage and loss moduli of the blends. A significant increase in the relaxation temperature of EVA and a broadening of the relaxation peaks occur during dynamic vulcanization, and this indicates the increased interaction between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2083–2099, 2003     

Morphological,mechanical, tribological,and thermal expansion properties of organoclay reinforced polyethylene composites

The morphological, mechanical, thermal, and tribological properties of high‐density polyethylene (HDPE) composites reinforced with organo‐modified nanoclay (3 and 6 wt%) were studied. A commercial maleic anhydride‐based polymeric compatibilizer (PEgMA) was used to improve the adhesion between the polyethylene and clay. Transmission electron microscopy (TEM) characterization of composites revealed that nanoclay exists mainly in a multilayered structure in the HDPE matrix. Mechanical testing of composites showed that Young's modulus and tensile strength increased with nanoclay content. Coefficients of the linear thermal expansion (CLTE) of HDPE–PEgMA–clay composites were slightly lower in the flow direction than those of HDPE–PEgMA. The tribological properties were measured in dry conditions against a steel counterface. The friction coefficient of the matrix was decreased by the addition of clay. Electron microscopic results suggested that the wear mechanism for HDPE and HDPE composites was mainly adhesive. Clay agglomerates were observed on the worn surfaces of the composites, which may partly explain decreased friction. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Alteration of the mechanical and thermal properties of nylon 6/nylon 6,6 blends by nanoclay

Nylon 6 [N(6)], nylon 6,6 [N(6,6)], and their blends at different clay loadings were prepared. The mix was melted and injected into strip‐shaped samples. Mechanical and thermal analyses were performed to investigate the effect of blending and the incorporated clay on the mechanical and thermal properties. Enhancements in the Young's modulus and hardness were obtained for all of the nanocomposites, with a 55% increase in Young's modulus after the addition of 6 wt % nanoclay, although the improvement in tensile strength depended on the blend ratio, with greatest effects on the 50% N(6)/50% N(6,6) blend with increases of 44 and 59% for 2 and 4% clay loadings, respectively. Thermogravimetric analysis showed an enhancement in the thermal properties in the 50% N(6)/50% N(6,6) blend at 2% clay loading, and the blend exhibited ductile behavior at this loading. Increases in the crystallization peak temperatures of 10–15° in N(6,6) and the two blends 30% N(6)/70% N(6,6) and 50% N(6)/50% N(6,6) were observed after the addition of the clay. The nanoclay enhanced the γ‐/β‐form crystals in N(6) and N(6,6) neat polymers and also in the blends. Fourier transform infrared spectroscopy FT‐IR revealed the formation of hydrogen bonding and the possible formation of ionic bonds between the polymers and the nanoclay, which resulted in enhancements in the mechanical properties of the blends. The distribution of the nanoclay in the blend was well dispersed, as shown by X‐ray diffraction analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

High density polyethylene/acrylonitrile butadiene rubber blends: Morphology,mechanical properties,and compatibilization

Polymer blends based on high-density polyethylene (HDPE) and acrylonitrile butadiene rubber (NBR) were prepared by a melt blending technique. The mixing parameters such as temperature, time, and speed of mixing were varied to obtain a wide range of properties. The mixing parameters were optimized by evaluating the mechanical properties of the blend over a wide range of mixing conditions. The morphology of the blend indicated a two-phase structure in which NBR phase was dispersed as domains up to 50% of its concentration in the continuous HDPE matrix. However, 70 : 30 NBR/HDPE showed a cocontinuous morphology. The tensile strength, elongation at break, and hardness of the system were measured as a function of blend compostion. As the polymer pair is incompatible, technological compatibilization was sought by the addition of maleic-modified polyethylene (MAPE) and phenolic-modified polyethylene (PhPE). The interfacial activity of MAPE and PhPE was studied as a function of compatibilizer concentration by following the morphology of the blend using scanning electron micrographs. Domain size of the dispersed phase showed a sharp decrease by the addition of small amounts of compatibilizers followed by a leveling off at higher concentrations. Also, more uniformity in the distribution of the dispersed phase was observed in compatibilized systems. The tensile strength of the compatibilized systems showed improvement. The mechanical property improvement, and finer and uniform morphology, of compatibilized systems were correlated with the improved interfacial condition of the compatibilized blends. The experimental results were compared with the current theories of Noolandi and Hong. © 1995 John Wiley & Sons, Inc.     

Thermal and mechanical properties of poly(methyl methacrylate) and ethylene vinyl acetate copolymer blends

A series of poly(methyl methacrylate) (PMMA) blends have been prepared with different compositions viz., 5, 10, 15, and 20 wt % ethylene vinyl acetate (EVA) copolymer by melt blending method in Haake Rheocord. The effect of different compositions of EVA on the physico‐mechanical and thermal properties of PMMA and EVA copolymer blends have been studied. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) has been employed to investigate the phase behavior of PMMA/EVA blends from the point of view of component specific interactions, molecular motions and morphology. The resulting morphologies of the various blends also studied by optical microscope. The DSC analysis indicates the phase separation between the PMMA matrix and EVA domains. The impact strength analysis revealed a substantial increase in impact strength from 19 to 32 J/m. The TGA analysis reveals the reduction in onset of thermal degradation temperature of PMMA with increase in EVA component of the blend. The optical microscope photographs have demonstrated the PMMA/EVA system had a microphase separated structure consisting of dispersed EVA domains within a continuous PMMA matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of composition on the linear viscoelastic behavior and morphology of PP/HDPE blends

In this paper the influence of temperature and composition on the dynamic behavior and morphology of polypropylene (PP)/high-density polyethylene (HDPE) blends were studied. The blend composition ranged from 5 to 30 wt% of dispersed phase (HDPE) and the temperatures ranged from 180 to 220 °C. The interfacial tension between PP and HDPE at temperatures of 180, 200 and 220 °C was obtained from fitting Palierne's emulsion model [1] to the experimental data of PP/HDPE blends with different compositions and from the weighted relaxation spectra of PP/HDPE blends with different compositions, following Gramespacher and Meissner [2] analysis. The interfacial tension between PP and HDPE as inferred from the rheological measurements was shown to depend on PP/HDPE blend composition. However, the results indicated that there is a range of PP/HDPE blend composition for which interfacial tension between PP and HDPE is constant. Considering these values, it was shown that interfacial tension between PP and HDPE decreases linearly with increasing temperature.     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.