PREPARATION AND PROPERTIES OF THERMOSETTING ACRYLIC COATINGS USING TITANIUM-OXO-CLUSTER AS A CURING AGENT

Thermosetting acrylic coatings were prepared by using carboxyl acid group-containing acrylic oligomer and curing with titanium-oxo-clusters which were first pre-hydrolyzed from titanium n-butoxide. The curing ability of the titanium-oxo-cluster was examined using a microdielectric analytical (DEA) curing monitor, Fourier transformed infrared spectroscopy (FTIR), and Soxhlet extraction experiments, and the properties of the resulted coatings were investigated with pendulum hardness tester, dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and ultraviolet-visible spectrometer. The effect of titania-oxo-cluster in leading acrylic oligomers to form thermosetting acrylic coatings was confirmed. An increasing pendulum hardness and modulus of acrylic coatings with increasing titania content was observed, which resulted from the increment of crosslinking degree rather than of the titania content. The thermosetting acrylic/titania coatings also showed better thermal stability and higher UV-blocking properties than those coatings using organic curing agent.

Spreading and Curing Behaviors of a Thermosetting Droplet-Silicone on a Heated Surface

Thermosetting materials are widely used as encapsulation in the electrical packaging to protect the core electronic components from external force, moisture, dust, and other factors. However, the spreading and curing behaviors of such kind of fluid on a heated surface have been rarely explored. In this study, we experimentally and numerically investigated the spreading and curing behaviors of the silicone(OE6550 A/B, which is widely used in the light-emitting diode packaging) droplet with diameter of ~2.2 mm on a heated surface with temperature ranging from 25 ℃ to 250 ℃. For the experiments, we established a setup with high-speed camera and heating unit to capture the fast spreading process of the silicone droplet on the heated surface. For the numerical simulation, we built a viscosity model of the silicone by using the Kiuna’s model and combined the viscosity model with the Volume of Fluid(VOF) model by the User Defined Function(UDF) method. The results show that the surface temperature significantly affected the spreading behaviors of the silicone droplet since it determines the temperature and viscosity distribution inside the droplet. For surface temperature varied from 25 ℃ to 250 ℃, the final contact radius changed from ~2.95 mm to ~1.78 mm and the total spreading time changed from ~511 s to ~0.15 s. By further analyzing the viscosity evolution of the droplet, we found that the decreasing of the total spreading time was caused by the decrease of the viscosity under high surface temperature at initial spreading stage, while the reduction of the final contact radius was caused by the curing of the precursor film. This study supplies a strategy to tuning the spreading and curing behavior of silicone by imposing high surface temperature, which is of great importance to the electronic packaging.

Molecular design of recyclable thermosetting polyimide and its composite with excellent mechanical and tribological properties

Recyclability of thermosetting polymers and their composites is a challenge for alleviating environmental pollution and resource waste.In this study,solvent-recyclable thermosetting polyimide(PI)and its composite were successfully synthesized.The tensile strength,elongation at break,and Young’s modulus of PI are 108.70±7.29 MPa,19.35%±3.89%,and 2336.42±128.00 MPa,respectively.The addition of reduced graphene oxide(RGO)not only enhances the mechanical properties of PI but also endows it with excellent tribological properties.The PI illustrates a high recycling efficiency of 94.15%,but the recycled composite exhibits inferior mechanical properties.The recycling and utilization of PI and its composite are realized through imine bonds(-C=N),which provides new guidance for solving the problem of environmental pollution and resource waste and is potential application in the field of sustainable tribology.

Thermosetting resin modified asphalt:A comprehensive review

Thermosetting resins have advantages such as high strength,corrosion resistance,and aging resistance,and have excellent prospects for practical application as asphalt modifiers.In order to promote the research of thermosetting resin modified asphalt,to provide direction for its further research,this paper reviews the research progress of thermosetting resin modified asphalt in recent years.The material composition,modification mechanism,and curing behavior of epoxy asphalt,thermosetting polyurethane modified asphalt,unsaturated polyester modified asphalt,and other thermosetting resin modified asphalts are overviewed.Different types of thermosetting resin modified asphalt have different performances,the performance advantages of different thermosetting resin modified asphalts are summarized.At the same time,the existing problems in thermosetting resin modified asphalt and further research directions are provided.Encouraging researchers to produce thermosetting resin modified asphalts using waste or bio-based materials,and to study the recycling technologies and life cycle assessment of thermosetting resin modified asphalt.This paper provides a reference for the study of thermosetting resin modified asphalt.

Highly Soluble Phenylethynyl-terminated Imide Oligomers and Thermosetting Polyimides Based on 2,2′3,3′-Biphenyltetracarboxylic Dianhydride

The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step method using 2,2′,3,3′-biphenyltetracarboxylic dianhydride(3,3′-BPDA) and aromatic diamines as the monomers, and 4-phenylethynyl phtlialic anhydride(PEPA) as the end-capping agent. The imide oligomers based on 3,3′-BPDA showed excellent solubility in low boiling point solvents and low melt viscosity, which were attributed to their unique bent architectures. High-performance thermosetting polyimides were produced from these oligomers via thermal crosslinking of the phenylethynyl groups. The mechanical and thermal properties of the thermosets were studied using tensile testing, dynamic mechanical thermal analysis(DMTA), and thermogravimetric analysis(TGA). The 3,3′EPDA-based thermosets exhibited excellent thermal properties, with glass transition temperatures of up to 455℃, and 5% mass loss temperatures of up to 569℃ in air. The thermosets based on 3,3-BPDA showed superior thermal properties compared to those derived from TriA-X series oligomers.

Phase separation time/temperature dependence of thermoplastics-modified thermosetting systems

The cure-induced phase separation processes of various thermoplastics(TP)-modified thermosetting systems which show upper critical solution temperature(UCST)or lower critical solution temperature(LCST)were studied with emphasis on the temperature dependency of the phase separation time and its potential application in the cure time-temperature processing window.We found that the phase separation time/temperature relationship follows the simple Arrhenius equation.The cure-induced phase separation activation energy E_(a)(ps)generated from the linear fitting of the Arrhenius equation is irrelevant to the detection means of phase separation time.We also found that E_(a)(ps)is insensitive to TP content,TP molecular weight and curing rate,but it changes with the cure reaction kinetics and the chemical environment of the systems.With the established phase separation time-temperature dependence relation,we can easily establish the whole cure time-temperature transformation(TTT)diagram with morphology information which is a useful map for the TP/TS composites processing industry.

Mechanical Properties of Carbon Epoxy Prepreg Insert Phenolic Resin Injection Moldings

This study focuses on the insert-injection molding process. The thermoset composite inserts in this study were carbon fiber/epoxy (CF/Epoxy) prepreg sheets. The injected molded part was glass fiber contained phenolic resin (GF/PF). The CF/Epoxy was placed in the mold cavity prior to injecting GF/PF onto the inserted injection molded CF/Epoxy specimens. The role of adhesion between the inserted part and injected resin on the mechanical properties was evaluated by 3 point bending and impact tests. In addition, the effect of prepreg orientation on the mechanical properties of the prepreg inserted-injection molding system was investigated. It was found that the prepreg with unidirectional orientation significantly improved flexural and impact strength of the inserted injection molding composites, providing better support and resistance to bending and impact loading. The main failure modes of the specimens were structural and adhesive failure.

Kinetic Laws of Heating Initiated Reactions for Materials in Aerospace Applications

Cure and decomposition reaction kinetics of typical organic materials in aerospace applications are introduced.From the data of dynamic differential scanning calorimetry(DSC)experiments,and based on changes of the peak temperatures(T_(p))with different heating rates(β),a linear equation,T_(p)=T_(1)+△Tlnβ,has been obtained more reasonably.The above equation can be used to explain some laws of higher or lower of apparent activation energies(E_(a)),by which the apparent activation energy(E_(a))is nearly equal to RT^(2)_(1)/△T.A number of kinetic investigations of typical thermosetting resins and energetic materials in aerospace applications were chosen to validate the above equations.

Challenging multiphase complex fluids for applications

Modern processing technology is calling the scientific understanding of dynamic processes,where the science of complex fluids plays a central role.We summarize our recent efforts using the generic approaches of multi-scale physics of complex fluids on apparently irrelevant processes,i.e.the mixing of polymer blends,the processing of thermoplastic(TP) toughened thermosetting(TS) composites using phase separation of TP in TS,as well as the enhanced oil recovery using polymer soft gel.It is emphasized that the thorough physical understanding in multi-scales of time and space through the joint efforts of experiment and theory in each scale is the key issue for the modeling of various processes.

Thermally Reversible,Self-Healing Polyurethane Based on Propyl Gallate and Polyurethane Prepolymers with Varied Isocyanate Content

Thermosetting polyurethanes are widely used in various fields owing to their excellent elasticity,strength and solvent resistance.Three environmental friendly propyl gallate-based self-healing polyurethanes were prepared from polyurethane prepolymers with varying isocyanate content.The thermal stabilities of the polyurethanes were tested using thermogravimetric analysis.Their self-healing and mechanical properties were analyzed using a universal testing machine and dynamic thermomechanical analysis.The polyurethanes were found with high self-healing ability and excellent mechanical properties due to the absence of phenolic carbamate.These qualities improved with increased isocyanate content and the prolonged selfhealing time.We found,therefore,that the propyl gallate-based polyurethane has potential for use in industrial applications as self-healing materials.

Thermal Polymerization of Cyanate Ester-Benzoxazine:Study of a Functional Model Compound

A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the blends are analyzed with the infrared radiation(IR),nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).The results show that an intermediate of the iminocarbonate and BOZ structures is formed by the ring-open BOZ reacting with the cyanate groups and ring-unopened BOZ.Moreover,rearrangement and ring-opening occur in the postcure of the intermediate to form the alkyl isocyanurate structure with polybenzoxazine.

The Effect of Epoxy Concentration and Fibre Loading on the Mechanical Properties of ABS/Epoxy-Coated Kenaf Fibre Composites

In this work, thermosetting resin, epoxy and fibre loading were used in optimizing the strength at which ABS/epoxy coated kenaf fibre (EKF) composites would perform apparently during mechanical stress. Kenaf bast fibres were resin coated before incorporated into engineering thermoplastic ABS at its processing temperature (230&degC), cured in-situ at internal mixer and later compression moulded at 210&degC under 65 kg/cm2pressure. The results showed the optimum level of tensile strength with thermoset and fibre loading as well as increase in strong interfacial bonding while the hardness values increased with increasing thermosetting and fibre contents. Both the tensile and flexural modulus apparently increased as the fibre contents increased.

低价、高效、微波产品用的TPA覆铜板

随着信息产业的飞速发展,高频信号设备,如高速计算机、移动电话、卫星通信等,都已从兆赫频段扩展到千兆赫,这就意味着对它们所用的微波电路基板提出了更高的要求。长期以来,高频微波基板几乎没有越出使用聚四氟乙烯的老传统,但是,它有若干缺点:玻璃化温度低,敌刚性差;加工复杂,故成本高;金属化孔镀层与孔壁的结合力弱,故可靠性不高。 多年来,美国GIL科技公司一直在研制替代聚四氟乙烯的材料,经过姐妹公司的合作,终于研制成功了TPA板材,这种材料克服了上述缺点,从而获得了美国专利。本文介绍了TPA层压板的电气特性、机械特性和热效应,给出了许多宝贵数据。

EXPERIMENTAL STUDY ON PEK -C MODIFIED EPOXIES AND THE CARBON FIBER COMPOSITES FOR AEROSPACE APPLICATION

The morphological structure of various epoxies toughened with a special amorphous thermoplastic PEK C and their carbon fiber composites were studied by using SEM. For both cases, phase separation and inversion took place to form fine epoxy rich globules dispersing in the PEK C matrix, in which the epoxy rich phase had the absolutely higher volume fraction. The phase structure and the interfacial properties were also studied by means of FTIR, DSC, and DMTA as well. An accompanying mechanical determination revealed that an improved toughness was achieved both in the blend casts and in the carbon fiber composites. A composite structural model was hence suggested.

A New DOPO-Eugenol Adduct as an Effective Flame Retardant for Epoxy Thermosets with Improved Mechanical Properties

The development of efficient green flame retardants is an important way to realize more sustainable epoxy thermosets and downstream materials.In this work,a monoepoxide is synthesized through O-glycidylation of eugenol,and then reacted with DOPO(9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide)to obtain a new bio-based flame retardant,DOPO-GE.DOPO-GE is blended with a bisphenol A epoxy prepolymer exhibiting good compatibility and DDS(4,4′-diaminodiphenylsulfone)is used as the curing agent to afford epoxy thermosets.Although DOPO-GE leads to the reduced glass transition temperature of the thermosets,the storage modulus increases considerably.The DOPO-GE-modified thermosets exhibit the high thermal stability with the onset thermal decomposition temperature in nitrogen and air exceeding 300℃.When the phosphorus content in the thermoset is 1.0%,the residual yield of the thermosets at 750℃ in nitrogen increases from 13.9%to 30.6%,due to the increased charring ability.More interestingly,when the phosphorus content is only 0.5%,the limiting oxygen index is as high as 30.3%with UL94 V0 achieved.Cone calorimeter results reveals the significantly decreased heat release rate,total heat release,mass loss and total smoke production.Furthermore,DOPO-GE can notably improve the flexural strength,flexural modulus and fracture toughness,whereas the shear and impact strength are reduced to varied extents.In short,DOPO-GE can be obtained via a facile way,and shows the good flame-retardant effect on the epoxy thermosets with an application potential.

A Vanillin-Derived,DOPO-Contained Bisphenol as a Reactive Flame Retardant for High-Performance Epoxy Thermosets

Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa-10-phosphophene-10-oxide(DOPO)and phenol via a facile way.VDP is characterized with^(1)H NMR,^(31)P NMR,FTIR and Time of Flight Mass Spectrometry,and used as a new reactive flame retardant for bisphenol epoxy thermosets.Thermogravimetry analysis shows that when the VDP loading is only 0.5P%(based on phosphorus content),the residue increases from 14.2%to 21.1%at 750℃ in N_(2)compare with neat DGEBA.Correspondingly,the limit oxygen index increased to 29.6%,and flame retardancy reaches UL-94 V0 grade.Micro combustion calorimetry(MCC)and cone calorimetry analyses demonstrate that VDP can significantly lower flammability of the epoxy thermoset.With only 0.5P%of VDP,the heat release rate,total heat release rate and smoke production are reduced markedly.At the same time,the mechanical properties of the modified epoxy thermosets are also improved.The impact strength increases by 34%and the flexural strength increased by 23%,with 1.5P%of VDP.In short,VDP not only improves the flame retardancy,but also improves the mechanical properties of the epoxy thermosets.

Respiratory Symptoms and Spirometry Profile of Plastic Factory Workers in Ogun State, Southwest Nigeria

Background: Exposure to plastic fumes can lead to severe occupational hazards due to inhalation, ingestion or direct contact wide variety of potentially harmful by-products during the manufacturing and burning of plastics. Objectives: To determine the prevalence of respiratory symptoms in plastic factory workers, evaluate the respiratory function of plastic factory workers and the association between respiratory symptoms and the duration of employment. Methods: This was a cross-sectional study done among plastic factory workers. Using a random sampling technique, 190 individuals (95 subjects and 95 control) above 18 years of age were recruited. Data were obtained with a validated questionnaire and Spirometry was done. Result: The mean age of the study group and control were 30.27 ± 7.38 and 25.92 ± 4.63 respectively (t = 4.877;p Conclusion: Workplace exposure to plastic fumes can lead to development of respiratory symptoms and impaired pulmonary function.

Bio-Based Polymers for Technical Applications: A Review — Part 2

Triglyceride oil of plant seed cannot be used on its own without further modification. The fatty acids must be suitably functionalized in order to add polymerisable functionalities which will help in the curing process. The purpose of these modifications is to reach a higher level of molecular weight and cross-link density, and also to incorporate chemical functionalities known to impart stiffness in a polymer network. The modification can go through various path ways which were described in this study.

Chemical and Morphological Surface Modification of Epoxy Based Thermosets

Recently developed low fluorine containing polymers are advanced materials which confer advantageous properties to surfaces at a lower cost than conventional fluoropolymers (like PTFE), and are also more easily processable. Fluoropolymer surfaces are characterized by a low surface energy, high oleo and hydrophobicity, low coefficients of friction, among many other properties. This makes them desired materials in microelectronics, antifogging, antifouling and medical applications, to name a few. Fluorinated compounds are not easily coupled with macromolecules or common organic systems, and great efforts are made to compatibilize fluorinated species with hydrocarbon polymers. In this work, two chemical routes were explored in order to incorporate perfluorinated alkyl chains in an epoxy-amine based thermoset. On one side, a perfluoroalkyl thiolated molecule was used as a stabilizing ligand for silver nanoparticles, which were incorporated in the matrix polymer. On the other hand, fluorinated chains containing epoxy functionalities, were used as the matrix modifier. In the first case, fluorinated chains covering the nanoparticles, were mixed with the matrix, while in the second case, the fluoroalkyl chains were chemically linked to the network. Fluorine migration to the air—polymer interface was confirmed by X-Ray photoelectron spectroscopy (XPS). The materials hydrophobicity was then studied in terms of their contact angle with water (CA), as a function of the surface composition and the topography. Scanning electron microscopy (SEM) and atomic force microscopy (AFM), operated in moderate and light tapping modes, were used to morphologically describe the surfaces. An exhaustive surface analysis was made in order to explain the different hydrophobicity grades found.

Progress in Recycling of Composites with Polycyanurate Matrix

Thermoset based composites are used increasingly in industry for light weight applications, mainly for aircraft, windmills and for automobiles. Fiber reinforced thermoset polymers show a number of advantages over conventional materials, like metals, especially their better performance regarding their strength-to-weight ratio. However, composite recycling is a big issue, as there are almost no established recycling methods. The authors investigate the recyclability of polycyanurate homo- and copolymers with different recycling agents under different conditions. Also the influence of the recycling process on the most important reinforcement fibers, i.e. carbon-, glass-, aramid-, and natural-fiber is investigated. The authors find that: the recycling speed is not only dependent on the temperature, but also is significantly influenced by the particular recycling agents and the polycyanurate formulation. Hence, the stability against the recycling media can be adjusted over a broad range by adjusting the polymer composition. Furthermore, the authors find that the inorganic reinforcement fibers (carbon and glass) are almost unaffected by neither recycling agent at either temperature. Aramid-fibers degrade, depending on the particular recycling agent, from slightly up to extremely strong. This leaves one with the possibility to find a combination of matrix resin and recycling agent, which does not affect the aramid-fiber significantly. In the case of natural fibers, the dependence on the particular recycling media is very strong: some media do not affect the fiber significantly;others reduce the mechanical properties (tensile strength and elongation at break) significantly, and still others even improve both mechanical properties strongly. From the Recyclate, the authors synthesize and subsequently characterize a number of new polyurethane thermosets (foamed and solid samples) with different contents of recyclate, exhibiting Tg in the range of 60°C to 128°C.