Fabrication of Ti3SiC2-based pastes for screen printing on paper-derived Al2O3 substrates

This paper describes the development and fabrication of pastes suitable for screen printing process using Ti₃SiC₂ as the ceramic filler and ethyl cellulose as the binder. With the aim of obtaining high quality screen printed films, the influence of different amounts of Ti₃SiC₂ filler (20–40?vol%) and binder (0–5?vol%) on the rheological properties of the pastes was investigated. Samples with higher viscosity, such as pastes containing 30?vol% and 40?vol% Ti₃SiC₂ filler, regardless of the amount of ethyl cellulose, showed a higher printing quality compared to the samples with other compositions. The different paste compositions were screen printed onto paper-derived Al₂O₃ substrates containing 28.6 ± 4.8% open porosity and sintered for 1?h under an argon atmosphere at 1600?°C. X-ray diffraction (XRD) measurements and scanning electron microscopy (SEM) analysis showed that the sintered films contained TiC as a primary phase and Ti₃SiC₂ as a secondary phase. The partial decomposition of Ti₃SiC₂ after sintering can be attributed to residual carbon from the organic additives, which decreases the thermal stability of this material.     

Influence of processing and conduction materials on properties of co-fired resistors in LTCC structures

The motivation of this study is the need for fundamental understanding of the effects of processing conditions on the electrical properties of low-temperature co-fired ceramic (LTCC) tapes, those screen printed with commercial thick-film pastes of electronic components for increased reliability. The method of the study is realized by analyzing the physical and chemical effects of mono/multilayer firing and firing temperatures on the temperature coefficient of resistance (TCR) and sheet resistance (SR) values of the positive temperature coefficient (PTC) resistors screen-printed on LTCC tapes. The results are discussed with respect to the information obtained by the scanning electron microscopy (SEM), electro dispersive X-ray analysis (EDXS), X-ray and dilatometry analysis. It is shown that the content of pastes combined with varying processing conditions result in deviation from expected TCR and SR values due to the chemical and/or mechanical reactions.     

Reversible crosslinked low density polyethylenes: structure and thermal properties

In the present study, low density polyethylene (LDPE) has been crosslinked at 170 °C with three different systems by a) using peroxide, b) peroxide and accelerator and c), peroxide, accelerator and sulfur. The effect of chemical crosslinking on LDPE structure has been investigated using torque measurements, Fourier transform infrared spectroscopy (FTIR), wide angle X-ray diffraction (WAXS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Therefore, effects of each crosslinking system on the structural and thermal properties of the material in terms of crystallinity, thermal transitions and stability have been discussed. The reversible crosslinking of LDPE allow the recyclability of polyolefins, increasing the thermal properties.     

Zero Shrinkage of LTCC by Self-Constrained Sintering

Low shrinkage in x and y direction and low tolerances of shrinkage are an indispensable precondition for high-density component configuration. Therefore, zero shrinkage sintering technologies as pressure-assisted sintering and sacrificial tapes have been introduced in the low-temperature co-fired ceramics (LTCC) production by different manufacturers. Disadvantages of these methods are high costs of sintering equipment and an additional process step to remove the sacrificial tapes. In this article, newly developed self-constrained sintering methods are presented. The new technology, HeraLock^®, delivers LTCC modules with a sintering shrinkage in x and y direction of less than 0.2% and with a shrinkage tolerance of ±0.02% without sacrificial layers and external pressure. Each tape is self-constrained by integration of a layer showing no shrinkage in the sintering temperature range of the LTCC. Large area metallization, integration of channels, cavities and passive electronic components are possible without waviness and camber. Self-constrained laminates are an alternative way to produce zero shrinkage LTCC. They consist of tapes sintering at different temperature intervals. Precondition for a successful production of a self-constrained LTCC laminate is the development of well-adapted material and tapes, respectively. This task is very challenging, because sintering range, high-temperature reactivity and thermal expansion coefficient have to be matched and each tape has to fulfill specific functions in the final component, which requires the tailoring of many properties as permittivity, dielectric loss, mechanical strength, and roughness. A self-constrained laminate is introduced in this article. It consists of inner tapes sintering at especially low-temperature range between 650°C and 720°C and outer tapes with an as-fired surface suitable for thin-film processes.     

溶胶—凝胶法制备SiO2玻璃

采用ＴＥＯＳ－ＥｔｏＨ－Ｈ２Ｏ－ＨＣｌ体系原料,应用低温合成技术制备了ＳｉＯ２玻璃。对合成材料进行了差热－失重分析,Ｘ射线衍射分析,红外透射光谱分析及理化实验,结果表明,无序ＳｉＯ２四面体网络已经形成,固体物理状态可控制为晶态,非晶态。     

Electron Microscopy Study of Ordinary Portland Cement and Ordinary Portland Cement–Pulverized Fuel Ash Blended Pastes

Many ordinary portland cement (OPC) OPC–pulverized fuel ash (pfa) blended pastes of various ages have been examined using transmission electron microscopy, energy dispersive X-ray analysis, and scanning electron microscopy. In addition to the phases commonly identified in OPC pastes, such as CH, CSH, AFt, and AFm, we found areas of pooriy crystalline iron-containing material intermixed with CSH and needles of hydrotalcite-like composition. The iron-containing material may be the precursor of hydrogarnet phases identified in older pastes by other authors. In the pfa-blended cements, some of the pfa particles reacted to give a radially fibrillar gel, and others showed areas of well-crystallized hydrogarnet within the clearly defined outer boundary of the particle. Unreactive pfa particles had a rim of fibrillar CSH gel around the particle. The general fine-scale microstructure of the OPC-pfa-blended pastes was similar to that in OPC pastes alone, but the CSH gel material had a lower C:S ratio.     

Physicochemical characteristics of acrylic-acid polymer-impregnated cement pastes

Various Portland cement pastes were made using water cement ratios of 0·20, 0·25, 0·35 or 0·40 and then cured for 1, 3, 7, 28, 90 or 180 days. These pastes were impregnated with acrylic acid monomer under vacuum and the monomer-impregnated samples were then treated at two different temperatures, 40 or 60°C, for the polymerization process, using benzoyl peroxide as initiator. Several physicochemical studies were carried out on each cement paste; these studies include compressive strength tests, bulk density, compressive strength versus gel/space ratio relationships, polymer load, X-ray diffraction analysis and differential thermal analysis. Results have indicated that compressive strength improvement in acrylic acid-polymer impregnated cement pastes is mainly dependent on initial water/cement ratio, curing time and gel/space ratio. The results of X-ray diffraction analysis and differential thermal analysis indicated that the intrusion of polymer into the cement paste matrix does not affect the phase composition of the Portland cement hydration products.     

Characterization and physiochemical studies of crosslinked thiolated polyvinyl alcohol hydrogels

Modification and crosslinking of polyvinyl alcohol (PVA) by thiolation using thioglycolic acid (TGlA) and various crosslinkers were carried out. The crosslinked thiolated PVA (TPVA) hydrogels were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Fourier transform infra red spectroscopy coupled with thermal analysis (TG-FTIR) techniques. The crosslinking of the resultant material was carried out using three crosslinker sodium trimetaphosphate (STMP), glyoxal and boric acid. The influence of esterification and crosslinking on the physical and chemical properties of the material was studied. XRD showed that after crosslinking the crystallinity of TPVA hydrogels decreased. These results were further substantiated by DSC observations. The thermal stability of the TPVA hydrogels is enhanced. A significant variation in the initial decomposition temperature was observed with respect to different STMP crosslinked samples having varying TGlA concentration and different crosslinkers. The coupled TG-FTIR studies of crosslinked samples at different temperatures show that the evolution of sulfur-containing gases (carbon disulfide and carbon monosulfide) is being prominent for this material.     

Polyimides as precursors for artificial carbon

The pyrolysis behavior of different commercially available polyimides has been studied by means of thermoanalysis, dilatometry and analysis of the gaseous pyrolysis products. Based on the results of these measurements the chemistry of the thermal degradation is discussed. The carboneous residues have been investigated by X-ray, nitrogen adsorption and elemental analysis. The polyimides were successfully applied as binder precursor for C/C-composites.     

Catalytic formation of carbon phases in metal modified, porous polymer derived SiCN ceramics

A novel method for the simultaneous formation of catalytic active metal nanoparticles, multiwall carbon nanotubes (MWCNTs) and/or turbostratic carbon and porous M@SiCN (M = Fe, Co, Pt, Cu, Ag, Au) ceramics during pyrolysis of metal modified polysilazanes and polyethylene (PE) particles as sacrificial filler is described. The thermal decomposition of the polyethylene leads not only to the generation of the porosity but also to an in situ reduction of the metal compounds to the metal nanoparticles, due to the reductive atmosphere. Depending on the metal, carbon nanotubes as well as turbostratic carbon were formed in different amounts, due to the chemical vapor deposition (CVD) like conditions. The resulting carbon phases, ceramics and metal nanoparticles were investigated using the combination of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) measurements, giving evidence for the presence of the carbon phases and the metal particles.     

Study of deformation and porosity evolution of low temperature co-fired ceramic for embedded structures fabrication

The deformation behaviors of suspended low temperature co-fired ceramic (LTCC) laminates over a cavity and the evolution of open porosity of LTCC are studied for the fabrication of embedded structures in a multi-layer LTCC platform using carbon material. The effects of the type of LTCC materials (self-constrained and unconstrained LTCC), cavity width, laminate thickness, and lamination conditions on the deformation of the suspended LTCC laminate over a cavity are studied. For suspended three-layers and six-layers LTCC laminates over cavity width ranges from 10 to 25 mm, the self-constrained LTCC laminates were more dimensionally stable (sagged by less than ?120 μm) after sintering as compared to the unconstrained LTCC. The evolution of open porosity and the distribution of open pores in the self-constrained LTCC with changes in sintering temperature and laminate thickness are also studied for process optimization.     

Impact of sintering temperature on phase composition,microstructure, and porosification behavior of LTCC substrates

Phase development and changes in crystalline composition of LTCC material during the sintering process were investigated using in-situ X-ray diffraction (XRD) measurements. CeramTape GC was chosen as the chemically simplest model system composed of alumina particles and glass for the investigations. The chemical characterization and microstructural analyses of the tapes sintered with some representative firing profiles were performed by techniques such as (scanning) transmission electron microscope, energy-dispersive X-ray spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and XRD. Moreover, the porosification behavior of LTCC substrates fired at different peak temperatures was studied. These investigations are important for the subsequent wet chemical etching, representing an approach which allows to reduce locally the permittivity of LTCC tapes. Treatment with a KOH solution shows non-selective etching behavior for all substrates. In addition, highly porous silica structures corresponding to Ca and Al depletion from the anorthite phase were observed in all samples after etching treatment.     

Processing, Microstructure, and Properties of Laminated Silicon Nitride Stacks

By lamination of silicon nitride tapes, components with complex geometries can be produced. Unstructured tapes can be laminated by common thermal compression. Structured tapes, however, have to be joined by pressureless processes using e.g. pastes as lamination aids because deformation of the structures would occur. These pastes usually contain a binder for maintaining the mechanical contact between the tapes during processing. To prevent the high mass loss of typical organic binders during burnout, pre-ceramic polymers were used in this work. These ceramic precursors convert partly into an inorganic material during heat treatment with a significant reduced mass loss compared with common organic binders. Thus, the porosity in the interlayer of a laminated stack is strongly decreased, which should be favorable for the mechanical and thermal properties. This work discusses the resulting microstructure, strength, and thermal diffusivity data of stacks laminated with pastes containing various precursor contents. These results are compared with those obtained by samples prepared by compression of green tapes. It is found that except for some large pores, the microstructure of the precursor-derived interlayers is qualitatively the same as in the tape material. For stacks made by both lamination methods, strength measurements reveal that the properties parallel and perpendicular to the layers are different. It is shown that the same strength level can be obtained both by using the pressureless route and by the compression method. Unlike the strength, the thermal conductivity does not change with the direction of measurement.     

Carbon materials for structural self-sensing,electromagnetic shielding and thermal interfacing

This paper reviews carbon materials for significant emerging applications that relate to structural self-sensing (a structural material sensing its own condition), electromagnetic interference shielding (blocking radio wave) and thermal interfacing (improving thermal contacts by using thermal interface materials). These applications pertain to electronics, lighting (light emitting diodes), communication, security, aircraft, spacecraft and civil infrastructure. High-performance and cost-effective materials in various forms of carbon have been developed for these applications. The forms of carbon materials include carbon fiber, carbon nanofiber, exfoliated graphite, carbon black and composite materials. Short carbon fiber cement-matrix composites and continuous carbon fiber polymer-matrix composites are particularly effective for structural self-sensing, with the attributes sensed including strain, stress, damage and temperature. Flexible graphite as a monolithic material and nickel-coated carbon nanofiber as a filler are particularly effective for electromagnetic shielding. Carbon black paste, graphite nanoplatelet paste and flexible graphite (filled with carbon black paste) are particularly effective for thermal interfacing; carbon nanotube arrays are less effective than these pastes. The associated science pertains to the relationship among processing, structure and properties in relation to the abovementioned applications. The criteria behind the design of materials for these applications and the mechanisms of the associated phenomena are also addressed.     

Controlling properties of ceramic formulations for porcelain robocasting

Porcelain pastes (PlotPastes) were formulated to be used on an additive manufacturing (AM) process (material extrusion) process, primarily robocasting (R3D) technique. The material morphological and thermal characteristics were evaluated by scanning electron microscopy (SEM), differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The rheology and the electrical potential of the ceramic particles were also studied to select and adequate the porcelain paste properties to the R3D AM technique. It was found that shifting the pH values to acidic, the surface charge of the particles changes and increases the pastes viscosity due to agglomeration effects. This behaviour was exploited to optimize the paste rheological behaviour which resulted in the optimum pH at 1.94 (PlotPaste 5). This paste was used in the study of R3D operating parameters. It was found that small variations in pressure and speed affects the dimensional accuracy of the printed models. The results showed the disruptive potential of porcelain R3D in the production of customized ceramic products.     

Low-Temperature Synthesis of Nanocrystalline Zinc Titanate Materials with High Specific Surface Area

Nanocrystalline zinc titanate (ZnTiO₃) was synthesized at low temperatures through the combination of a sol–gel processing and a polymer binder method. ZnTiO₃ powders of ∼5 nm in size were obtained by heating pastes, which were composed of a Zn-Ti methanolic solution containing acetylacetone and an organic polymer binder, at 500°C in air. Thermal decomposition behavior of the pastes was analyzed by thermogravimetry-differential thermal analysis. Crystallinity of ZnTiO₃ was examined by transmission electron microscopy. The BET measurement revealed that the powders had a relatively high specific surface area of 106 m²/g.     

Synthesis and characterization of low crystalline waterborne polyurethane for potential application in water-based ink binder

Waterborne polyurethane dispersions (PUDs) with low crystallization and narrow nanoparticles distribution were synthesized from poly(propylene glycol) (PPG), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA) via a environmental and simple process combined prepolymer isocyanate process with acetone process. For used as ink binder, the acid numbers of PUDs were analyzed. It was found that the acid number changed with the solid content and mainly increased with increasing hard-/soft-segment molar ratio. Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance spectroscopy (¹H NMR), transmission electron microscope (TEM), differential scanning calorimetry (DSC), thermogravimetric (TG), X-ray diffractometer (XRD) and polarizing optical microscopy (POM) measurements were utilized to characterize the bulk structures and thermal properties of PUDs. The results show that nanoscale waterborne polyurethane dispersions synthesized through the combined process have good thermal stability and weakly crystallinity, which is suitable for the use of water-based ink binder. The performance of PUDs can be optimized for the application as ink binder when the hard-/soft-segment molar ratio is 4 or 5.     

Evaluation of the pozzolanic activity of fluid catalytic cracking catalyst residue (FC3R). Thermogravimetric analysis studies on FC3R-Portland cement pastes

Spent fluid catalytic cracking catalyst (FC3R) from a petrol refinery has shown a great pozzolanic activity in lime pastes as have been demonstrated in previous studies. Based on these results, the pozzolanic activity of the FC3R in Portland cement pastes has been investigated. This evaluation has been carried out by means of thermogravimetry (TG) of cured FC3R-Portland cement pastes. The influence of water/binder ratio and the replacement percentage of FC3R on the pozzolanic reaction were investigated. Due to the chemical composition of FC3R that is similar to metakaolin (MK), and knowing that MK has a high pozzolanic activity, the latter was used as a material of comparison in the study of the water/binder ratio influence. The scope of this study is the determination of pozzolanic activity of FC3R when incorporated to Portland cement, and the evaluation on amount and nature of pozzolanic products. FC3R has shown a similar reactivity to MK, yielding similar pozzolanic products: CSH, CAH and CASH. The optimum replacing percentage in Portland cement pastes was in the 15-20% range.     

Functionalization of multi-walled carbon nanotubes with perfluoropolyether peroxide to produce superhydrophobic properties

Multi-walled carbon nanotubes (MWCNTs) have been functionalized through perfluoropolyether (PFPE) radicals obtained by thermal decomposition of linear PFPE peroxide. The reactivity of MWCNTs with PFPE peroxide has been compared with the direct fluorination of MWCNTs using elemental fluorine in mild conditions. The experimental results indicated that the functionalization with PFPE peroxide and the direct fluorination with elemental fluorine were suitable techniques to modify and control the physical-chemical properties of MWCNTs. After the introduction of PFPE chains on the MWCNT surface, the wettability of MWCNTs changed from hydrophilic to superhydrophobic, because the low surface energy properties of PFPE were transferred to the MWCNT surface. However, the linkage of PFPE chains weakly influenced the electrical properties of conductive MWCNTs. The amount of PFPE chains linked to the carbon nanotubes, the PFPE fluids obtained by homocoupling side-reactions and the decomposed portion of PFPE have been evaluated by mass balance. The modified MWCNTs have been characterized by X-ray photoelectron spectroscopy, thermal gravimetric analysis, X-ray diffraction, scanning electron microscopy, contact angle and surface area measurements. The effects of the chemical treatment on the conductive properties of MWCNTs have been studied by resistivity measurements at different applied pressures.     

Effect of carbon content on the microstructure and mechanical properties of Ti(C, N)-based cermets

Three series of Ti(C, N)-based cermets with various carbon content were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). Hardness (HV) and transverse rupture strength (TRS) were also measured. A lower carbon content resulted in the aggregation of ceramic grains because the absorbed oxygen of the powder mixture could not be outgassed completely, and then the ceramic grains could not be well-wetted by liquid metal during sintering. On the contrary, too high carbon content resulted in the formation of graphite phase. An increased carbon content decreased the dissolution of tungsten, titanium and molybdenum in the binder phase. The volume fraction of the binder is not much influenced by the carbon content. The highest hardness and TRS were found for the cermet with 1.5 wt.% carbon addition, which was characterized by fine grains and moderate thickness of rim phase.