Study on the grafting of PET onto the glass fiber surface during in situ solid‐state polycondensation

An in situ solid‐state polymerization process was developed to produce long glass fiber reinforced poly(ethylene terephthalate) (PET) composites. As reported in our last article, one advantage of this new process is that the good wetting of reinforcing fiber can be obtained for using low‐viscosity oligomer as raw materials. In this article, the grafting of PET macromolecular chain onto the surface of reinforcing glass fiber during in situ solid‐state polycondensation (SSP) will be investigated, which was believed to be another advantage for this new process and should be very important for thermoplastic composite. The reinforcing glass fiber after removing ungrafted PET from a long glass fiber reinforced PET composite by solvent extraction was investigated by SEM, pyrolysis‐gas chromatography mass spectrometry (Py‐GC/MS), DSC, and FTIR. The information from morphology of SEM photos of glass fiber surface, the spectrum of Py‐GC/MS, the melt peak at differential scanning calorimetric (DSC) curve, and the spectrum of Fourier transform infrared Raman spectroscopy (FTIR) gave a series evidence to prove the presence of grafted PET layer on the surface of silane‐coupling‐treated glass fiber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 775–781, 2006     

Synthesis and characterization of a rigid-rod dihydroxy poly(<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) fiber with excellent surface and axial compression properties

A series of dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO) were prepared by introducing binary hydroxyl polar groups into poly(p-phenylene benzoxazole) PBO macromolecular chains and the effects of hydroxyl polar groups on surface wettability, interfacial adhesion and axial compression property of PBO fiber were investigated. Contact angle measurement showed that the wetting process both for water and for ethanol on DHPBO fibers were obviously shorter than that on PBO fibers, implying DHPBO fibers have a higher surface free energy. Meanwhile, single fiber pull-out test showed that DHPBO fibers had higher interfacial shear strength than that of PBO fibers. Scanning electron microscope proved that there was more resin remained on the surface of DHPBO fibers than on PBO fibers after pull-out test. Furthermore, axial compression bending test showed that the introduction of binary hydroxyl groups into macromolecular chains apparently improved the equivalent bending modulus of DHPBO fibers.     

Grafting of a liquid crystal polymer on carbon fibers

Covalent grafting of mesogenic chains on carbon fiber surfaces was attempted as part of a study on composite materials containing liquid crystal polymer matrices. Grafting in these composite systems is viewed not only as a mechanism to achieve interfacial bonding but also as an approach to modify the interphase physical structure. The synthetic approach to grafting involved the in-situ polymerization of monomers in the presence of functionalized fibers in order to grow chains covalently attached to the fibers. The chemical mechanism may be viewed as the “transesterification of car boxy lated fibers” with acetylated monomers. The monomers used were pimelic acid, p-acetoxybenzoic acid and diacetoxy hydroquinone which are known to yield upon condensation a chemically aperiodic nematic polymer. Evidence for grafting was obtained from X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis on fibers retrieved from composite samples. Interestingly, SEM micrographs of fractured composite specimens containing the mesogen-grafted fibers reveal excellent wetting and interfacial bonding of a liquid crystalline matrix on the carbon surfaces. Based on theoretical considerations for end-adsorbed macromolecules and the nematogenic nature of the grafted chains we infer that dense layers of adsorbed polymer may form at the interfaces studied. From a materials point of view the in situ growth of liquid crystal polymer chains on fibers may offer mechanisms to control composite properties through both bonding and molecular orientation in interfacial regions.     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (M_W) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na⁺. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers     

Solid‐state polymerization of poly(ethylene terephthalate): Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites of different organoclay concentrations were prepared using a water‐assisted extrusion process. The reduction of the molecular weight (M_w) of the PET matrix, caused by hydrolysis during water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). Viscometry, titration, rheological, and dynamic scanning calorimetry measurements were used to analyze the samples from SSP. The weight‐average molecular weight (M_w) of PET increased significantly through SSP. PET nanocomposites exhibited solid‐like rheological behavior, and the complex viscosity at high frequencies was scaled with the M_w of PET. The Maron–Pierce model was used to evaluate the M_w of PET in the nanocomposites before and after SSP. It was found that the extent and the rate of the SSP reaction in nanocomposites were lower than those for the neat PETs, due to the barrier effect of clay platelets. Consequently, the SSP rate of PET increased with decreasing particle size for the neat PET and PET nanocomposites. The effect of the M_w of PET on the crystallization temperature, crystallinity, and the half‐time, t_½, of nonisothermal crystallization was also investigated. With increasing M_w of PET, t_½ increased, whereas T_c and X_c decreased. POLYM. ENG. SCI., 54:2925–2937, 2014. © 2014 Society of Plastics Engineers     

Dispersion of nanoclays with poly(ethylene terephthalate) by melt blending and solid state polymerization

Melt intercalation of clay with poly(ethylene terephthalate; PET) was investigated in terms of PET chain mobilities, natures of clay modifiers, their affinities with PET, and nanocomposite solid state polymerization (SSP). Twin screw extrusion was used to melt blend PET resins with intrinsic viscosities of 0.48, 0.63, and 0.74 dL/g with organically modified Cloisite 10A, 15A, and 30B montmorillonite clays. Clay addition caused significant molecular weight reductions in the extruded PET nanocomposites. Rates of SSP decreased and crystallization rates increased in the presence of clay particles. Cloisite 15A blends showed no basal spacing changes, whereas the basal spacings of Cloisite 10A and Cloisite 30B nanocomposites increased after melt extrusion, indicating the presence of intercalated nanostructures. After SSP these nanocomposites also exhibited new lower angle X‐ray diffraction peaks, indicating further expansion of their basal spacings. Greatest changes were seen for nanocomposites prepared from the lowest molecular weight PET and Cloisite 30B, indicating its greater affinity with PET and that shorter more mobile PET chains were better able to enter its galleries and increase basal spacing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fiber-reinforced cellulosic thermoplastic composites

Steam-exploded fibers from Yellow poplar (Liriodendron tulipifera) wood were assessed in terms of their thermal stability characteristics, their impact on torque during melt processing of a thermoplastic cellulose ester (plasticized CAB) matrix, their fiber–matrix adhesion and dispersion in composites, and their mechanical properties under tension. Fibers included water-extracted steam-exploded fibers (WEF), alkali extracted fibers (AEF), acetylated fibers (AAEF), and a commercial milled oat fiber sample (COF) (i.e., untreated control). The results indicate that the thermal stability of steam-exploded fibers increases progressively as the fibers are extracted with water and alkali and following acetylation. The greatest improvement resulted from the removal of water-soluble hemicelluloses. The modification by acetylation contributed to improved interfacial wetting that was revealed by increased torque during melt processing. Whereas modulus increased by between 0 and 100% with the incorporation of 40% fibers by weight, tensile strength either declined by ⅓ to ½ or it increased by a maximum of 10%, depending on fiber type. AAEF composites produced the best mechanical properties. Fiber–aspect ratio was reduced to an average of 25–50 from ≫ 200 during compounding. The superior reinforcing characteristics of AAEF fibers were also reflected by SEM, which revealed better fiber–matrix adhesion and failure by fiber fibrillation rather than by fiber pullout. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1329–1340, 1999     

Microstructure and properties of poly(ethylene terephthalate)/organoclay nanocomposites prepared by water‐assisted extrusion: Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites containing different concentrations of the organoclay were prepared using two different twin‐screw extrusion processes: conventional melt mixing and water‐assisted melt mixing. The reduction of the molecular weight of the PET matrix, caused by hydrolysis during the water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses showed intercalated/exfoliated morphology in all PET/C30B nanocomposites, with a higher degree of intercalation and delamination for the water‐assisted process. Rheological, thermal, mechanical, and gas barrier properties of the PET nanocomposites were also studied. Enhanced mechanical and barrier properties were obtained in PET‐C30B nanocomposites compared to the neat PET. The nanocomposites exhibited higher tensile modulus and lower oxygen permeability after SSP. The elongation at break was significantly higher for SSP nanocomposites than for nanocomposites processed by conventional melt mixing. POLYM. ENG. SCI., 54:1879–1892, 2014. © 2013 Society of Plastics Engineers     

Superfine structure,physical properties,and dyeability of alkaline hydrolyzed soly(ethylene terephthalate)/silica nanocomposite fibers prepared by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure, physical properties, and dyeability of alkaline hydrolyzed PET/SiO₂ nanocomposite fibers were studied. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. PET/SiO₂ nanocomposite fibers were treated with aqueous solution of sodium hydroxide and cetyltrimethyl ammonium bromide at 100°C for different time. The differences in the alkaline hydrolysis mechanism between pure PET and PET/SiO₂ nanocomposite fibers were preliminarily investigated, which were evaluated in terms of the weight loss, tensile strength, specific surface area, as well as disperse dye uptake. PET/SiO₂ nanocomposite fibers showed a greater degree of weight loss as compared with that of pure PET fibers. More and tougher superfine structures, such as cracks, craters, and cavities, were introduced, which would facilitate the certain application like deep dyeing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3691–3697, 2006     

Chain extension reaction in solid‐state polymerization of recycled PET: The influence of 2,2′‐bis‐2‐oxazoline and pyromellitic anhydride

Conventional and chain extended‐modified solid‐state polymerization (SSP) of postconsumer poly(ethylene terephthalate) (PET) from beverage bottles was investigated. SSP was carried out at several temperatures, reaction times, and 2,2′‐bis‐2‐oxazoline (OXZ) or pyromellitic anhydride (ANP) concentrations. The OXZ was added by impregnation with chloroform or acetone solution. Higher molecular weights were reached when the reaction was carried out with OXZ, resulting in bimodal distribution. The molecular weights of the flakes reacted at 230°C for 4 h were 85,000, 95,000, and 100,000 for samples impregnated with 0, 0.5, and 1.25 wt % OXZ solution, respectively. In the case of reactions with ANP, branched chains were obtained. The thermal and thermal‐mechanical‐dynamic properties of these high‐molecular‐weight recycled PET were determined. For OXZ‐reacted samples, the reduction of crystallinity was observed as the reaction time was increased, becoming evident the destruction of the crystalline phase. The chain extended samples did not show changes in thermal relaxations or thermal degradation behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Phenol‐modified polypropylenes as adhesion promoters in glass fiber–reinforced polypropylene composites

This publication is based on research work done on functional phenol‐modified polypropylenes (PPs) as adhesion promoters in glass fiber–reinforced PP composites. The glass fiber roving was first impregnated with different combinations of functional polymers and polypropylene in a melt impregnation die attached to an extruder to obtain prepreg. The prepreg was then tested in many ways both macro‐ and micromechanically. The tests included notched tensile tests, optical and electron microscopy, and DMTA (dynamic mechanical thermal analyzer) and DSC (differential scanning calorimetry) analyses as well as determination of the glass content. The tests were run on prepregs containing pure PP, PP with a commercial adhesion promoter, and PP with a number of functional, mostly phenol‐based, polymers. Also, single‐fiber tests were performed on individual glass fibers to test the level of adhesion with the above‐mentioned material combinations. With these tests it could be seen that some of the phenol‐based functional polymers provided the prepreg with better adhesion between the fibers and the matrix than did the commercial adhesion promoter. Optical and electron microscopy also were used in determining the level of adhesion as well as the deformation and fracture mechanisms of the prepreg. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1203–1213, 2002; DOI 10.1002/app.10441     

High molecular weight poly (L‐lactic acid) clay nanocomposites via solid‐state polymerization

We propose here, a novel technique to synthesize high molecular weight (MW) poly (L ‐lactic acid)‐clay nanocomposite (PLACN), via solid state polymerization (SSP). We synthesize prepolymer of PLACN (pre‐PLACN) from both, L ‐lactic acid and L ‐lactide, as starting materials. Synthesis of pre‐PLACN from L ‐lactic acid is carried out via in situ melt polycondensation (MP) of L ‐lactic acid oligomer, followed by SSP, to achieve high MW PLACN (M_w ∼ 138,000 Da). In case of L ‐lactide as the starting material, we prepare L ‐lactide–clay intercalated mixture which yields moderate MW pre‐PLACN during subsequent ring opening polymerization (ROP). Interestingly, ROP is performed by using hydroxyl functionalized ternary catalyst system (L ‐lactide–Sn(II) octoate–oligo (L‐lactic acid) complex), which provides the terminal hydroxyl end‐groups, required for step‐growth SSP. Pre‐PLACN MW is now increased to M_w ∼ 127,000 Da, by the subsequent SSP process. ¹H NMR analyses confirm that these end‐groups, are indeed consumed during SSP. During SSP, the PLACN also achieves up to 90% crystallinity, which may be due to the synchronization of the slow step‐growth SSP of poly(L ‐lactic acid) (PLA) with the crystallization kinetics. Optical purity of PLACNs is similar to that of neat PLA, whereas the thermal stability of PLACNs is significantly superior. As evidenced by wide‐angle X‐ray scattering/small‐angle X‐ray scattering analyses and in line with the literature, both, intercalated and exfoliated PLACN morphologies, have been synthesized, by suitable selection of clays. We also verify the correlation between the PLA semicrystalline morphology and the PLACN morphology, which is consistent with those of PLACN synthesized by other techniques. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Recycled poly(ethylene terephthalate) reinforced with basalt fibres: Rheology,structure, and utility properties

Utilization of recycled poly(ethylene terephthalate) (PET) as a matrix for composite materials prepared by continuous compounding is challenging from the environmental as well as industrial point of view. In our work, cut basalt fibers and talc powder of various compositions were used and their reinforcing effect on recycled PET was tested by rheology (Advanced Rheometric Expansion System), differential scanning calorimetry, and tensile experiments. The quality of filler dispersion in recycled PET matrix was investigated by scanning electron microscopy (SEM) and melt rheology. Processing and utility properties of composites were enhanced as compared with those of unfilled matrix. Higher melt elasticity, interfacial adhesion, and better mechanical performance of the composites were in a good agreement with the structure observed from SEM micrographs. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Preparation and properties of deep dye fibers from poly(ethylene terephthalate)/SiO2 nanocomposites by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure and properties of PET/SiO₂ fibers were studied in detail by means of TEM, DSC, SEM, and a universal tensile machine. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. The DSC results indicated that the SiO₂ nanoparticles might act as a marked nucleating agent promoting the crystallization of the PET matrix from melt but which inhibited the crystallization from the glassy state, owing to the “crosslink” interaction between the PET and SiO₂ nanoparticles. The tensile strength of 5.73 MPa was obtained for the fiber from PET/0.1 wt % SiO₂, which was 17% higher than that of the pure PET. The fibers were treated with aqueous NaOH. SEM photographs showed that more and deeper pits were introduced onto PET fibers, which provided shortcuts for disperse dye and diffused the reflection to a great extent. According to the K/S values, the color strength of the dyeing increased with increasing SiO₂ content. It is found that the deep dyeability of PET fibers was improved greatly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Properties of poly(ethylene terephthalate) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane

Poly(ethylene terephthalate) (PET) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS) was prepared by melt‐mixing and in situ polymerization methods. The melt‐mixed composite showed phase separation while the in situ polymerized composite did not, based on SEM characterization. During melt mixing, the reaction between the epoxy groups of POSS and hydroxyl groups of PET occurred, based on DSC results. DSC results on the in situ polymerization product showed formation of a lower‐melting component compared with PET. The tensile strength and modulus of the melt‐mixed composite fiber decreased compared with those properties of PET, whereas those of the in situ polymerized composite showed slightly higher values than PET despite the relatively small amounts (1 wt%) of POSS used. Dynamic mechanical analysis results showed an increase in storage modulus for the in situ polymerized composite of POSS and PET compared with PET over the temperature range of 40 °C to 140 °C. Copyright © 2004 Society of Chemical Industry     

Effect of copolymer mixing on elongation property of as‐spun PET fibers

The change of elongation property in the melt spinning process of polyethylene terephthalate (PET) fibers, mixed with small amount of additive copolymer less than 5% by weight, was studied. The additive polymer was synthesized to improve the extensibility of matrix PET in the spinning process. The amount, molecular weight of additive polymer, and spinning conditions were changed to investigate the extensibility of as‐spun fibers. Experimental results show that the blend of copolymer improves the extensibility of as‐spun PET fibers. The elongation at break of as‐spun fibers increases with molecular weight and amount of additive polymer. The additive polymer prevents the fiber orientation and this causes the increase of extensibility of as‐spun fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1426–1431, 2006     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

Plasma treatment‐induced fluorine‐functionalized multi‐walled carbon nanotubes to modify poly(ethylene terephthalate) obtained via in situ polymerization

The introduction of carbon nanotubes in a polymer matrix can markedly improve its mechanical properties and electrical conductivity, and much effort has been devoted to achieve homogeneous dispersions of carbon nanotubes in various polymers. Our group previously performed successfully fluorine‐grafted modification on the sidewalls of multi‐walled carbon nanotubes (MWCNTs), using homemade equipment for CF₄ plasma irradiation. As a continuation of our previous work, in the present study CF₄ plasma‐treated MWCNTs (F‐MWCNTs) were used as a nanofiller with poly(ethylene terephthalate) (PET), which is a practical example of the application of such F‐MWCNTs to prepare polyester/MWCNTs nanocomposites with ideal nanoscale structure and excellent properties. As confirmed from scanning electron microscopy observations, the F‐MWCNTs could easily be homogeneously dispersed in the PET matrix during the in situ polymerization preparation process. It was found that a very low content of F‐MWCNTs dramatically altered the crystallization behavior and mechanical properties of the nanocomposites. For example, a 15 °C increase in crystallization temperature was achieved by adding only 0.01 wt% F‐MWCNTs, implying that the well‐dispersed F‐MWCNTs act as highly effective nucleating agents to initiate PET crystallization at high temperature. Meanwhile, an abnormal phenomenon was found in that the melt point of the nanocomposites is lower than that of the pure PET. The mechanism of the tailoring of the properties of PET resin by incorporation of F‐MWCNTs is discussed, based on structure–property relationships. The good dispersion of the F‐MWCNTs and strong interfacial interaction between matrix and nanofiller are responsible for the improvement in mechanical properties and high nucleating efficiency. The abnormal melting behavior is attributed to the recrystallization transition of PET occurring at the early stage of crystal melting being retarded on incorporation of F‐MWCNTs. Copyright © 2009 Society of Chemical Industry