Preceramic Polymer Research Articles

Synthesis and characterization of soluble and meltable Zr-containing polymers as the single-source precursor for Zr(C, N) multinary ceramics

Soluble and meltable Zr-containing preceramic polymers were synthesized in this work by the polymerization of ZrCl4 and different diamines, followed by preparation of Zr(C, N) multinary ceramics via pyrolysis. The composition, structure and morphology were investigated by Fourier transform infrared spectroscopy, nuclear magnetic resonance, as well as thermogravimetric-mass spectrometry, X-ray diffraction, elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy. Results showed that although the precursor could be formed by the reaction between Zr–Cl and N–H bonds, the ceramic yield was low due to the release of NH3 and CH4 gases during the ceramization process. To improve the ceramic yield, allyl amine was applied to tailor the polymer structure. With allyl groups acting as the “bridge” during crosslinking process, the precursor had a higher ceramic yield of 62.5% and melting point of 280–300 °C with Zr content of 49.7 wt% in the derived Zr(C, N) ceramics. Annealing experiments in an inert atmosphere at temperatures in the range of 1200–1400 °C showed the transformation of the amorphous state to dense polycrystalline ceramics. When temperature was increased to 2000 °C, the ceramics got quite dense without obvious phase separation. The precursors could be applied as promising candidates for non-oxide ceramic matrix composites and fibers at ultra-high temperatures and even in harsh environments.

Synthesis and Characterization of a Novel Preceramic Polymer for SiBNC Ceramic Fibers

A new approach for the synthesis of polymer precursor for quaternary SiBNC fibers is presented. The inexpensive, commercially available reactants n-propylamine (C3H7NH2), trichlorosilane (SiHCl3) and boron trichloride (BCl3) were used in a simple one-step reaction. The reaction mainly involved the co-polymerization between Si-Cl, B-Cl and N-CH2CH2CH3 with C3H7NH2 evaporation. Characterization of synthesized polymer was performed by FT-IR and NMR. The polymer has a relatively linear-chain chemical structure, and could be easily converted into flexible green fibers by melt-spun with diameter of 24 μm. After pyrolysis process at 1000 °C under nitrogen atmosphere, SiBNC ceramic fibers were obtained with a diameter of about 19 μm. Those fibers showed average tensile strength of 1.05 GPa and it remained in the amorphous state up to 1600 °C, which made them as the promising candidates for reinforcements in ceramic matrix composites for hightemperature application.

Hierarchically Porous Zirconia Monolith Fabricated from Bacterial Cellulose and Preceramic Polymer.

A hierarchically porous zirconia (ZrO2) monolith was successfully fabricated by using bacterial cellulose (BC) as a biotemplate and preceramic polymer as a zirconium resource, via freeze-drying and two-step calcination process. Images of scanning electron microscopy showed that the ZrO2 monolith well-replicated a three-dimensional reticulated structure of pristine BC and possessed good morphology stability till 1100 °C in air. Results of N2 adsorption/desorption and mercury porosimetry analysis revealed the hierarchically porous structure and large specific area (9.7 m2·g–1) of the ZrO2 monolith, respectively. Patterns of X-ray powder diffraction indicated that the monoclinic phase and tetragonal phase coexisted in the ZrO2 monolith with the former as the main phase. In addition, the ZrO2 monolith possessed low bulk density (0.13 g·cm–3) and good mechanical strength. These properties suggest that the as-prepared ZrO2 monolith has a great potential to serve as an ideal catalyst or catalyst support.

Optimization and Characterization of Preceramic Inks for Direct Ink Writing of Ceramic Matrix Composite Structures.

In a previous work, an ink based on a preceramic polymer, SiC fillers, and chopped carbon fibers was proposed for the production of Ceramic Matrix Composite (CMC) structures by Direct Ink Writing (DIW) and subsequent pyrolysis. Thanks to the shear stresses generated at the nozzle tip during extrusion, carbon fibers can be aligned along the printing direction. Fumed silica was added to the ink in order to enhance its rheological properties; however, the printed structures still showed some deformation in the Z direction. In this work, a second ink was successfully developed to limit deformation and at the same time avoid the addition of fumed silica, which limited the potential temperature of application of the composites. Instead, the positive role of the preceramic polymer on the ink rheology was exploited by increasing its concentration in the ink. Rheological characterization carried out on both inks confirmed that they possessed Bingham shear thinning behavior and fast viscosity recovery. Single filaments with different diameters (~310 µm and ~460 µm) were produced with the latter ink by DIW and subsequent pyrolysis. Tested under a four-point flexural test, the filaments showed a mean flexural strength above 30 MPa, graceful failure, and fiber pull-out. The results of this work suggest that CMC components can effectively be fabricated via DIW of a preceramic ink with embedded short fibers; the preceramic polymer is able to provide the desired rheology for the process and to develop a dense matrix capable of incorporating both fibers and ceramic particles, whereas the fibers addition contributes to an increase of the fracture toughness of the material and to the development of a graceful failure mode.

Polymer‐derived SiCN cellular structures from replica of 3D printed lattices

AbstractIn comparison with metals and polymers, ceramics and/or carbon are more difficult to process into well‐defined cellular architectures (e.g., cubic, tetrakaidecadehron, etc.) using Additive Manufacturing techniques. The present work reports a simple method for generating complex and precise SiCN ceramic lattices using a preceramic polymer and applying the replica approach to structures fabricated using stereolithography of plastic materials, with the associated ease of fabrication. Three‐dimensional printed plastic lattices impregnated with a polysilazane were converted to SiCN by pyrolysis at 1000°C in inert atmosphere. In spite of the high amount of mass loss (~58%) and volume shrinkage (~65%), the impregnated structures did not collapse during pyrolysis, leading to highly porous (total porosity ~93 vol%) components possessing suitable strength for handling and potential use as lightweight components.

Synthesis and ceramic conversion of novel silazane modified phenol formaldehyde resin

Novel silazane modified phenol formaldehyde (SPF) resins were synthesized by reacting varying amounts of 1, 3, 5-trimethyl-1', 3', 5'-trivinylcyclotrisilazane (CTS) with phenol formaldehyde (PF) resin. For the selection of an appropriate pyrolysis condition, polymer-to-ceramic conversion of SPF was carried out at 1450 °C and 1650 °C under argon and nitrogen atmosphere. The pyrolysis conditions significantly affected the evolution of ceramic phases, excess carbon and morphology which were thoroughly investigated through XRD, Raman and FESEM techniques. This study establishes silazane modified phenol formaldehyde as a new class of preceramic polymer for high-temperature applications. The study also reveals that nitrogen atmosphere is a more suitable gas atmosphere than argon atmosphere for preparation of desired C/Si3N4/SiC ceramics with higher ceramic yield.

IR investigation on silicon oxycarbide structure obtained from precursors with 1:1 silicon to carbon atoms ratio and various carbon atoms distribution

Silicon oxycarbide is a material with a number of advantageous properties that strongly depend on its structure. The most common approach to its tailoring is based on varying the silicon to carbon atoms ratio in the preceramic polymeric precursor. This work is the first comparison of the materials obtained from precursors with the same Si to C atoms ratio, but with various distribution of these atoms in the preceramic polymer. In addition to standard mixtures of monomers containing single silicon atom, a number of monomers with high molar masses and well defined structure was used. The IR was used to investigate the structure of the precursors and materials obtained after their annealing in 800 °C. The results show, that not only the distribution of carbon containing groups among the monomers is important, but also the (in)ability of these groups to end up in each other vicinity in the precursor as well as the degree of condensation of each structural unit.

Multiple metals doped polymer-derived SiOC ceramics for 3D printing

Multiple metals doped polymer-derived SiOC ceramics with octet truss structure were prepared by employing a photosensitive methyl-silsesquioxane as preceramic polymer through sol-gel method and Digital Light Processing 3D printing. The physical and chemical properties of the preceramic polymers and printed octet truss structure SiOC ceramics were investigated. Results show that the organosilicon preceramic polymers have outstanding photocuring properties and could transform into amorphous SiOC ceramics at 800–1200 °C. It is illustrated that the excellent mechanical properties of SiOC ceramics with octet truss structure (after 3D printing and pyrolysis) are attributed to the metal elements pinning in the amorphous matrix on the atomic level. Doping other metal elements such as Fe, Ni, Co, Pt, etc, is thought to bring promising properties for the lattice structure SiOC ceramics and potentially further expand its applications in the future.

Reactive Atmosphere Synthesis of Polymer‐Derived Si–O–C–N Aerogels and Their Cr Adsorption from Aqueous Solutions

Polymer derived ceramic (PDCs) aerogels belonging to the Si–O–C–N system are synthesized by crosslinking a preceramic polymer in a diluted solution followed by supercritical or atmospheric drying and pyrolysis in inert (N2) or reactive (NH3/CO2) atmosphere. Accordingly, aerogels with hierarchical porosity ranging from some microns to few nanometers together with high specific surface area in the range 30–400 m2 g−1 have been obtained. Moreover, their surface contains a broad range of moieties (Si–OH, Si–NH, C=O, etc.) that can interact and bind metal ions thanks to electrostatic interactions. This combination of hierarchical porosity, high SSA, and broad range of chemical functionalities makes these PDCs aerogels interesting candidates for water purification. In this work, SiOC and SiCN aerogels have been tested as adsorbents for Cr(III)/(VI) ions from aqueous solutions with promising results for the SiOC aerogel pyrolyzed in N2 and the SiCN treated in NH3. Correlations and similarities among the Cr(VI)/(III) adsorption capacity with the main features of the porous substrates (SSA, N2 TPV, amount of free C, bulk density, isoelectric point, main IR peaks (Si–OH, OH, NH, C=O, C=C, Si–O, C–N, Si–N) have been investigated by applying the Principal Component Analysis (PCA).

Process modeling of the low‐temperature evolution and yield of polycarbosilanes for ceramic matrix composites

AbstractThe volatilization of polycarbosilanes is important to the processing and performance of polymer infiltration and pyrolysis‐based ceramic matrix composites. Low molecular weight (MW) polycarbosilane is often present in preceramic polymers and enhances viscosity for the purpose of composite infiltration. Due to the volatility of low MW chains, a model was developed to semi‐empirically determine the MW distribution and then predict the mass yield and evolution of the MW distribution as a function of temperature and time for StarPCS™ SMP‐10. The enthalpy of vaporization, the temperature dependence of the enthalpy of vaporization, the temperature dependence of the normal boiling point and a representation of the molecular weight distribution were fit using a series of thermogravimetric measurements, involving isothermal holds on a particular batch of SMP‐10. Once calibrated for SMP‐10 in this fashion, the molecular weight distribution of different batches of SMP‐10 could be fit using a thermogravimetric measurement involving a reduced temperature‐time series. The model was then predictive of mass loss over time for temperatures below the onset of curing (>90°C). Understanding this volatilization enables improved SiC yield, reduced processing time and minimizing void/bubble formation.

Polymer‐derived ceramic adsorbent for pollutant removal from water

AbstractPolymer‐derived ceramic components (SiOC, sample W) were produced from preceramic polymer mixture and a catalyst. After curing and pyrolysis, some of the samples etched by hydrofluoric acid to obtain carbonaceous SiOC (C‐rich SiOC, sample W‐HF). W and W‐HF were tested as an adsorbent material to remove both heavy‐metal ions (Cr (III), Pb (III), and Cd (II)) and cationic dyes (Methylene Blue (MB), Rhodamine B (RB), and Crystal Violet (CV)) from aqueous solutions. HF‐treated high surface area SiOC samples had quite high adsorption affinity for cationic dyes. According the Langmuir isotherm model the maximum dye uptake values were found to be around to 50 mg/g for sample W, whereas those for sample W‐HF ranged from 104 to 186 mg/g. Regeneration studies were conducted both by heat treatment and leaching, high recovery yields (always above 97%) of MB adsorption were obtained.

Porous SiC ceramics with dendritic pore structures by freeze casting from chemical cross-linked polycarbosilane

In this study, a commercial polycarbosilane (PCS) and divinylbenzene (DVB) were used as the preceramic polymer precursor and crosslinking agent, respectively to form porous silicon carbide (SiC) ceramics by freeze casting DVB/camphene/PCS solutions. Porous silicon carbide (SiC) with a dendritic pore structure and connecting bridges was obtained after pyrolysis at 1200°C. The effects of DVB and PCS content on the rheological properties of the solution and the morphological characteristics and the compressive strengths of SiC ceramics were investigated. The use of DVB and the resulting chemical cross-linking yielded modified pore characteristics and much lower oxygen content in pyrolyzed SiC compared to the conventional thermal curing method. A compressive strength of 18.7MPa was obtained for pyrolyzed SiC prepared with 20wt% PCS and a 0.2 DVB/PCS mass ratio.

Crosslinking chemistry of poly(vinylmethyl-co-methyl)silazanes toward low-temperature formable preceramic polymers as precursors of functional aluminium-modified Si-C-N ceramics.

Crosslinking chemistry of a liquid poly(vinylmethyl-co-methyl)silazane with an alane hydride-based complex according to Si : Al ratios varying from 5 to 2.5 has been investigated in detail through the characterization of the as-obtained polymers using solid-state NMR, FT-IR and elemental analyses. This reaction allows tailoring the chemical and physical properties of the neat liquid polysilazane while extending its processability to lead to a series of low-temperature formable aluminium-modified polysilazanes. Structural models have been established based on solid-state NMR spectroscopy. Then, pyrolysis under nitrogen occurring the conversion of polymers into ceramics has been studied by coupling TG experiments with FTIR of pyrolysis intermediates. Pyrolysis at 1000 °C leads to X-ray amorphous Al-modified silicon carbonitride materials with higher ceramic yields compared to the materials obtained from the neat polysilazane. However, the increase of the ceramic yield is minimized with the decrease of the Si : Al ratio from 5 to 2.5 in the as-obtained polymers. This is due to the introduction of -NR3 (R = CH3 and C2H5) units as side groups during the polymer synthesis which are released in the low temperature regime of the pyrolysis. The structural evolution of the amorphous network of ceramics has been studied by annealing up to 1800 °C though X-ray diffraction and Raman spectroscopy. Such studies point out that samples remain amorphous even after annealing at 1400 °C (low Si : Al ratio) and 1600 °C (high Si : Al ratio) before forming Si3N4/SiC/AlN and AlN/SiC/C composites after annealing at 1800 °C depending on the Si : Al ratio fixed in the early stage of the process. Dense pieces could be prepared from these low-temperature formable polymers. The latter, especially those containing a certain portion of -NR3 (R = CH3 and C2H5) units acting as plasticizing groups during the process, display appropriate requirements for pressing at low temperature forming dense pieces with hardness and Young's modulus as high as 21.7 GPa and 192.7 GPa, respectively.

Composites Obtained from Alumina and Polymer Derived Ceramic

Alumina-mullite composites with low shrinkage can be made by reaction bond using mixtures of alumina, aluminum and silicon carbide. In this work, an alternative route is used to produce alumina composites with low shrinkage. Here alumina samples containing additions of 10 and 20 wt% of a preceramic polymer were warm-pressed and treated in the range of 900 -1500°C to produce alumina based composites. The obtained composites were analyzed by linear shrinkage and compared to pure alumina samples sintered at the same temperature range. It were also evaluated the density variation and crystalline phases formed during heat treatment of alumina composites. Results showed that alumina-silicon oxycarbide and alumina-mullite composites were obtained with lower shrinkage than pure alumina samples.

Polymer-derived ceramic/graphene oxide architected composite with high electrical conductivity and enhanced thermal resistance

A low temperature method for the fabrication of architected ceramic composites contining graphene is developed based on the infiltration of lightweight graphene oxide (GO) micro-lattices with a preceramic polymer. Self-supported highly porous three-dimensional (3D) GO structures fabricated by direct ink writing are infiltrated with a liquid organic-polysilazane (a compound of Si, C, H, N), and subsequently pyrolyzed at temperatures of 800–1000 ºC to activate the ceramic conversion. These ceramic composites replicate the patterned GO skeleton and, whereas the graphene network provides the conductive path for the composite (electrical conductivity in the range 0.2–4 S cm−1), the ceramic wrapping serves as a protective barrier against atmosphere, temperature (up to 900 °C in air) and even direct flame. These structured composites also show hydrophobicity (wetting angle above 120°) and better load bearing capacity than the corresponding 3D GO lattice. The process is very versatile, being applicable to different liquid precursors.

Fabrication of porous Al2O3-based ceramics using ball-shaped powders by preceramic polymer process in N2 atmosphere

Porous Al2O3-based ceramics were successfully fabricated using ball-shaped powders by preceramic polymer process in N2 atmosphere. These results showed that the amorphous Si-O-C ceramics were formed on the surface of ball-shaped Al2O3 particles by the pyrolysis of the silicone resin during sintering in N2 atmosphere, which played a role in connecting the Al2O3 particles by forming the sintering necks. When the sintering temperatures increased from 1100°C to 1600°C, the formed Si-O-C ceramics still existed in the amorphous state and had no crystallization. Interestingly, the amorphous β-SiC formed at 1300°C and its amount gradually increased with further increasing temperatures. The linear shrinkage rate of the samples varied from 0.49% to 0.73% and the weight loss rate increased from 2.01% to 10.77%. The apparent porosity remarkably varied with the range of 24.9% and 34.5%, as the bulk-density varied from 2.66 to 2.47g/cm3. The bending strength gradually increased from 9.36 to 22.51MPa with increasing temperatures from 1100°C to 1500°C, however, the bending strength remarkably decreased at 1600°C, which was attributed to the comprehensive function of the high porosity, broken Al2O3 particles and weak connection between Al2O3 particles in the samples.

Amorphous fine-diameter SiC-based fiber from a boron-modified polytitanocarbosilane precursor

An amorphous SiC-based fiber was successfully prepared by the preceramic polymer route from a boron-modified polytitanocarbosilane. It was found that the addition of titanium and boron had adverse effect on melt-spinning, while the tensile strength of the obtained SiC-based fibers increased with the contents of titanium and boron increasing. It is worth mentioning that the decomposition of SiCO phase and the resultant β-SiC crystallization were retarded by the incorporation of titanium and boron into the SiC-based fiber.

Synthesis of SiCN@TiO2 core-shell ceramic microspheres via PDCs method

A facile and effective polymer-derived ceramics (PDCs) emulsification-crosslinking-pyrolysis method was developed to fabricate SiCN@TiO2 core-shell ceramic microspheres with polyvinylsilazane (PVSZ) and tetrabutyl titanate (TBT) as precursors. The TBT: PVSZ mass ratios, emulsifier concentrations and the pyrolysis temperature were examined as control parameters to tune the size and morphology of microspheres. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed the synthesized SiCN@TiO2 microspheres to be comprised of SiCN core coated with TiO2 crystals, with an average size of 0.88 μm when pyrolyzed at 1400 °C. The analysis of Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) ensured that SiCN@TiO2 core-shell ceramic microspheres composed of rutile TiO2, β-SiC and Si3N4 crystalline phases, The thermal properties were characterized by thermogravimetric analysis (TGA). The obtained SiCN@TiO2 core-shell ceramic microspheres were the promising candidate of the infrared opacifier in silica aerogels and this technique can be extended to other preceramic polymers.

Preparation and properties of a novel precursor-derived Zr-C-B-N composite ceramic via zirconocene and borazine

A novel preceramic polymer polyzirconocenyborazane (PZCBN) was synthesized by the polymerization of Bis(cyclopentadienyl)zirconium divinyl and borazine, introducing Zr, B, C, N together. The formation and concentration of elements Zr, C, B, N in the precursor and ceramic were detected through FTIR NMR, XRD, SEM and TEM. From the analysis, the Cp2Zr(CH˭CH2)2 and borazine linked together via the addition reaction between C˭C and B-H. And after pyrolysis at 1200°C, the precursor turned to ZrC/ZrB2/BN composite ceramics, with a yield of 52wt%. EDX resulted showed that the elements were well dispersed in the ceramics. According to SEM and TEM, the ceramic had a relatively dense structure with nano crystalline areas of ZrC embedded in the amorphous Zr-C-B-N matrix. TGA in air demonstrated that the ceramic had a favorable property on oxidation resistance.

Macroporous SiOC Ceramics with Dense Struts by Positive Sponge Replication Technique

Highly porous SiOC ceramics (≥90% open porosity) containing dense struts have been prepared following positive sponge replication technique using silsesquioxane based preceramic polymer. The morphological features including cell size, cell window size, and strut size of the macroporous SiOC ceramics have been analyzed using electron microscopy. Subtle variation in the crosslinking condition of the preceramic polymer infiltrated polyurethane template enables the formation of hollow as well as dense struts, which has a profound influence on compressive strength of the macroporous bodies. Synchrotron radiation micro computed tomography is used to construct the three dimensional images of the macroporous ceramics that indicate isotropy of the pores and excellent interconnectivity.