Improved peel strength in vulcanized sbr rubber roughened before chlorination with trichloroisocyanuric acid

The effectiveness of chlorination as surface treatment to improve the adhesion of synthetic vulcanized styrene-butadiene rubber (SBR) depends on several experimental variables. Solutions of trichloroisocyanuric acid (TCI) in methyl ethyl ketone (MEK) have been used as effective chlorination agents for several rubbers. In this study, the influence of roughening prior to chlorination treatment of a SBR rubber (R2) and the durability of the modifications produced as the time after chlorination increased have been considered. Two concentrations of the chlorination agent (0.5 and 2 wt% TCI/MEK) have been used and the chlorination treatment was applied on the R2 rubber surface using a brush. Characterization of the treated surfaces was carried out using contact angle measurements, ATR-IR spectroscopy and Scanning Electron Microscopy (SEM). T-peel tests of treated R2 rubber/polyurethane adhesive joints have been carried out to determine the adhesion properties. Roughening was an effective treatment to remove paraffin waxes (antiadherent moieties) from the R2 rubber surface. When the chlorination is produced on the roughened R2 rubber, more noticeable chemical and morphological modifications were produced, and higher adhesion was obtained. On the other hand, TCI particles appeared on the roughened and unroughened chlorinated R2 rubber surface, and the size of these TCI particles were decreased by increasing the time after treatment. Furthermore, similar peel strength values were obtained for time after halogenation higher than 2 hours; for shorter time, a decrease in peel strength was found by increasing the time, due to the migration of paraffin wax to the rubber surface.     

IMPROVED PEEL STRENGTH IN VULCANIZED SBR RUBBER ROUGHENED BEFORE CHLORINATION WITH TRICHLOROISOCYANURIC ACID

The effectiveness of chlorination as surface treatment to improve the adhesion of synthetic vulcanized styrene-butadiene rubber (SBR) depends on several experimental variables. Solutions of trichloroisocyanuric acid (TCI) in methyl ethyl ketone (MEK) have been used as effective chlorination agents for several rubbers. In this study, the influence of roughening prior to chlorination treatment of a SBR rubber (R2) and the durability of the modifications produced as the time after chlorination increased have been considered. Two concentrations of the chlorination agent (0.5 and 2 wt% TCI/MEK) have been used and the chlorination treatment was applied on the R2 rubber surface using a brush. Characterization of the treated surfaces was carried out using contact angle measurements, ATR-IR spectroscopy and Scanning Electron Microscopy (SEM). T-peel tests of treated R2 rubber/polyurethane adhesive joints have been carried out to determine the adhesion properties. Roughening was an effective treatment to remove paraffin waxes (antiadherent moieties) from the R2 rubber surface. When the chlorination is produced on the roughened R2 rubber, more noticeable chemical and morphological modifications were produced, and higher adhesion was obtained. On the other hand, TCI particles appeared on the roughened and unroughened chlorinated R2 rubber surface, and the size of these TCI particles were decreased by increasing the time after treatment. Furthermore, similar peel strength values were obtained for time after halogenation higher than 2 hours; for shorter time, a decrease in peel strength was found by increasing the time, due to the migration of paraffin wax to the rubber surface.     

Surface Analysis of Debonded Chlorinated Vulcanized Styrene-Butadiene Rubber Joints

A synthetic vulcanized styrene-butadiene rubber (R) was treated with a halogenation agent (TCI = trichloroisocyanuric acid) to produce improved adhesion (i.e. high T-peel strength) in joints prepared with a one-component, solvent-based polyester urethane adhesive. Several amounts (0.5 to 7 wt%) of TCI solutions in ethyl acetate were applied to the rubber surface and, after T-peel tests were carried out, the surfaces of the debonded chlorinated rubber pieces were analyzed with XPS, ATR-infra-red (ATR-IR) spectroscopy, Scanning Electron Microscopy (SEM) coupled with EDX analysis, and contact angle measurements. The T-peel strength of unchlorinated rubber (0 wt% TCl) joints was small due to the migration of low molecular species (mainly microcrystalline wax) to the rubber surface during the cure of the adhesive, creating a weak layer in which the failure was produced. Chlorination with amounts of TCI up to 2 wt% produced a noticeable increase in T-peel strength, but treatment with higher amounts of TCI resulted in a decrease in joint strength. Although chlorination with TCI created chlorinated hydrocarbon groups and C-O moieties on the rubber surface, the surface in contact with the adhesive was additionally degraded and, consequently, the locus of failure of the joints varied in a manner which depended on the amount of TCI applied to the surface. Treatment with amounts of TCI up to 2 wt% did not greatly degrade the rubber surface and the mode of failure of the joint was mainly interfacial. Chlorination at higher TCI concentration produced a weak chlorinated surface layer which was was mechanically weak, facilitating the failure in this layer during the T-peel test. The thickness of the chlorinated layer created on the treated rubber is about 5 Fm, and the thickness seemed to be independent of the amount of TCI applied to the rubber surface.     

MEK wiping prior to chlorination to improve the adhesion of vulcanized SBR rubber containing paraffin wax

In this study, it was shown that the degree of effectiveness produced by halogenation with trichloroisocyanuric acid (TCI) was influenced by previous methyl ethyl ketone (MEK) wiping of a synthetic vulcanized styrene-butadiene rubber (R2) surface. The MEK wiping of the R2 rubber surface prior to chlorination with TCI removed the paraffin wax layer from the surface, which favoured the chlorination and oxidation reactions of the rubber. Chlorination with TCI decreased the contact angle values (increased the wettability) mainly due to the creation of C–Cl and C=O moieties, as well as roughness. The amount of these chemical moieties increased when the MEK wiping was applied prior to chlorination, so higher degrees of chlorination and oxidation were obtained on the R2 rubber surface. T-peel strength values increased more markedly if the MEK wiping was carried out before chlorination with TCI, in agreement with the higher degree of modifications produced in the R2 rubber surface. In fact, a cohesive failure in the R2 rubber was obtained in the adhesive joint produced with MEK wiped + TCI chlorinated R2 rubber.     

Chlorination of vulcanized styrene-butadiene rubber using solutions of trichloroisocyanuric acid in different solvents

The chlorination of vulcanized styrene-butadiene rubbers (SBRs) with trichloroisocyanuric acid (TCI) has been studied. The solvent used to apply the TCI chlorinating solutions on the rubber plays an important role in the effectiveness of the treatment since the solvent determined the degree of penetration of TCI into the rubber and also different chlorinating species were produced depending on the nature of the solvent. Surface modifications produced on a synthetic sulfur-vulcanized SBR using TCI solutions in ethyl acetate (EA), methyl ethyl ketone (MEK), and EA + MEK mixtures have been compared. Furthermore, the effects of a solvent wipe with EA or MEK prior to the chlorination process were also considered. Surface modifications produced by the treatments were analyzed using ATR-IR spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Adhesion was obtained from the T-peel strength of treated rubber/polyurethane adhesive joints. TCI/MEK solutions produced a higher degree of surface modification than TCI/EA solutions, but TCI/EA solutions were more effective in removing zinc stearate from the rubber surface. When high TCI percentages (5-7 wt%) in EA solutions were used, a weak boundary layer (WBL) was created on the rubber surface as a consequence of the deposition of an excess of chlorinating agent on the rubber surface and of by-products (cyanuric and/or isocyanuric acid). The formation of the WBL led to a lack of adhesion in the rubber towards the polyurethane adhesive. When MEK was used as a solvent for TCI, this WBL was not produced on the rubber surface, and thus adhesion was considerably higher even when high concentrations of TCI/MEK were used. Similar effects were produced using EA + MEK mixtures as the solvent for TCI. The wiping of the rubber surface with MEK prior to the chlorination treatment led to good adhesion, irrespective of the percentage of TCI and the solvent used in the chlorinating solution.     

Influence of Chlorinating Solution Concentration on the Interactions Produced Between Chlorinated Thermoplastic Rubber and Polyurethane Adhesive at the Interface

Chlorination of a thermoplastic styrene-butadiene-styrene rubber (S0) with different amounts of trichloroisocyanuric acid (TCI) solutions in ethyl acetate improved its adhesion to polyurethane adhesives. A strong interaction of the PU (polyurethane) adhesive and the chlorinated S0 rubber chains is produced at the interface. The increase in the concentration of TCI from 0.5 wt% up to 2-7 wt% resulted in the deposition of crystallites of unreacted TCI on the rubber surface. The remaining TCI on the rubber surface migrates through the PU adhesive producing some chlorination of the PU chains. The failure of the joint is located in this interface composed of both chlorinated S0 rubber and partially-chlorinated PU adhesive.     

Influence of Chlorinating Solution Concentration on the Interactions Produced Between Chlorinated Thermoplastic Rubber and Polyurethane Adhesive at the Interface

Chlorination of a thermoplastic styrene-butadiene-styrene rubber (S0) with different amounts of trichloroisocyanuric acid (TCI) solutions in ethyl acetate improved its adhesion to polyurethane adhesives. A strong interaction of the PU (polyurethane) adhesive and the chlorinated S0 rubber chains is produced at the interface. The increase in the concentration of TCI from 0.5 wt% up to 2-7 wt% resulted in the deposition of crystallites of unreacted TCI on the rubber surface. The remaining TCI on the rubber surface migrates through the PU adhesive producing some chlorination of the PU chains. The failure of the joint is located in this interface composed of both chlorinated S0 rubber and partially-chlorinated PU adhesive.     

Chlorination of vulcanized SBR rubber by immersion or brushing in TCI solutions

The effectiveness of the chlorination treatment of synthetic vulcanized styrene-butadiene rubbers is determined by several experimental variables. In this study, trichloroisocyanuric acid (TCI) solutions in butanone have been used as chlorinating agents for a difficult-to-bond vulcanized styrene-butadiene rubber (R2). The influence of the TCI concentration (0.5 and 2 wt% TCI/MEK) was studied and a comparison between the immersion and brushing procedures to apply the chlorinating agent has been carried out. Characterization of the chlorinated surfaces was carried out using contact angle measurements (water, 25°C), ATR-IR spectroscopy, and scanning electron microscopy (SEM). T-peel tests on similarly treated R2 rubber/polyurethane adhesive joints were carried out to quantify adhesion. The chlorination by immersion of R2 rubber with TCI/MEK solutions was less effective than using a brush. The effects of the chlorination were similar using both procedures (creation of roughness, improved wettability, C Cl moieties formation and deposition of TCI particles), but the extent of the modifications was more marked when using a brush. The higher concentration of chlorinating agent allows a higher degree of chlorination. Peel strength values were lower for brush-chlorinated R2 rubber because the migration of wax (which created a weak layer on the rubber surface) from the bulk to the R2 rubber surface was favoured. However, the presence of waxes on the R2 rubber surface still allowed a reasonable level of adhesion due to the predominance of polar moieties.     

A new water-based chemical treatment based on sodium dichloroisocyanurate (DCI) for rubber soles in the footwear industry

A new water-based chemical treatment based on sodium dichloroisocyanurate (DCI) solutions for rubber soles of different natures is reported in this study. Different concentrations (1-5 wt%) of DCI and two rubber formulations (vulcanized styrene-butadiene rubber, R2; thermoplastic rubber, TR) were considered. The effects produced by treatment of the rubber soles with DCI were compared with the standard halogenation method using trichloroisocyanuric acid (TCI) solutions in an organic solvent (ethyl acetate). The effects of chlorination on the rubber surfaces were studied using contact angle measurements, ATR-IR spectroscopy, and scanning electron microscopy. The adhesion strength was obtained from T-peel strength tests on canvas/PUD adhesive/treated rubber joints. The adhesive used throughout this study was a water-based polyurethane dispersion (PUD). The surface treatment with aqueous DCI solutions modified the surface chemistry of both the TR and R2 rubbers, creating C—Cl moieties on the surface and removing the zinc stearate from the R2 rubber surface. The use of a low DCI concentration in water was less effective in modifying the TR rubber, but was sufficient to obtain good T-peel strength values for the R2 rubber joints. On the other hand, heterogeneities and cracks were created on the rubber surface (mainly on the R2 rubber surface), which may contribute to an increase in the mechanical interlocking with the adhesive. A noticeable increase in the T-peel strength and a cohesive failure in the rubber for the joints produced with TR rubber were obtained when the rubber was treated with aqueous DCI solutions. For the canvas/PUD adhesive/chlorinated R2 rubber joint, the failure was located in a thin surface layer on the canvas. Finally, the surface treatment with TCI in ethyl acetate produced a more significant surface modification on both the TR and the R2 rubber, creating deeper roughness on the R2 rubber surface. Consequently, higher peel strength values were obtained using TCI solutions in ethyl acetate. Furthermore, the T-peel strength values were high in all joints produced with TR rubber treated with either TCI solution in ethyl acetate or aqueous DCI solution.     

Different surface modifications produced by oxygen plasma and halogenation treatments on a vulcanized rubber

The surface modifications of a synthetic vulcanized styrene-butadiene rubber (R1) using a chemical treatment [halogenation with trichloroisocyanuric acid (TCI)] and a treatment with oxygen plasma were compared. Treatment of R1 rubber with 2 wt% TCI produced greater surface modification than the oxygen plasma and the modification was extended over a thicker region of the rubber when it was treated using TCI. The degree of oxidation obtained with only 1 min of oxygen plasma treatment was greater than that obtained by chlorination with different amounts of TCI. This agreed with the improved interaction among polar groups evaluated from the higher acid–base contribution to the surface energy of the oxygen plasma-treated R1 rubber surface. However, higher T-peel strength values and more noticeable cohesive failure in the rubber were obtained for joints produced with chlorinated R1 rubber than for those produced with oxygen plasma-treated R1 rubber, due to the creation of a less rough and weaker oxygen plasma-treated surface.     

TREATMENT OF THERMOPLASTIC RUBBERWITH CHLORINE BLEACH AS AN ALTERNATIVE HALOGENATION TREATMENT IN THE FOOTWEAR INDUSTRY

Avoidance of solvents in bonding operations is a current demand in the footwear industry. Halogenation of rubber soles with solutions of trichloroisocyanuric acid (TCI) in different solvents has been successfully used to improve bonding to the leather uppers. In this study, the use of chlorine bleach as an alternative water surface treatment for a rubber has been tested. A thermoplastic block styrene thermoplastic (TR) was treated with bleach to improve its adhesion to a water-based polyurethane dispersion adhesive (PUD). T-peel testing, scanning electron microscopy (SEM), contact angle measurements (ethanediol, 25°C), and infrared spectroscopy (ATR-IR) were used to analyze the modifications produced on the rubber surface. Adhesion values were obtained from T-peel testing of joints produced with similarly treated TR rubber test pieces. Different experimental variables were considered in this study, namely the immersion time (0.5-2 min) in bleach, the active chlorine content (43.9- 55.6 g/l) in the bleach, the addition of a wetting agent (1-octyl-2-pyrrolidone) to the bleach, and the application of the surface treatment using an ultrasonic bath. The treatment with bleach produced the chlorination of the hydrocarbon chains on the TR rubber surface and slightly changed the surface roughness. Chlorination of the TR rubber with bleach (free active chlorine=55.6 g/l) was fast and needed only 30 sec immersion in the reagent mixture to produce high adhesion. Furthermore, the active chlorine content in the bleach was critical to assure an adequate T-peel strength value. The addition of 1-octyl-2-pyrrolidone to the bleach increased the wettability of the rubber surface, although it was necessary to carry out the surface treatment in the ultrasonic bath to obtain adequate adhesion to the PUD adhesive.

Thermoplastic styrene-butadiene rubber Water-based polyurethane adhesive Bleach Halogenation Water-based surface treatment Contact angle ATR-IR spectroscopy SEM T-peel strength     

Treatment of thermoplastic rubberwith chlorine bleach as an alternative halogenation treatment in the footwear industry

Avoidance of solvents in bonding operations is a current demand in the footwear industry. Halogenation of rubber soles with solutions of trichloroisocyanuric acid (TCI) in different solvents has been successfully used to improve bonding to the leather uppers. In this study, the use of chlorine bleach as an alternative water surface treatment for a rubber has been tested. A thermoplastic block styrene thermoplastic (TR) was treated with bleach to improve its adhesion to a water-based polyurethane dispersion adhesive (PUD). T-peel testing, scanning electron microscopy (SEM), contact angle measurements (ethanediol, 25°C), and infrared spectroscopy (ATR-IR) were used to analyze the modifications produced on the rubber surface. Adhesion values were obtained from T-peel testing of joints produced with similarly treated TR rubber test pieces. Different experimental variables were considered in this study, namely the immersion time (0.5-2 min) in bleach, the active chlorine content (43.9- 55.6 g/l) in the bleach, the addition of a wetting agent (1-octyl-2-pyrrolidone) to the bleach, and the application of the surface treatment using an ultrasonic bath. The treatment with bleach produced the chlorination of the hydrocarbon chains on the TR rubber surface and slightly changed the surface roughness. Chlorination of the TR rubber with bleach (free active chlorine=55.6 g/l) was fast and needed only 30 sec immersion in the reagent mixture to produce high adhesion. Furthermore, the active chlorine content in the bleach was critical to assure an adequate T-peel strength value. The addition of 1-octyl-2-pyrrolidone to the bleach increased the wettability of the rubber surface, although it was necessary to carry out the surface treatment in the ultrasonic bath to obtain adequate adhesion to the PUD adhesive. Thermoplastic styrene-butadiene rubber Water-based polyurethane adhesive Bleach Halogenation Water-based surface treatment Contact angle ATR-IR spectroscopy SEM T-peel strength     

Influence of calcium carbonate added to the SBS rubber formulation on the surface modifications produced by halogenation

To improve the adhesion properties of styrene–butadiene–styrene (SBS) rubber sole to polyurethane adhesive, surface treatments are required, of which halogenation with trichloroisocyanuric acid (TCI) solutions in organic solvents is the most commonly used treatment in the footwear industry. Calcium carbonate filler is commonly added to improve the mechanical properties and to reduce shining of SBS rubber formulations. The influence of the filler on the effectiveness of surface chlorination of SBS rubber had not been considered in the existing literature. Therefore, 10 wt% calcium carbonate filler was added to the SBS rubber formulation and the surface modifications and adhesion properties produced by treatment with TCI solutions were investigated. The resulting surface modifications and adhesion were compared to those obtained in unfilled SBS rubber. It is shown that the treatment with TCI solutions was less effective in the calcium-carbonate-filled SBS rubber and a lower peel strength to polyurethane adhesive was obtained; however, a cohesive failure in the rubber was always obtained.     

Surface Characterization of Chlorinated Synthetic Vulcanized Styrene-Butadiene Rubber Using Contact Angle Measurements,Infra-Red Spectroscopy and XPS

The surface of a sulfur-vulcanized synthetic styrene-butadiene rubber (SBR) was treated with ethyl acetate solutions containing different amounts of trichloroisocyanuric acid (TCI). The chlorinated SBR surfaces were characterized using contact angle measurements (water, ethane diol, n-hexadecane), infra-red (IR) spectroscopy and XPS. Chlorination produced an increase of surface free energy which was mainly due to the enhancement of the acid-base component of the surface free energy, which remained almost unchanged when the amount of TCI was increased. Depending on the amount of chlorination agent, several chemical species were present on the SBR surface: i) For low amounts of TCI (up to 2 wt%), mainly chlorinated hydrocarbon and C – O species were present on the surface; ii) For medium amounts of TCI (between 2 and 5 wt%), an excess of unreacted TCI remained on the surface and a relatively small amount of isocyanuric acid was deposited; iii) For high amounts of TCI (larger than 5 wt%), a weak boundary layer (mainly composed of isocyanuric acid) was formed on the surface and thus the effects due to chlorination were decreased. There was good agreement between the experimental results obtained with contact angle measurements and XPS because both provided information on a surface region close to 100 Å, whereas IR spectroscopy results showed deeper penetration of the chlorinating agent into the SBR surface. The estimated thickness of the chlorinated layer was near 5000 Å as estimated from XPS measurements of SBR surfaces modified by argon ion bombardment.     

Halogenation of styrene-butadiene rubber to improve its adhesion to polyurethanes

Halogenation of styrene-butadiene rubbers has been carried out using solutions containing different amounts (0.1-5 wt%) of trichloroisocyanuric acid in butan-2-one. The treated rubber surface showed increased peel strength in joints made with polyurethane adhesive. The effects of chlorination on the rubber surface were studied using scanning electron microscopy, contact angle measurements, and infrared spectroscopy. It was shown that cracks appear in the rubber surface after halogenation, a factor which favours adhesion; the larger the amount of trichloroisocyanuric acid used, the larger the number of cracks. On the other hand, chlorination of the carbon double bond (butadiene) and the formation of carboxylic acid groups seem to be the most important chemical changes in the chlorinated rubber surfaces. Chlorination increases the surface energy of the rubber, although this increase is a function of the rubber composition. In fact, for a simple rubber formulation, the polar component of the surface energy increases for the highest concentrations of chlorine on the rubber surface; but for rubber with a more complicated formulation, the same value of surface energy after chlorination was obtained, independently of the amount of trichloroisocyanuric acid added. A good correlation was found between the contact angle measurements, the infrared spectra, and the peel strength values.     

Influence of the nature and formulation of sty rene-butadiene rubber on the effects produced by surface treatment with trichloroisocyanuric acid

The nature and formulation of two synthetic sulfur-vulcanized styrene-butadiene rubbers affected the extent, but not the nature, of the surface modification produced by halogenation with different amounts (1-7 wt%) of trichloroisocyanuric acid (TCI) solutions in ethyl acetate. R1 rubber had a low oil and plasticizer content, whereas R2 rubber contained a smaller amount of styrene than R1, and a relatively significant amount of oil and plasticizer. Chlorination of the rubbers decreased their tensile strength (more markedly in R2) without noticeable changes in elongation at break, and heterogeneities and cracks were created on the rubber surface (mainly in R2). The surface modifications were not influenced by the manner in which the post-chlorination agent was removed (air or vacuum). Chlorination with TCI created C-Cl, C-O, and COO- moieties on the rubber surface which were responsible for its enhanced acid-base contribution to the surface energy. The extent of chlorination was more extensive in R1 (the rubber with a smaller butadiene content). The surface modification was less effective for R2, due to its noticeable amount of oil and plasticizer. On the other hand, when the chlorination was carried out with 7 wt% TCI, removal of the excess of the post-chlorination agent in vacuum prevented the formation of weak boundary layers (due to isocyanuric acid + mechanically damaged surface) in the treated surfaces. The nature and formulation of the rubber determined the thickness of the weak boundary layer (thinner in R1). On the other hand, a relatively deep penetration (at least 10 nm) of the chlorination agent into the rubber bulk was produced.     

Effects of overhalogenation of a synthetic vulcanized styrene–butadiene rubber sole on its adhesion behavior

The effects of halogenating the same synthetic vulcanized styrene–butadiene rubber (R2) (used as a sole material in the shoe industry) twice (double halogenation) using solutions of trichloroisocyanuric acid (TCI) in MEK were studied. The R2 rubber was treated with 0.5 and 2 wt% TCI/MEK solutions and after 1 h re-treated with additional 0.5 (0.5 + 0.5 wt% TCI/MEK) and 2 wt% TCI/MEK (2 + 2 wt% TCI/MEK) solutions. The results obtained were compared with those obtained by treating the R2 rubber once with 1 and 4 wt% TCI/MEK solutions. The surface modifications produced by the double halogenation of the R2 rubber were analyzed using advancing and receding contact angles (variations in wettability), XPS and ATR-IR spectroscopy (characterization of chemical modifications) and SEM (morphological modifications). T-peel tests on doubly halogenated R2 rubber/polyurethane adhesive joints were carried out to quantify the adhesion properties of the treated R2 rubber. The degree of chlorination was higher with increasing amount of chlorinating agent. Furthermore, the most efficient removal of hydrocarbon substances from the R2 rubber surface was obtained by double halogenation and by increasing the TCI concentration. Similar trends in surface chemistry of the R2 rubber were obtained using 0.5–2 wt% TCI/MEK, with or without double halogenation. On the other hand, by comparing the effects of treatments with 0.5 + 0.5 wt% TCI/MEK and 1 wt% TCI/MEK or with 2 + 2 wt% TCI/MEK and 4 wt% TCI/MEK, less effective removal of zinc stearate and less degree of chlorination were obtained by double halogenation although similar outermost surface modifications were produced. The second application of the TCI/MEK solution on the already halogenated R2 rubber dissolved the unreacted TCI and/or the isocyanuric acid crystals on its surface. The mechanical properties of the treated R2 rubber decreased because it became stiffer. Higher and relatively similar peel strength values were obtained in all adhesive joints prepared using treated R2 rubber. A cohesive failure in the rubber close to the chlorinated layer was always obtained.     

TREATMENT OF VULCANIZED STYRENE-BUTADIENE RUBBER (SBR) WITH MIXTURES OF TRICHLOROISOCYANURIC ACID AND FUMARIC ACID

In this study, mixtures of trichloroisocyanuric acid (TCI) and fumaric acid (FA) solutions were applied to a difficult-to-bond, vulcanized styrene-butadiene rubber (R2) to analyze the combined effect of both surface treatments. The treated R2 rubber surfaces were characterized using advancing contact angle measurements, ATR-IR and XPS spectroscopy, and SEM. T-peel tests of treated R2 rubber/ polyurethane adhesive/leather joints have been obtained in order to quantify the adhesion properties. The wettability of R2 rubber was improved by treatment with 3 wt% TCI/EA (ethyl acetate) or 0.5 wt% FA/EtOH, and lower contact angles were obtained by treatment with both 3 wt% TCI/EA and 0.5 wt% FA/EtOH. The improved wettability was ascribed to the creation of carbon-chlorine moieties, the removal of zinc stearate and paraffin wax, and the creation of surface roughness on the R2 rubber surface. Treatment of R2 rubber with 3 wt% TCI/EA before or after treatment with 0.5 wt% FA/EtOH, or with a solution containing 3 wt% TCI/EA + 0.5 wt% FA/EtOH mixture produced a noticeable increase in peel strength. Always, the effects of the treatment of R2 rubber with 3 wt% TCI solution were dominant over those produced by treatment with 0.5 wt% FA solution in ethanol (FA/EtOH). On the other hand, the treatment of R2 rubber with 3 wt% TCI/EA + 0.5 wt% FA/EtOH mixture was more effective than the treatment with 0.5 wt% TCI/EA+ 2 wt% FA/EtOH because the lower amount of chlorinating agent in this mixture.     

一种用于消防鞋的耐磨橡胶材料及其制备方法

采用粘接技术对防毒面具用天然胶(NR)罩体和浇注型聚氨酯弹性体(CPU)柔性镜片进行连接。通过XPS、EDS、ATR-FTIR、SEM等分析手段对化学处理前后NR罩体材料的表面组成、形貌进行分析,并对NR罩体/CPU镜片接头的粘接性能进行考察。结果表明：对NR罩体材料进行表面化学处理可通过氯化反应、环氧化反应摄入大量的Cl和O元素,同时表面形貌也发生显著变化;采用聚氨酯(PU)胶黏剂对NR罩体和CPU柔性镜片进行粘接可以取得令人满意的粘接效果,单搭接头T-剥离强度~3.7KN/m,嵌槽接头拔出应力~560N;表面化学处理是提高接头粘接性能的有效手段。     

Prompt modification of styrene‐butadiene rubber surface with trichloroisocyanuric acid by increasing chlorination temperature

In this article, the surface of styrene‐butadiene rubber (SBR) was brushed with trichloroisocyanuric acid (TCI) (1 or 2 wt % in ethyl acetate) and then thermally treated under different conditions. The chemical modification was characterized by contact angle measurement and surface energy, ATR‐FTIR spectroscopy, scanning electron microscopy (SEM), and single‐lap shear test. The results revealed that the increase of the chlorination temperature was very effective for SBR surface modification by TCI, leading to enhanced surface wettability and shear strength within several minutes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012