Curing reaction and mechanism of phenol-formaldehyde novolac resins for foundry

In this study on the curing dynamics of phenol-formaldehyde novolac resins(PFNR) and hexamethylene tetramine(HMTA), two typical commercial PFNR were selected as examples and the curing reactions of the resins with HMTA were studied by differential scanning calorimetry(DSC). Based on the data calculated by the Kissinger equation and the Crane equation, a thermocuring dynamic model was established, from which the process conditions, activation energy, reaction kinetics equation and a f irst-order reaction of the curing reactions were derived.

SYNTHESES AND ADSORPTION PROPERTIES OF PHENOL-FORMALDEHYDE-TYPE CHELATING RESINS BEARING THE FUNCTIONAL GROUP OFTAR TARIC ACID

Several kinds of novel chelating resins bearing the functional group of tartaric acid (TTA-FQ-12, TTA-FQ-23, and TTA-FQ-34) were synthesized by reacting epoxy maleic anhydride, which was prepared through the oxidization reaction of maleic anhydride by hydrogen peroxide, with phenol-formaldehyde resin containing polyamine (FQ resins series). The effects of such factors as reaction time, reaction temperature and pH value on the loading capacity of TTA in resins were investigated. The results showed that the optimum reaction conditions are as follows: time 9-12 h; temperature 90-105'C; pH value 6-10. The loading capacities of TTA can reach 0.15, 0.14, and 0.11 mmol/g-1 when the functional group of FQ resin was - OCH2CH2NHC2H4NH2, - O(CH2CH2NH)2C2H4NH2 and - O(CH2CH2NH)3C2H4NH2), respectively. The structures of resins were characterized by FTIR spectra. The primary study on the adsorption properties of the resins for metal ions showed that there are two kinds of adsorption mechanisms i.e. ion exchange and chelate in the adsorption process. TTA-FQ resins have much higher adsorption selectivity for Pb2+and Zn2+ than for Cu2+ and Ni2+. These resins can probably be used for separating Pb2+ or Zn2+ in the mixture of metal ions or for treating wastewater containing heavy metal ions.

Effect of Phenolation, Lignin-Type and Degree of Substitution on the Properties of Lignin-Modified Phenol-Formaldehyde Impregnation Resins: Molecular Weight Distribution, Wetting Behavior, Rheological Properties and Thermal Curing Profiles

Here,the effects of substituting portions of fossil-based phenol in phenol formaldehyde resin by renewable lignin from two different sources are investigated using a factorial screening experimental design.Among the resins consumed by the wood-based industry,phenolics are one of the most important types used for impregnation,coating or gluing purposes.They are prepared by condensing phenol with formaldehyde(PF).One major use of PF is as matrix polymer for decorative laminates in exterior cladding and wet-room applications.Important requirements for such PFs are favorable flow properties(low viscosity),rapid curing behavior(high reactivity)and sufficient self-adhesion capacity(high residual curing potential).Partially substituting phenol in PF with bio-based phenolic co-reagents like lignin modifies the physicochemical properties of the resulting resin.In this study,phenol-formaldehyde formulations were synthesized where either 30%or 50%(in weight)of the phenol monomer were substituted by either sodium lignosulfonate or Kraft lignin.The effect of modifying the lignin material by phenolation before incorporation into the resin synthesis was also investigated.The resins so obtained were characterized by Fourier Transform Infra-Red(FTIR)spectroscopy,Size Exclusion Chromatography(SEC),Differential Scanning Calorimetry(DSC),rheology,and measurements of contact angle and surface tension using the Wilhelmy plate method and drop shape analysis.

Kinetic Study of Curing Phenol-Formaldehyde/Tannin-Formaldehyde Composite Resins

This work presents a study on the uses of tannin-formadehyde derivative into phenolic resins. Eucalyptus tannins (T) were reacted with formaldehyde to form tannin-formaldehyde resin (TF). Then this derivative was used to prepare tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 %w/w. The kinetic values of thermal curing of Phenol-formaldehyde (PF), tannin-formaldehyde and tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 wt% from TF were studied by monitoring the weight changes which occurred in the samples weight during thermosetting process at four temperature (160°C, 180°C, 200°C and 220°C). The total evolved condensation products from curing reactions were about 32% - 36% per sample weight, and the rate of curing reaction constants was ranged between 0.163 %wt·min-1 at 160°C and 0.50 %wt·min-1 at 220°C. The path of TFPF curing and kinetic values indicated that these resins could be cured with the behavior and velocity comparable to that of PF. The activation energy of TFPF cross-linking was higher than that of PF. Increasing TF level to 20% and 40% into PF can reduce the amount of PF curing reactions density and weight loss percentage. The global kinetic properties showed that the TF participated in the thermoset network formation with acceptable activity and performance. The general results of this paper show that the TF is a suitable alternative material for partially replacement into PF resin.

Complexation Between Borate ion and Hydroxyl Groups of Phenol-Formaldehyde Resol Resin

The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy. The results show that the complexation can proceed completely and rapidly at room temperature. Borate ion attacks phenol hydroxyl groups and adjacent position hydroxymethyl groups on the phenol ring of the resin, and forms the coordinate bond between boron atom in borate ion and oxygen atom in the hydroxyl groups. The complexation is a quantitative reaction. The complex is a six member ring containing two oxygens and one boron. The complexation can release hydrogen ions resulting in the decreasing pH in the resin solution.

Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin

This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.

Using optical coherence tomography images to evaluate fungal growth in reline resins

As changes in hard or soft oral tissues normally have a microbiological component,it is important to develop diagnostic techniques that support clinical evaluation,without destroying microbio-logical formation.The optical coherence tomography(OCT)represents an alternative to analyze tissues and microorganisms without the need for processing.This imaging technique could be defined as a fast,real-time,in situ,and non-destructive method.Thus,this study proposed the use of the OCT to visualize biofilm by Candida albicans in reline resins for removable prostheses.Three reline resins(Silagum-Comfort,Coe Comfort,and Soft-Confort),with distinct char-acteristics related to wa ter sorption and fungal inhibition were used.A total of 30 samples(10 for each resin group)were subjected to OCT scanning before and 96 h after inoculation with Candida albicans(URM 6547).The biofilm analysis was carried out through a 2D optical Callisto SD-OCT(930 nm)operated in the spectral domain.Then,the images were preprocessed using a3×3 Gaussian filter to remove the noise,and then Otsu binarization,allowing segmentation and pixel counting.The layer's biofilm formed was clearly defined and,indeed,its visualization is modified by water sorption of each material.Silagum-Comfort and Soft.Confort showed some similarities in the scattering of light between the clean and inoculated samples,in which,the latter samples presented higher values of light signal intensity.Coe-Comfort samples were the only ones that showed no di®erences between the clean or inoculated images.Therefore,the results of this study suggest that OCT is a viable technique to visualize the biolm in reline materials.Becausendings in the literature are still scarcely using the OCT technique to visualize biolm in reline resins,further studies are encouraged.It should not contain any references or displayed equations.

MUF Resins Improved by Citric Acid as Adhesives for Wood Veneer Panels

This article presents the first applied results of using citric acid in combinations with a melamine-urea-formal-dehyde(MUF)resin for bonding wood veneers.The chemical reactions involved are shown based on a MALDI ToF analysis of the reaction of the MUF resin with citric acid.The preliminary results of the physical and mechanical properties of the LVL prepared are also presented.Veneers from Populus sp were used to manufacture 5-layer laminated veneer lumber(LVL)of small dimensions.Five combinations of the amount of citric acid,MUF spread rate and pressing parameters were tested.LVL bonded with 20%of citric acid+100 g/m^(2)of MUF,hot-pressed using a 3-step process with maximum 1.5 MPa of pressure yielded the board with better dimensional stability and mechanical properties.It could be concluded that citric acid in combination with MUF can be used for bonding wood veneer and the research should be continued to study further the parameters involved and to enhance the results.

Plasma Treatment Induced Chemical Changes of Alkali Lignin to Enhance the Performances of Lignin-Phenol-Formaldehyde Resin Adhesive

Alkali lignin was processed by plasma and then used in modification of phenol formaldehyde resin in this study.Chemical structural changes of lignin which was processed by plasma as well as bonding strength,tensile property,curing performance and thermal property of the prepared phenol formaldehyde resin which was modified by the plasma processed lignin were analyzed.Results demonstrated that:(1)Alkali lignin was degraded after the plasma processing.The original groups were destroyed,and the aromatic rings collected abundant free radicals and oxygen-containing functional groups like hydroxyls,carbonyls,carboxyls and acyls were introduced into increase the reaction activity of lignin significantly.(2)The introduction of alkali lignin decreased the free formaldehyde content and increased bonding strength and toughness of the prepared phenol formaldehyde resin,especially after the introduction of lignin treated with plasma.(3)The introduction of alkali lignin led to high curing temperature for the prepared phenol formaldehyde resin,but that was reduced by the plasma processed alkali lignin.(4)The introduction of alkali lignin could also increase thermal stability of phenol formaldehyde resin,but that was modified by plasma processed alkali lignin was better than the unprocessed lignin.Based on the results,the plasma processed lignin was used to modify phenol formaldehyde resin,which could increase the strength and toughness of phenol formaldehyde resin significantly.

Study on binder system of CO_2-cured phenol-formaldehyde resin used in foundry

A new aqueous alkaline resol phenol-formaldehyde resin has been prepared from phenol and formaldehyde using NaOH as catalyst; the optimum synthetic process has been determined. With addition of some cross-linking agents, after passing carbon dioxide gas through the resin bonded sand, high as-gassed strength and 24 h strength are achieved. The bonding bridge of the resin bonded sand fracture has been analyzed by using SEM.

Room-Temperature Phosphorescence and Lifetime of Fossil Resins (Amber) from Dominican Republic, Mexico, Baltic Sea, Myanmar, and Fushun, China

Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Republic,Mexico,Baltic sea,Myanmar,and Fushun,China.The results show that amber from the same geographic origin has similar shape in phosphorescence spectra.However,the shape of the amber phosphorescence spectra varies depending on their different localities.Burmite(amber from Myanmar)and Fushun amber have a bright yellow phosphorescence with a long lifetime,while the Dominican and Mexican ones are weaker and last shorter.The irradiation of Baltic amber becomes faint or even inert.Phosphorescence spectral Gaussian fitting results suggest an emission maximum near 550 nm in most amber samples.Their phosphorescence lifetime,analyzed through the exponential function fitting,is up to 1 second in Burmite and Fushun samples,shorter in the Dominican and Mexican ones,about 0.230 s,and the shortest in Baltic amber,close to 0.151 s.These variations of phosphorescence lifetime and intensity are related to the relative geological ages of these amber.It indicated that the phosphorescence agent was probably formed during the long geological time.While the anomaly occurred in Baltic amber,the only one found in a sea secondary deposit form,it demonstrated that the terrestrial geological environment these amber preserved has prevented the phosphorescence agent to be deactivated.

Effect of benzoxazine resin on mechanical properties of nitrile rubber composites: Experiment and molecular simulation

Benzoxazine resin,being a new type of phenolic resin deve-loped to overcome the shortcomings of traditional phenolic resins,has been synthesized from phenol,formaldehyde and amine,and does not require solvent elimination or monomer purification to obtain a relatively clean precursor.It has potential application in the field of aerospace due to its low expansion coefficient,high weather resistance,high carbon yield,good mechanical strength,and excellent ablation resistance[1].It can be mixed with various other resins or polymers to produce new resins with a broad range of applications[2-3].

Cardo poly (ether sulfone) toughened E51/DETDA epoxy resin and its carbon fiber composites

A toughener that can effectively improve the interlaminar toughness in carbon fiber composites is crucial for various applications.We investigated,the toughening effects of phenolphthalein-based cardo poly(ether sulfone)(PES-C)on E51/DETDA epoxy and its carbon fiber composites(CFCs).Scanning electron microscopy showed that the phase structures of PES-C/epoxy blends change from island(of dispersed phase)structures to bi-continuous structures(of the matrix)as the PES-C content increased,which is associated with reaction-induced phase separation.After adding 15 phr PES-C,the glass transition temperature(T_(g))of the blends increased by 51.5℃,and the flexural strength,impact strength and fracture toughness of the blends were improved by 41.1%,186.2%and 42.7%,respectively.These improvements could be attributed to the phase separation structure of the PES-C/epoxy sys-tem.A PES-C film was used to improve the mode-II fracture toughness(G_(IIC))of CFCs.The G_(IIC) value of the 7μm PES-C film toughened laminate was improved by 80.3%compared to that of the control laminate.The increase in G_(IIC) was attributed to cohesive failure and plastic deformation in the interleaving region.

Effect of Epoxy Resin on the Properties of Recycled Asphalt

To promote the recycling of reclaimed asphalt pavement(RAP),epoxy resin was used to prepare the epoxy-recycled asphalt mixtures.The effect of epoxy resin on the properties of aged asphalt binder was investigated based on the tensile test,flexural creep test,and laser scanning confocal microscopy.The curing characteristics and the mechanical performance of recycled asphalt with different epoxy contents were explored.The results show that the low-temperature performance,ductility,and strength of the aged asphalt binder were significantly improved when the epoxy content reached 40%.The curing time of epoxy-recycled asphalt should be at least 4 d to ensure the formation of good internal spatial network structure.

B-COPNA resin formation from ethylene tar light fractions:Process development and mechanical exploration by molecular simulation

An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear aromatic resin of moderate condensation degree(B-COPNA)is a widely used carbon material due to its superb processability,the production of which is,however,seriously limited by the high cost of raw materials.Under such context,an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar(ETLF,boiling point<260℃)facilitated by molecular simulation.1,4-Benzenedimethanol(PXG)was first selected as the crosslinking agent according to the findings of molecular simulation.The effects of operating conditions,including reactions temperature,crosslinking agent,and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process.The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents.It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents.In addition to the highest yield and greatest heat properties,PXG-prepared resin contained the most condensed aromatics.The corresponding optimized conditions of resin preparation were 180℃,1:1.9(PXG:ETLF),and 3%(mass)of catalyst content with a resin yield of 78.57%.It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation,according to the experimental characterization and molecular simulation.Hence,it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation,bringing huge economic value to the current petrochemical industry.

Kinetics and Mechanism of Hydration of Acrylic Acid over Ion-exchanged Resin:Experimental Exploration and DFT Calculation

Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.

Enhanced corrosion resistance of epoxy resin coating via addition of CeO_(2) and benzotriazole

The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.

Preparation of Environmentally Friendly Urea-Hexanediamine-Glyoxal(HUG)Resin Wood Adhesive

Using non-toxic,low-volatile glyoxal to completely replace formaldehyde for preparing urea-glyoxal(UG)resin adhesive is a hot research topic that could be of great interest for the wood industry.However,urea-glyoxal(UG)resins prepared by just using glyoxal instead of formaldehyde usually yields a lower degree of polymerization.This results in a poorer bonding performance and water resistance of UG resins.A good solution is to pre-react urea to preform polyurea molecules presenting already a certain degree of polymerization,and then to condense these with glyoxal to obtain a novel UG resin.Therefore,in this present work,the urea was reacted with hexamethylene diamine to form a polyurea named HU,and then this was used to react it with different amounts of glyoxal to synthesize hexamethylenediamine-urea-glyoxal(HUG)polycondensation resins,and to use this for bonding plywood.The results show that the glyoxal can well react with HU polyuria via addition and schiff base reaction,and also the HUG resin exhibits excellent bonding strength and water resistance.The shear strength of the plywood bonded with this HUG at 160°C hot press temperature as high as 1.93 MPa,2.16 MPa and 1.61 MPa,respectively,which meets the requirement of the China national standard GB/T 9846-2015(≥0.7 MPa),and can be a good choice as a wood adhesive for industrial application.

Optimization Mechanism of Mechanical Properties of Basalt Fiber-Epoxy Resin Composites by Interfacially Enriched Distribution of Nano-Starch Crystals

Fibre reinforced polymer composites have become a new generation of structural materials due to their unique advantages such as high specific strength,designability,good dimensional stability and ease of large-area monolithic forming.However,the problem of interfacial bonding between the resin matrix and the fibres limits the direct use of reinforcing fibres and has become a central difficulty in the development of basalt fibre-epoxy composites.This paper proposes a solution for enhancing the strength of the fibre-resin interface using maize starch nanocrystals,which are highly yield and eco-friendly.Firstly,in this paper,corn starch nanocrystals(SNC)were prepared by hydrolysis,and were deposited on the surface of basalt fibers by electrostatic adsorption.After that,in order to maximize the modification effect of nano-starch crystals on the interface,the basalt fiber-epoxy resin composite samples were prepared by mixing in a pressureless molding method.The test results shown that the addition of basalt fibers alone led to a reduction in the strength of the sample.Deposition of 0.1 wt%SNC on the surface of basalt fibers can make the strength consistent with pure epoxy resin.When the adsorption amount of SNC reached 0.5 wt%,the tensile strength of the samples was 23.7%higher than that of pure epoxy resin.This is due to the formation of ether bond homopolymers between the SNC at the fibre-epoxy interface and the epoxy resin,which distorts the originally smooth interface,leading to increased stress concentration and the development of cracks.This enhances the binding of basalt fibers.The conclusions of this paper can provide an effective,simple,low-cost and non-polluting method of interfacial enhancement modification.

Evaluating two stages of silicone-containing arylene resin oxidation via experiment and molecular simulation

Silicon-containing aryl acetylene resin(PSA)is a new type of high-temperature resistant resin with excellent oxidation resistance,whereas antioxidant reaction mechanism of PSA resin under ultra-high temperatures still remains unclear.Herein,the oxidation behavior and mechanisms of PSA resin are systematically investigated combining kinetic analysis and Reax FF molecular dynamics(MD)simulations.Thermogravimetric analysis indicates that the oxidation process of PSA resin undergoes two main steps:oxidative mass gain and oxidative degradation.The distributed activation energy model(DAEM)is employed for describing oxidation processes and the best-fit one is obtained using genetic algorithms and differential evolution.DAEM model demonstrates that the oxidative weight gain stage is dominated by two virtual reactants and the oxidative degradation stage consists of three virtual reactants.Correspondingly,the observation of MD reaction pathways indicates that oxygen oxidation of unsaturated structures occurs in the initial stage,which results in the formation of PSA resin oxides.Furthermore,cracked pieces react with O_(2)to generate CO and other chemicals in the second step.The resin matrix's great antioxidation resilience is illustrated by the formation of SiO_(2).The analysis based on MD simulations exhibits an efficient computational proof with the experiments and DAEM methods.Based on the results,a two-stage reaction mechanism is proposed,which provides important theoretical support for the subsequent study of the oxidation behavior of silica-based resins.