Curing Mechanism of Condensed Polynuclear Aromatic Resin and Thermal Stability of Cured Resin

In order to improve the thermal stability of condensed polynuclear aromatic(COPNA) resin synthesized from vacuum residue, 1,4-benzenedimethanol was added to cure COPNA resin. The curing mechanism was investigated by proton nuclear magnetic resonance spectrometry, solid carbon-13 nuclear magnetic resonance spectrometry and Fourier transform infrared spectroscopy. Microstructures of the uncured and the cured COPNA resins were studied by scanning electron microscopy and X-ray diffractometry. The thermal stability of COPNA resins before and after curing was tested by thermogravimetric analysis. The element composition of the cured COPNA resin heated at different temperatures was analyzed by an element analyzer. The results showed that the uncured COPNA resin reacted with the cross-linking agent during the curing process, and the curing mechanism was confirmed to be the electrophilic substitution reaction. Compared with the uncured COPNA resin, the cured COPNA resin had a smooth surface, well-ordered and streamlined sheet structure with more crystalline solids, better molecular arrangement and orientation. The weight loss process of the uncured and cured COPNA resins was divided into three stages. Carbon residue of the cured COPNA resin was 41.65% at 600 ℃, which was much higher than 25.02% of the uncured COPNA resin, which indicated that the cured COPNA resin had higher thermal stability.

COMPARISON OF THE E44 EPOXY RESINS IN DIFFERENT CONTENTS OF CURING AGENT BY MICROWAVE AND THERMAL CURING METHODS

This paper discusses the fundamental principle of microwave heating, and based on the advantages of microwave heating, use maleic anhydride as curing agent. The technology of microwave curing E44 epoxy resins is investigated, the mechanical properties of cured epoxy resin samples in different contents of curing agent by microwave and thermal curing methods are measured respectively, and then some experimental results for which are obtained. At last, this paper analyses why microwave curing can improve mechanical property of epoxy resin.

A Dielectric Ink Combining Acrylate and Cyanate Moieties for Inkjet 3D Printing with Good Thermal Stability

Inkjet 3D printing has potential in the additive manufacturing of electronic circuits and devices.However,inks that can be used for printing layers with T5%>300℃ or hardness>200 MPa have been rarely reported.Cyanate ester(CE)polymers have excellent thermal stability,high strength,and low shrinkage compared to other common dielectric inks for inkjet 3D printing,but cannot be quickly shaped by ultraviolet(UV)irradiation or thermal treatment.Combining CEs with UV-curable monomers may be a possible way to accelerate crosslinking,but there are challenges from the adverse effects of the dilution of both monomers.In this study,dielectric inks with acrylate and cyanate moieties were developed.The low viscosity and surface tension of the CE precursor(Bisphenol E cyanate ester)were combined with photocurable acrylate diluent monomers and cross-linker to realize an ink suitable for inkjet 3D printing.An internal dual three-dimensional cross-linked network structure resin was prepared by a combination of photocuring and thermal curing with T5%up to 326.69℃,hardness up to 431.84 MPa,dielectric constant of 2.70 at 8 GHz,and shrinkage of 1.64%.The developed dielectric inks can be applied to the 3D printing of printed circuit boards and other electronic devices that require dielectric properties.

Preparation, Curing Reactivity and Thermal Properties of Titanium-doped Silicone Resins

Novel titanium-doped silicone resins were synthesized from low-cost silane monomers and tetrabutyl titanate as raw materials and hydrochloric acid as catalyst, with titanium element as dopant into principal chain of Si-O-Si. The resins were characterized by means of FTIR, IH NMR and 13C NMR spectra, their thermal properties and curing properties were investigated and their corresponding films were determined. The results show that the thermal stability and storage stability of the resins were influenced by the types of silane monomers containing dif- ferent carbon atomicities of organic group. The thermal stability of the titanium-doped silicone resin with a molar ratio of silane monomer B（n-propyl triethoxysilane） to silane monomer C（n-octyl triethoxysilane） being 1：1 is superior to that of the resin with a molar ratio of silane monomer B to silane monomer C being 1：3. However, the storage stability of the former is inferior to that of the latter. This work also showed that the synthesized titanium-doped silicone resins have the highest thermal stability up to 450--500℃ with an atomicity molar ratio of 1：4 of titanium to silicon in the reactants. But the best storage stability of the resin prepared from the reactants with an atomicity molar ratio of 1：6[n（Ti）：n（Si）] was obtained. The effect of the type and content of curing agent on the curing properties of the resin was also studied. Moreover, thermal mechanism and curing mechanism were proposed in this work.

CURING KINETICS AND THERMAL STABILITY OF EPOXY BLENDS CONTAINING PHOSPHOROUS-OXIRANE WITH AROMATIC AMIDE-AMINE AS CURING AGENTS

This article describes the synthesis of a series of aromatic amide-amines and their potential use as epoxy hardeners. These amines were synthesized by the reaction of L-phenylalanine （PA） with diamines of different structures i.e. 1,4- phenylene diamine （PD）, 1,5-diamino naphthalene （N）, 4,4＇-（9-fluorenyllidene）-dianiline （F）, 4,4＇-diaminodiphenyl sulphide （DS） and 3,4＇-oxydianiline （O） in a stoichiometric ratio （I ：1）. Structural characterization of synthesized amide-amines was done with the help of elemental analysis and spectroscopic techniques viz. FT-IR, 1H-NMR and 13C-NMR. An epoxy blend was prepared by mixing tris（glycidyloxy） phosphine oxide （TGPO） with conventional epoxy i.e. diglycidyl ether of bisphenol-A （DGEBA） in an equivalent ratio of 2：3 to incorporate phosphorous into the main chain. The curing kinetics of the epoxy blend with synthesized aromatic amide-amines was investigated by non-isothermal DSC technique using multiple heating rate method （5, 10, 15 and 20 K/min.）. The activation energies were determined by fitting the experimental data into Kissinger and Ozawa kinetic models. The activation energies obtained through Ozawa method were slightly higher than those of Kissinger method but were comparable. However, both the energies were found to be dependent on the structure of amines. The thermal stability and weight loss behavior of isothermally cured thermosets were also investigated using thermogravimetric analysis （TGA） in nitrogen atmosphere. All the samples showed improved thermal stability in terms of char yield than using only amines as hardeners.

Thermal stability and curing kinetics of polycarbosilane fibers

Thermal stability and curing kinetics of polycarbosilane (PCS) fibers were studied by thermogravimetry (TG), Fourier transform infrared spectroscopy(FT-IR). Curing is an essential step in the preparation of SiC fibers and the properties of SiC fibers are affected greatly by curing conditions. TG measurement performed in air shows that mass gain starts at approximately 200℃ and PCS fibers are sensitive to oxygen. Curing with oxygen, which results in crosslinking on the surface, enabled PCS fibers to retain its shape during high-temperature pyrolysis. The curing of PCS fibers is oxidation of Si─H and Si─CH3, then Si─O─Si and Si─O─C bonds are formed. This is a first order reaction, with activation energy of 79.27 kJ/mol, and the pre-exponential factor is calculated as 3.07×106. The kinetics model was obtained and the experimental data of PCS fibers show good agreement with the kinetics model.

Curing mechanism of furan resin modified with different agents and their thermal strength

The curing mechanism of furfuryl alcohol and urea-formaldehyde furan resins was investigated using infrared spectroscopy(IR) technique.The curing productions of urea-formaldehyde furan resins modified with different agents(i.e.sorbitol,polyester polyol,phenol and acetone) and the productions of incomplete curing were characterized by differential thermal analysis(DTA) and thermal gravity analysis(TG).The results indicate that except for polyester polyol,the other modifiers have little effect on the thermal strength of urea-formaldehyde furan resin.Furthermore,the thermal strength can be improved at a temperature of higher than 550℃.

Investigation on Thermal and Dimensional Stability of Epoxy Resin In-Situ Modified by Cyanate Ester Resin and Polydimethylsiloxane

The thermal and dimensional stability of epoxy resin(EP)in-situ modified by cyanate ester(CE)and polydimethylsiloxane(PDMS)are investigated by means of experiments and numerical simulation.Thermal gravimetric analysis(TGA)and differential scanning calorimeter(DSC)are used to analyze the heat resistance of the modified EP.The dimensional stability is characterized by the volume shrinkage of the series PDMS/CE/EP obtained by the density method.The chemical structure of the PDMS/CE/EP is analyzed by Fourier transform infrared spectroscopy(FTIR).The results of TGA and DSC indicate that the thermal stability of PDMS/CE/EP decreases firstly and then increases with the increase in the amount of CE.The addition of PDMS shows a slight effect on the thermal stability.The 40%CE makes the blending system exhibit the lowest initial decomposition temperature,which reduces by 15.5%and 40.8%compared with pure EP and CE,respectively.The FTIR results suggested that the influence of CE on the thermal stability of the modified EP is mainly ascribed to the generation of oxazolidinone ring with low thermal stability and the increase in the triazine ring with high thermal stability.The volume shrinkage measurement results show that the introduction of CE and PDMS are both beneficial to the improvement of the dimensional stability of the blending systems.The in-situ addition of 80%CE shows the lowest volume shrinkage of6.11%.The thermal stress distribution of PDMS/CE/EP generated during the solidification process is simulated by the finite element analysis.The results suggested that the introduction of 80%CE into EP results in the lowest thermal stress in the blending system,which indicates that the system has the lowest volume shrinkage,which agrees well with the experimental results.

Synthesis and Thermal Properties of a Novel Nitrogen-containing Epoxy Resin

A new nitrogen-containing epoxy resin (XT resin) was synthesized from chain extension of xylenephenolformaldehyde resin (XPF) and triglycidyl isocyanurate (TGIC) in the presence of base catalyst. FT-IR and H-NMR analysis confirmed the chemical structure of XT resin. It was 1 cured with dicyandiamide (DICY) and diaminodiphenyl sulfone (DDS). Dynamic mechanical analysis (DMA) results showed that the introduction of triazine ring provides epoxy polymer with good thermal stability. Furthermore, high char yields at 800℃ in thermogravimetric (TGA) analysis indicated that XT resin had potential flame retardance.

CHARACTERIZATION AND THERMAL STABILITY OF PMR POLYIMIDES USING 7-OXA-BICYCLO[2,2,l]HEPT-5-ENE-2,3-DICARBOXYLIC ANHYDRIDE AS END CAPS

An anhydride monomer containing ether oxide bridge, 7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride （ONA）, was successfully synthesized by Diels-Alder reaction of furan and maleic anhydride. The ONA was also studied as an end-cap for the polymerization of monomer reactant （PMR） type polyimides. Three molecular weight levels of the ONA end-capped PMR resins were evaluated. The effects of process conditions of these novel PMR resins on thermal and mechanical properties were investigated. It was demonstrated that the imidized prepolymers using the end-cap have good processability, and the cured polyimide specimens exhibited good thermal stability. The initial decomposition temperature, Td （ca. 580℃） and glass transition temperature, Tg （330℃） of the novel resin （PI-20）, prepared trader optimum process conditions, compare favorably with the Td （ca. 620℃） and Tg （ca. 348℃） of the state-of-the-art resin （PI＇-20）, respectively.

Non-isothermal curing kinetics and thermal properties of benzoxazine-phenolic copolymers

Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular structure of the novolac-type phenolic resin and the benzoxazine-phenolic copolymer BP31. In order to understand the curing process of the copolymers, the curing behavior and curing kinetic characteristics were studied by differential scanning calorimetry （DSC）, and the catalytical effect of phenolic hydroxyl on the curing behavior of copolymers was investigated. To investigate the thermal properties of this resin, the thermal degradation behaviors of the cured samples were studied by thermal gravimetric （TG） method, and glass-transition temperatures （Tg） of the cured copolymers were also evaluated by DSC. The dynamic Ozawa method was adopted to determine the kinetic parameters of the curing process as well. The activation energy is 78.8 kJ/mol and the reaction rate constant is in the range from 40.0 to 5.2 （K/min）＂ according to reaction temperatures. The Ozawa exponent decreases from 2.4 to 0.7 with the increase of reaction temperature, and curing mechanism is expounded briefly according to the results. TG result shows that the highest char yield of copolymers is 50.3%. The highest Tg of copolymers is 489 K, which is much higher than that of pure benzoxazine resin.

Engineering phosphorus-containing lignin for epoxy biocomposites with enhanced thermal stability,fire retardancy and mechanical properties

Fabricating a high-performing thermoset using bio-based flame retardant is critical for the sustain-able development of engineering materials with superior fire safety and robust mechanical properties.Herein,the epoxy(EP)composites with the industrial requirements are manufactured with a novel high-efficient,lignin-based flame retardant named DAL-x,which is fabricated by grafting 9,10-dihydro-9-oxa-10-phosphaze-10-oxide(DOPO)onto lignin.The resulting DAL-x/EP composite exhibits excellent flame retardancy with a desirable UL-94 V-0 rating and a satisfactory limiting oxygen index(LOI)of 29.8%due to the appropriate phosphorus content of DAL-x with adjustable molecular chain structure.More-over,the DAL-x/EP composite shows an unexpected improvement in the elastic modulus(∼36%)and well-preserved strength and ductility compared with those of pure EP.This work offers a feasible strat-egy for creating efficient bio-based flame retardants utilizing industrial waste lignin and preparing high-performance EP composites that meet the demanding requirement of fire retardancy in industries,con-tributing to the circular economy and sustainability.

Study of catalytic effect of ammonium molybdate on the bisphthalonitrile resins curing reaction with aromatic amine

A kind of catalyst, ammonium molybdate was developed in this paper to promote the curing reaction of bisphthalonitrile resins with aromatic amine as curing agent, and the catalytic effect was studied by differential scanning calorimetry （DSC）, rheometric measurements and thermogravimetric analysis （TGA）. The results indicated that the catalyst could improve the curing rate and increase the curing degree, which could be regulated by the content of the catalyst used in the reaction.

Enhanced Thermal Resistance of Boron Phenolic Composites by Addition of TiSi_(2) Particles

TiSi_(2) reinforced boron phenolic composites(TP)and Vitreous silica fabric reinforced TiSi_(2)/boron phenolic composites(VTP)were prepared by compression molding,and their thermal,mechanical,ablation properties were studied.TG results show that thermal stabilities and residual carbon rate of boron phenolic are improved after introducing TiSi_(2) particles.Compared with VTP-0(containing 0 phr TiSi_(2)),flexural strength of VTP-60(containing 60 phr TiSi_(2))pyrolysis product increases by 29.5%at 1200℃.Raman spectrum shows that TiSi_(2) particles promote the ordering of the glass carbon structure of VTP pyrolysis product.Compared to VTP-0,the linear and mass ablation rates of VTP-60 reduce by 32.1%and 77.5%,respectively.XRD and SEM indicate the formation of an oxide coating layer,TiO_(2)-SiO_(2),integrates the bulk and protects the underlying materials from damage under high temperature oxygen-containing airstream.All these results prove that mechanical properties of pyrolysis product,thermal,and ablation resistance are improved by addition of TiSi_(2) particles.

SYNTHESIS,CHARACTERIZATION OF DIAMIDE-DIIMIDE-DIAMINES BASED ON L-CYSTEINE AMINO ACID AND THEIR EFFECT ON THE THERMAL PROPERTIES OF DIGLYCIDYL ETHER OF BISPHENOL-A(DGEBA)

The curing behavior of diglycidyl ether of bisphenol-A(DGEBA) with aromatic diamide-diimide-diamines having aryl ether,sulfone and methylene linkages was studied by differential scanning calorimetry(DSC).Nine diamide-diimide-diamines of varying structure were synthesized by reacting 1 mole of dianhydride with 2 moles of L-cysteine(S) in a mixture of acetic acid and pyridine(3:2 V/V) followed by activation with thionyl chloride(SOCl_2) and then condensation with excess of diamines.Structural characterization...

Study on the Stability of Ion-exchange Resin Catalysts:Ⅰ. TGA as a Rapid Evaluating Method

The thermal stability of five commercial ion-exchange resin catalysts was studied by means of thermal gravimetric analysis （TGA） at elevated temperatures of up to 600℃ and isothermal temperatures in the range of 150℃ and 200 ℃. Resin samples with different initial water contents were also investigated. The study indicated that TGA, as a complementary evaluating method for the plug flow reactor system approach, could be used as a fast analyzing means for study on the thermal stability of ion-exchange resin catalysts. The stoichiometric calculation of the isothermally treated resin catalysts based on the FTIR analysis and acid capacity confirmed that the weight loss of the resins at 150℃ and 200℃ was caused by the desulfonation process and that desulfonation occurred mainly at the para-position of the benzene ring in the resins. H＋ ions and moisture played an important role in the desulfonation process.

Numerical Study on the Resin Transfer Molding Curing Process for Thick Composites Materials

The successful manufacture of thick composites is challenging since the highly exothermic nature of thermoset resins and limited temperature control make avoiding the onset of detrimental thermal gradients within the composite relatively difficult.This phenomenon is mainly caused by exothermic heat reactions.The so-called Michaud's model has been largely used in the literature to reduce the gap between experience and simulation with regard to the effective prediction of the temperature cycle in these processes.In this work,another solution is proposed to simulate the curing process for thick composites,namely preheating the resin to activate the curing reaction before resin injection into the mold.A good agreement between the experiment and the simulation is found.Moreover,in order to minimize the thermal gradient in the final composite,the thermophysical properties of the fiber and the torque(temperature,time)of the Plate have been varied leading to interesting results.

Sawdust Short Fiber Reinforced Epoxidized Natural Rubber: Insight on Its Mechanical, Physical, and Thermal Aspects

In this work,Epoxidized natural rubber/sawdust short fiber(ENR-50/SD)composites at different fiber content(5,10,15 and 20 phr)and size(fine size at 60–100μm and coarse size at 10–20 mm)were prepared using two-roll mill and electrical-hydraulic hot press machine respectively.Curing characteristics,water uptake,tensile,morphological,physical,and thermal properties of the composites were investigated.Results indicated that the scorch time and cure time became shorter whereas torque improved as SD content increase.Though the decline of tensile strength and elongation at break values,modulus,hardness and crosslinking density have shown enhancements with the increasing of SD content.The water uptake percentage of all samples has shown an increasing as SD content increase.However,the low SD content,particularly fine size have presented lower water uptake.The temperature of weight%loss(5 and 50 wt%loss)of 5 phr SD(low content)have recorded higher temperature compared to 20 phr SD(high content)in the rubber composites,which indicated higher thermal stability.The fine size of SD has recorded better overall properties than SD coarse size at same loading in the rubber composites.

Nanocomposites of a Silicon-containing Arylacetylene Resin with Octakis(dimethylsiloxy)octasilsesquoixane

Nanocomposites（PMSEPE/Q8M8^H） were prepared via solution blending of octakis（dimethylsiloxy）octasilsesquoixane（Q8M8^H） into poly（dimethylsilyleneethynylenephenyleneethynyle ne）（PMSEPE）. PMSEPE/Q8M8^H nanocomposites were characterized by Fourier transform infrared（FT-IR） spectroscopy, rheological measurement, differential scanning calorimetry（DSC）, scanning electron microscopy（SEM） and thermal gravimetric analysis（TGA）. The experimental results show that the hydrosilylation reaction in PMSEPE/Q8M8^H nanocomposites occurs slowly exceeding 180 ℃. PMSEPE/Q8M8^H nanocomposites can be cured at temperatures less than 260 ℃ and the cube structure of Q8M8^H keeps stable during the curing process. POSS domains are evenly dispersed in the cured nanocomposite. However, serious aggregation of POSS occurs at 15% Q8M8^H content. The thermal and thermooxidative stabilities of PMSEPE/Q8M8^H nanocomposites obviously depend on the content of Q8M8^H. The incorporation of Q8M8^H can effectively enhance the thermal and thermooxidative stabilities of cured PMSEPE. PMSEPE/Q8M8^H nanocomposites can be the candidates for applications in high temperature environment.

Bio-Based Hyperbranched Toughener From Tannic Acid and Its Enhanced Solvent-Free Epoxy Resin with High Performance

It is essential to design economic and efficient tougheners to prepare high-performance epoxy resin;however,this has remained a huge challenge.Herein,an eco-friendly,low-cost,and facile-fabricated bio-based hyperbranched toughener,carboxylic acid-functionalized tannic acid(CATA),was successfully prepared and applicated to the preparation of solvent-free epoxy resins.The mechanical performance,morphology,structural characterization,and thermal characterization of toughened epoxy resin system were studied.The toughened epoxy resin system with only 1.0wt%CATA reached the highest impact strength,111%higher than the neat epoxy resin system.Notably,the tensile strength and elongation at break of toughened epoxy resin systems increased moderately with increasing CATA loading.Nonphase-separated hybrids with significant toughening effect were obtained.Additionally,the thermal stabilities of toughened epoxy resin systems decreased with increasing CATA loading.This study provides an eco-friendly,cost-effective,and facile approach for the preparation of high-performance,solvent-free epoxy resins with potential for practical applications in sealing integrated circuits and electrical devices fields.