The impact of strain-induced crystallization on strain during mechanical cycling of cross-linked natural rubber

The improvement of X-ray diffraction techniques since the last ten years allowed a renewal of the study of strain-induced crystallization in natural rubber. In particular real-time measurements are now commonplace. However, due to experimental difficulties, the exploitation of the X-ray data as far as the strain state of the remaining molten fraction is concerned has been left aside. Indeed the knowledge of the local extension of the molten chains is crucial for understanding the peculiar stress behavior observed during the crystallization process. This paper presents a systematic study of this parameter during mechanical cycling performed at various temperatures. It is shown that crystallization limits the amplitude of strain endured by the molten fraction during traction. This process of strain regulation may be one explanation for the protective effect of crystallization against tearing. A precise evaluation of the contribution of the molten fraction to the retraction force during mechanical cycling is made. The role of crystallites as nanofillers may be quantified this way.     

“Mechanism of the self-reinforcement of cross-linked NR generated through the strain-induced crystallization”

The author proposed new models and concept for the self-reinforcement of NR. The first model indicates that general rubber vulcanizate consists of the heterogeneous structure, partially continuous cross-linked phase (75%) and continuous uncross-linked phase (25%). In addition, the author proposed other new models and concept for the strain-induced crystallization in vulcanized NR, in which the strain-induced crystallization takes place in the uncross-linked phase in cross-linked rubber. In the uncross-linked phase under large extension, molecular flow and orientation occur due to the very high compressive, shear and tensile stresses generated by the surrounding hard cross-linked phases, which makes the strain-induced crystallization possible in the uncross-linked phase. As macroscopic extension increases, the crystallization spreads over the whole uncross-linked phases, thus the uncross-linked phase changes its character from original soft rubber to the strong super network consisting of a bundle of extended molecules interconnected at the crystals. The characteristic phenomena observed in the stress-strain relation of NR such as the stress-upturn, high tensile strength and large stress-softening (Mullins effect) can be reasonably explained using these models and concepts.     

Strain-induced crystallization of natural rubber as studied by high-resolution solid-state C NMR spectroscopy

A series of high-resolution solid-state ¹³C NMR experiments were performed on both unstretched and in situ stretched natural rubber samples. From the ¹³C CP/MAS spectra, it was found that natural rubber does form small crystals at room temperature though the degree of crystallinity is very small. Furthermore, from the ¹³C DD/MAS spectra, the crystalline signals were found to increase with the increase of draw ratio. ¹³C spin-lattice relaxation time (T₁) and ¹H spin-spin relaxation time (T₂) of in situ stretched natural rubber were measured for the first time, which provided further evidences for the conclusion that there exist crystals in both stretched and unstretched natural rubber samples. Quantitative ¹³C NMR measurements indicated that strain-induced crystallization occurs when the draw ratio reaches about 2.0 and the maximum crystallinity of our natural rubber samples can be as high as 19.3% upon stretching.     

Changes in crosslinking structure of thermo-oxidative aging chloroprene rubber and its effect on strain-induced crystallization

Chloroprene rubber (CR) is frequently quoted as an example of strain-induced crystallizing elastomer. Many researchers have focused on studying the aging mechanism and mechanical properties of aged CR, little has been done on the effect of crosslinking structure on strain-induced crystallization (SIC). The present paper related systematic investigations combining the changes of crosslinking structure and its influence on SIC. It was firstly investigated based on FTIR, crosslinking density test and GPC. The results showed that the molecular chains were oxidized in the early stage of aging, but the crosslinking reaction still dominated. At the same time, sol content and polydispersity decreased. In the later stage of aging, CR was oxidized, resulted in severe molecular chains fracture and an increase in the free sol content and polydispersity. The impact of aging on SIC under tensile condition was further investigated by the tensile tests. An obvious stress-hardening was found for unaged CR, but not in aged CR. The crystallinity and microcrystalline region orientation tests showed that oxidation, crosslinking by double bonds and dechlorination during aging were not conducive to the orientation of molecular chains during stretching. It is the aging process that has an adverse effect on the SIC of CR.     

Molecular weight between physical entanglements in natural rubber: A critical parameter during strain-induced crystallization

The purpose of this paper is to clarify the role of crosslink density of natural rubber on its strain-induced crystallization. A series of new in situ synchrotron X-ray diffraction experiments were performed during the stretching process of weakly and highly vulcanized natural rubber samples. The experimental data have been analysed in terms of both crystallite size and crystallization rate. Moreover, a careful treatment of previously published data that might appear contradictory has been done. The comparison between all these data, coming from NR of different origins and with different crosslinking states, demonstrates that the molecular weight between physical entanglements in natural rubber appears as a key parameter for strain-induced crystallization (SIC).     

Structural development of natural rubber during uniaxial stretching by in situ wide angle X-ray diffraction using a synchrotron radiation

Structural development of natural rubber during uniaxial stretching was examined by an in situ wide angle X-ray diffraction measurement using a synchrotron. During stretching, the amorphous part showed little change, i.e. an amorphous halo remained clear even at 500% strain. The fraction of induced crystals was very small, though a clear crystalline pattern was observed at 400% strain. Some polymer chains were oriented and crystallized, but most of the chains were not oriented at all in spite of large deformations of the specimen. Only a small amount of polymer chains contributes to the stress and hysteresis loss during elongation.     

New insights into thermodynamic description of strain-induced crystallization of peroxide cross-linked natural rubber filled with clay by tube model

Clay changes the strain-induced crystallization behavior of natural rubber and induces a dual crystallization mechanism due to the orientation of clay layers during deformation. The structure evolution was probed by in-situ synchrotron wide-angle X-ray diffraction, while the thermodynamics of the onset of crystallization was analyzed by the tube model. The entropy change required for the onset of the strain-induced crystallization of the clay filled rubber is composed of the entropy reduction due to the rubber-filler interactions and also the stretching. The summation of the two kinds of the entropy reduction is nearly equal to that of the neat rubber. The thermodynamic analysis reveals that the orientation of clay layers along the direction of stretching reduces the chain conformational entropy and changes the crystallization mechanism. These results give some new insights into the strain-induced crystallization process and the reinforcement mechanism for the clay filled rubber.     

Parameters governing strain induced crystallization in filled natural rubber

A series of in situ synchrotron X-ray diffraction experiments are performed during the stretching of weakly and highly vulcanized carbon black (CB), silica and grafted silica filled natural rubber sample (NR). Conversely to literature, Mullins effect observed after one stretching cycle modifies the strain induced crystallization (SIC) behaviour of the sample. The onset of crystallization is ruled by the strain amplification induced by the filler presence. Moreover, fillers (CB and silica) behave as additional crosslinks into NR network, through filler-rubber interactions that either accelerate or slow down the crystallization rate depending on NR matrix chemical crosslink density. This is consistent with the assumption that effective network density, which is due to chemical crosslinks, entanglements, and filler-rubber interactions, controls the crystallization rate.     

Crosslinking junctions of vulcanized natural rubber analyzed by solid-state NMR spectroscopy equipped with field-gradient-magic angle spinning probe

Crosslinking junctions of vulcanized natural rubber were analyzed by solid-state NMR spectroscopy equipped with a field-gradient high speed magic angle spinning probe. Resolution of ¹H and ¹³C NMR spectra and correlations between ¹H and ¹³C of the vulcanized natural rubber were investigated by one- and two-dimensional measurements, including inverse correlation measurements. The number of substitution of the carbon atom at the crosslinking junctions was determined by solid-state NMR spectroscopy.     

A stroboscopic X-ray apparatus for the study of the kinetics of strain-induced crystallization in natural rubber

A stroboscopic X-ray diffraction machine is described that allows studying kinetics aspects of strain-induced crystallization in natural rubber. Besides conventional mechanical cycling in extension, samples may be submitted to periodic extension cycling over a 0.05 Hz–30 Hz frequency range and for various amplitudes of elongation. Pertinent parameters as crystalline content, crystallite orientation and segmental order parameter for the amorphous fraction are determined. The existence of a regulation process of the strain experienced by the chains that remain molten due to the phenomenon of strain-induced crystallization is clearly demonstrated during conventional mechanical cycling at low deformation rate. Melting retardation is shown to lead to an equalization of crystalline content in conditions of periodic cycling of moderate amplitude and below some average elongation. On the other hand, crystallization appears to be a rapid process subsisting up to the maximal cycling frequency corresponding to a stretching time of 17 ms. This is confirmed by periodic cycling of higher amplitude that suggests that strain-induced crystallization may appear within millisecond time. An approximate logarithmic dependence of the crystalline content and elongation of the amorphous fraction upon stretching time is further found.     

Role of stearic acid in the strain-induced crystallization of crosslinked natural rubber and synthetic cis-1,4-polyisoprene

Strain-induced crystallization of crosslinked natural rubber (NR) and its synthetic analogue, cis-1,4-polyisoprene (IR), both mixed with various amounts of stearic acid (SA), were investigated by time-resolved X-ray diffraction using a powerful synchrotron radiation source and simultaneous mechanical (tensile) measurement. No acceleration or retardation was observed on NR in spite of the increase of SA amount. Even the SA-free IR crystallized upon stretching, and the overall crystallization behavior of IR shifted to the larger strain ratio with increasing SA content. No difference due to the SA was detected in the deformation of crystal lattice by stress for both NR and IR. These results suggested that the extended network chains are effective for the initiation of crystallization upon stretching, while the role of SA is trivial. These behaviors are much different from their crystallization at low temperature by standing, where SA acts as a nucleating agent.     

Molecular structure and storage hardening of natural rubber: Insight into the reactions between hydroxylamine and phospholipids linked to natural rubber molecule

The effect of hydroxylamine on the molecular structure and storage hardening of natural rubber (NR) was investigated by the treatment of deproteinized NR (DPNR) latex with hydroxylamine. The hydroxylamine treatment decreased the content of long‐chain fatty acid ester groups in DPNR from about 2–0.7 mol per rubber molecule. The molecular weight and molecular weight distribution changed apparently after treatment with hydroxylamine. The relative intensity of the ¹H NMR signals corresponding to phospholipids at the α‐terminal group decreased after the hydroxylamine treatment. The Huggins ‘k’ constant of hydroxylamine‐treated DPNR showed the liberation of linear rubber molecules caused by decomposition of branch points derived from phospholipids. The absence of storage hardening in hydroxylamine‐treated DPNR was observed to be caused by not only the reaction of hydroxylamine and aldehyde groups but also the removal of phospholipids as well as the breakdown of phospholipid aggregations as a result of hydroxylamime, contributing to the establishment of a newly proposed mechanism of hydroxylamine on the inhibition of storage hardening in NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43753.     

Effect of fatty acids on the strain‐induced crystallization of natural rubber detected by tear energy measurements

The strain‐induced crystallization of natural rubber (NR) was investigated by the measurement of the tear energy of a crosslinked blend consisting of NR and noncrystalline styrene–butadiene rubber (SBR). When NR was dispersed into the SBR matrix, the tear energy of SBR increased at various temperatures and tear rates. After the application of the principle of time–temperature superposition to the tear energy according to the Williams–Landel–Ferry equation, two distinct curves were found for the NR/SBR blend with respect to the reduced tear rate, despite the fact that the tear energy of SBR or the SBR/SBR blend gave its own single composite curve. When the fatty acid in the NR/SBR blend was removed by acetone extraction, the tear energy of the blend drew a single composite curve. The conversion of the two curves into the single composite curve for the NR/SBR blend suggested that the tear energy depended on the strain‐induced crystallization of NR dispersed in the SBR matrix, which was suppressed by the removal of the fatty acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 613–619, 2005     

Rupture, orientation and strain-induced crystallization of polymer chain and network in vulcanized polyisoprene during uniaxial deformation by in-situ Electron Spin Resonance (ESR) and synchrotron X-ray analysis

Different network structures of vulcanized polyisoprene rubbers were studied by in-situ ESR and synchrotron X-ray during deformation to analyze the rupture, orientation, and strain-induced crystallization of polymer chains and network points. Rupture of network points occur, depending on network structure, and create an un-reversible change in vulcanized rubber. The flexibility of network points affects the possibility of rupture, polymer orientation and strain-induced crystallization. Peroxide vulcanized network is rigid and un-rupturable. Poly-sulfide rich vulcanized network is more flexible and less rupturable than mono-sulfide rich vulcanized network. Chain flexibility and rupturability of network points affect the strain-induced crystallization and stress-strain relation.     

Cure index and activation energy of vulcanization of natural rubber and epoxidized natural rubber vulcanized in the presence of antioxidants

The cure index and apparent activation energy of vulcanization of one grade of natural rubber (SMR L) and two grades of epoxidized natural rubbers (ENR 25 and ENR 50) were studied in the presence of three types of antioxidants [viz., 2,2′methylene‐bis(4‐methyl‐6‐tertbutylphenol) (AO 2246), poly‐2,2,4‐trimethyl‐1,2‐dihydroquinoline (TMQ), and N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine (IPPD)] in the temperature range of 120–180°C by using a Monsanto automatic Mooney viscometer. Accelerated sulfur vulcanization system and up to 5 phr of antioxidant concentration was used throughout the investigation. Results indicate that both cure index and apparent activation energy of vulcanization are dependent on the type and concentration of the antioxidant used. AO 2246 (a phenol‐based antioxidant) would retard vulcanization as reflected by the higher cure index and activation energy, an observation which is attributed to the solvation and steric hindrance effects of the antioxidant. On the contrary, both TMQ and IPPD (amine‐based antioxidants) exhibit reverse behavior due to the catalytic effect of the antioxidants in generating more active sulfurating agents for vulcanization. In all cases, SMR L gives higher cure index and apparent activation energy than the corresponding ENR, a phenomenon which is associated with the activation of the adjacent double bond by epoxide group in the latter. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3234–3238, 2000     

Thermo-oxidative ageing and its effect on the network structure and fracture mode of natural rubber vulcanizates

The changes in network structure and fracture mode of unfilled and filled natural rubber vulcanizates, during ageing at 100°C have been studied by chemical analyses and scanning electron microscopy. The fall in properties during ageing is caused mainly by chain scission. The increase in crosslink density during the initial periods of ageing causes an increase in modulus and tensile strength. Carbon black accelerates ageing, probably by surface catalysis. The simple network structure of efficiently vulcanized rubber results in better retention of properties during ageing. Antioxidant retards ageing. The extent of degradation of vulcanizates is reflected in the nature of the fracture surfaces. The roughness of the tensile fracture surface is affected to varying degrees depending upon the ageing resistance of the vulcanizates. However, in tear, the mode of fracture propagation is affected by ageing.     

Preparation and characterization of natural rubber dispersed in nano-matrix

Preparation of a model nano-matrix-dispersed polymer was investigated in terms of graft-copolymerization of deproteinized natural rubber latex with styrene, using tert-butyl hydroperoxide/tetraethylenepentamine as an initiator. The products were characterized by ¹H-NMR spectroscopy and size-exclusion-chromatography after ozonolysis. The grafting efficiency of styrene was found to be more than 90% under the best condition of the graft-copolymerization. The morphology of the film specimens, prepared from graft-copolymers, was observed by transmission electron microscopy after staining the films with OsO₄. Natural rubber particle of about 0.5 μm in diameter was dispersed in polystyrene matrix of about 15 nm in thickness.     

A wide-angle X-ray study of the development of molecular orientation in crosslinked natural rubber

Molecular orientation parameters have been measured for the non-crystalline component of crosslinked natural rubber samples deformed in uniaxial tension as a function of the extension ratio and of temperature. The orientation parapeters 〈P₂(cosα)〉 and 〈P₄(cosα)〉 were obtained by an analysis of the anisotropy of the wide-angle X-ray scattering functions. For the measurements made at high temperatures the level of crystallinity detected was negligible and the orientation-strain behaviour could be compared directly with the predictions of molecular models of rubber elasticity. The molecular orientation behaviour with strain was found to be at variance with the estimates of the affine model particularly at low and moderate strains. Extension of the crosslinked rubber at room temperature led to strain-crystallization and measurements of both the molecular orientation of the non-crystalline chains and the degree of crystallinity during extension and relaxation enabled the role of the crystallites in the deformation process to be considered in detail. The intrinsic birefringence of the non-crystalline component was estimated, through the use of the 〈P₂(cosα)〉 values obtained from X-ray scattering measurements, to be 0.20±0.02.     

The formation of fibrous structure of polyamide 6 induced by the three-step forming process and its prominent reinforcement in nitrile rubber

Nitrile rubber (NBR) blends with excellent performance have always been a hot research topic in petroleum field. Due to the excellent performance and compatibility of polyamide 6 (PA6), it provides an opportunity for the preparation of high-performance NBR/PA6 blends. In this article, NBR/PA6 blends were prepared by the three-step molding process. Experimentally, it was found that PA6 has a prominent reinforcement effect in NBR matrix. The variation of this mechanical property was investigated from different aspects of the crystal structure, crystallinities, phase morphology, and so on. It can be cleared that the formation of fibrous structure of PA6 phase is the main factor for reinforcement of the polymer blends. Meanwhile, the formation mechanism of the special phase structure induced by the three-step process is deeply expounded and its structural evolution schematic is established. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47472.     

Molecular orientation and structural development in vulcanized polyisoprene rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction

Molecular orientation and strain-induced crystallization of vulcanized natural rubbers (by sulfur and peroxide) and synthetic polyisoprene rubber (by sulfur) during uniaxial deformation at 0 °C were studied by in situ synchrotron wide-angle X-ray diffraction. The high intensity of synchrotron X-rays and new image analysis methods made it possible to estimate the mass fractions of strain-induced crystals and amorphous chains in both oriented and unoriented states. Most of the polymer chains (∼75%) were found to be in the random coil state even at large strains (>5.0). Only about 5% the amorphous chains were oriented, whereas the rest of the chains (∼20%) were in the crystalline phase. Sulfur vulcanized and peroxide vulcanized natural rubbers did not exhibit notable differences in structure and property relationships. In contrast, synthetic polyisoprene rubber showed a different behavior of deformation-induced structural changes, which can be attributed to the difference in cross-link topology. Our results indicated that strain induces a network of microfibrillar crystals in both natural and synthetic polyisoprene rubbers due to the inhomogeneity of cross-link distribution that is responsible for their elastic properties.