Surface modification of ceramic powders by titanate coupling agent for injection molding using partially water soluble binder system

In the conventional process of ceramic injection molding (CIM), wax-based binders could only be removed by thermal or organic solvent debinding. Recently, water solvent debinding, with its high efficiency and environmental acceptability, has appeared as a good alternative. In this study, zirconia powder modified by titanate coupling agent was applied in partially water soluble binder system for injection molding. In contrast to previous researches about titanate modification mainly focusing on rheological behavior and modification mechanism, investigations on the sintering behavior and densification process were also made in this study. Experimental results reveal that titanate modified powder exhibits densification temperature almost 100 °C lower than that required for the pure, original powder, giving rise to finer microstructure and therefore hopefully improved mechanically properties. It suggests a novel modification route to fabricate injection molded ceramic components using partially water soluble binder system.     

Binder jetting of ceramics: Powders,binders, printing parameters,equipment, and post-treatment

Binder jetting is expected to become the universal process for preparing ceramic parts because it can overcome multiple problems, such as the difficulty to prepare complex-shaped ceramic parts and the shrinkage of the sintering process, which appear in conventional ceramic preparation process. This paper introduces principles, steps, and applications of binder jetting printing ceramics. Furthermore, five key factors of binder jetting printing ceramics (powders, binders, printing parameters, equipment, and post-treatment process) have been investigated. Accordingly, effects of powders (including shape, particle size and distribution, and additives), binders (including binding method, droplet-formation mechanism, and droplet-infiltration kinetics), printing parameters (including layer thickness, saturation, solid binder, and printing orientation), equipment, and post-treatment (including de-powdering process, and densification process) on density, roughness, strength, accuracy, and resolution of ceramic parts have been discussed and summarized. This paper provides detailed analysis of techniques and mechanisms of binder jetting of ceramics, giving guidance on how to handle raw materials and select various processing parameters for achieving desired performance.     

Powder-binder separation in injection moulded green parts

For powder injection moulding (PIM) the ceramic powder is mixed with a thermoplastic binder system to achieve an injectable feedstock. In contrast to injection moulding of polymeric components, the binder must be removed after the shaping step before sintering the ceramic part to full density. During the mould filling process shear forces act on the blend that might cause separations of powder particles and binder. In this case polymer films form at the mould surface and at internal interfaces which induce microstructural defects in the debinded part. In particular for multi-component parts this effect is critical since binder films in the joining zone weaken the bonding strength between the two components that might even lead to delamination.For detecting binder separations within the injection moulded bulk material and at joining zones of two-component parts the microstructure of green samples has been studied. Since conventional machining techniques like grinding and polishing modify the original structure, e.g. when particles are pulled out of the matrix and binder smears onto the surface, a special ceramographic method for the preparation of cross-sections was applied. This approach bases on broad ion beam techniques and enables the simultaneous polishing of hard ceramic particles and soft polymer molecules without destroying the structure or producing a relief at the surface. In the analysed samples binder accumulations were found along flow lines, at weld lines, at boundaries of so-called dead water regions and at the interface of two-component parts.     

A simple model for viscosity of powder injection moulding mixes with binder content above powder critical binder volume concentration

A simple model is proposed for the variation of viscosity of powder injection moulding mixes with binder content above Critical Binder Volume Concentration (CBVC), a characteristic of powder. Coarse silica and fine alumina powders are mixed with different types of low viscosity binders at different binder proportions. The viscosities of these mixes are measured by capillary rheometry with a special die at different shear rates. The CBVC values of the powders estimated by the model from the viscosity data of the mixes are matching with those values arrived from the experimental torque rheometry and temperature measurement methods. The proposed model has shown excellent correlation between the calculated and experimentally measured viscosity data at different shear rates, binder contents with different binders and powders. The model also gave precise CBVC values with the viscosity data of the previous authors validating the model to other powders and binders. The model is useful for the prediction of viscosity of PIM mix with known binder content, viscosity of binder and CBVC of the powder.     

Binder jetting yttria stabilised zirconia ceramic with inorganic colloid as a binder

ABSTRACT

The new inorganic colloid is a particle-free decomposable binder that can solve the nozzle clogging problem and precipitate zirconia particle upon heating. The inorganic colloidal binder can be used as a binder precursor to replace commonly used PVP binder in printing ZrO₂ ceramics parts using binder-jet technology. Green bodies were printed using inorganic colloid binders with different saturation level and PVP binder separately, then cured and sintered. The effects of binder saturation level and sintered temperature on the properties of the green and sintered bodies were investigated. After being deposited into the powder bed interstices and cured, the inorganic colloidal binder containing zirconium basic carbonate decomposes and forms ZrO₂ ceramic particles that are filled the interstices and sintered to provide bonding strength to the printed parts. Samples with inorganic colloidal binder eventually perform better surface quality and denser sintered body than polymer binder when using same saturation ratio.     

Effect of a binder system on the low-pressure powder injection moulding of water-soluble zircon feedstocks

Micronized natural zircon sand powders were used as a raw material to conduct low-pressure powder injection moulding (LPPIM) processes. PIM could lead to new technological applications for this mineral, which has very stable dimensional behaviour with changing temperature. Zircon powders that have unconventional attributes for PIM (in terms of size and morphology) were mixed with poly(ethylene glycol) (PEG) based binders. Combinations of this water-soluble substance with different polymers, including low-density polyethylene (LDPE) and several types of acetate butyrate celluloses (CAB), were investigated. The influence of acetyl, butyryl and hydroxyl groups on the behaviour of the created feedstocks at different process stages and on the final piece properties were studied. The higher affinity of CAB with PEG and zircon powders compared with LDPE could result in improved densification and properties, but the butyryl, acetyl and hydroxyls groups affect the processability of these feedstocks.     

Fabrication of coloured zirconia ceramics by infiltrating water debound injection moulded green body

Abstract

Abstract

The authors developed a new technique combining ceramic injection moulding and liquid precursor infiltration, presenting a new strategy for fabrication of coloured zirconia ceramics. The authors’ strategy includes ceramic injection moulding 3Y‐TZP powder using a water debinding binder system, debinding moulded parts in water and drying, immersing debound parts in solutions containing different colouring ions and then sintering and creating coloured zirconia ceramics. The fabricated coloured ceramic bars exhibit a core shell structure, and the thickness of the coloured shell can be tailored by adjusting immersion time and temperature. Using solutions containing different colouring ions, ceramic bars with various colours can be prepared.     

Injection molding of surface modified powders with high solid loadings: A case for fabrication of translucent alumina ceramics

Solid loading is a critical key to the fabrication of ceramic compacts with high densities via ceramic injection molding. As reported in most previous work, solid loading of ultra-fine alumina feedstock system could be achieved only up to ∼58 vol% with stearic acid (SA) as the surface modification agent. In present work, different from the traditional work in which SA has been introduced just in the powder blending process, we have successfully prepared the feedstock with a much higher solid loading up to ∼64 vol% by a prior ball milling treatment of ceramic powders with a small amount of SA before the traditional blending process. It can be attributed to that SA can be coated homogeneously around the powder surfaces by a chemical reaction induced by ball milling treatment. Highly translucent Al₂O₃ ceramics have been fabricated, which suggests an alternative route for fabrication of translucent ceramics with high quality.     

Slurry-based selective laser sintering of polymer-coated ceramic powders to fabricate high strength alumina parts

Instead of conventional powder-based selective laser sintering, a novel slurry-based process to fabricate high strength ceramic parts is proposed. A slurry which was composed of alumina powder coated with water-insoluble semi-crystalline polyvinyl alcohol (PVA) as a structure material, water-soluble PVA as an organic binder, ammonium polymethacrylate (DARVAN C-N) as a dispersant, and deionized water as a solution, could be prepared with colloidal processing. A rigid green block could be built with a self-made rapid prototyping apparatus. The polymers contained in the scanned region were melted to connect the alumina powders, but transformed to be water-insoluble. However, the un-scanned region remained water-soluble. Due to dissolving of the polymers in water, the un-scanned region could collapse to obtain the green part. After binder removing and sintering, an alumina ceramic part could be obtained. An average flexural strength of 363.5 MPa and a relative density of 98% were achieved.     

Ceramic dies selection for electrical resistance sintering of metallic materials

Processing metallic powders by electrical resistance sintering requires the use of insulating ceramics dies. Selecting the appropriate ceramic material according to the electrical, thermal and mechanical properties is a need. Dies produced with several ceramic materials have been tested during the production of cemented carbide in order to check their behaviour in the process and final product properties. Tialite/mullite, zircon/mullite, zirconium phosphate based ceramic, yttria-stabilized zirconia and sialon, in most cases with modified compositions and shaping processes in order to achieve a high density, have been tested. Dry powder processing by cold isostatic pressing and furnace sintering resulted to be the better process for dies production. The effect of die properties on the produced cemented carbide, and the behaviour and life of the die during the production have been analysed. Very smooth die surface increases the number of cycles withstood during metallic parts production, because of lower extraction stresses, as checked for sialon dies. Zirconium phosphate based dies, with low thermal conductivity, show the most densified hard metal parts surface.     

Yttria stabilized zirconia formed by micro ceramic injection molding: Rheological properties and debinding effects on the sintered part

Micro Ceramic Injection Molding (μCIM) is a near net-shape process to produce smaller and intricate parts at a competitive cost. The application of nano-sized ceramic powder in μCIM has the advantages of fine grain size growth and good surface finish. However, the nano size effect causes agglomeration and low powder loadings, which result in defects during the μCIM process and in the sintered components. This study extensively investigated the debinding and sintering of yttria-stabilized zirconia (YSZ), as well as its rheological properties, using polypropylene (PP) as the primary binder and palm stearin as the secondary binder. 50 nm Yttria stabilized zirconia (YSZ) powders were mixed with palm stearin and PP at a powder loading of 37–43 vol%. The results of rheological studies showed that the feedstock had a dilatant flow characteristic and a viscosity of around 10–40 Pa s. Feedstock with 38 vol% powder loading had the lowest activation energy of 9.48 kJ/mol. The green part of the injected feedstock had flexural strength ranging from 13 to16 MPa, within which the feedstock with 43 vol% powder loading had the highest green density. Solvent debinding was carried out at three temperatures (50, 60, and 70 °C) using heptane. A large porous region was clearly identified at 70 °C compared with 50 °C. A debinding split furnace with argon gas was used to remove PP at 450 °C for 4 h. The debound samples did not shrink when 94%–98% of the binder system was removed. All debound samples sintered at 1350 °C and 41 vol% had the highest mechanical properties with hardness of 900 HV and a flexural strength of 400 MPa.     

Improving the properties of binder jetted ceramics via nanoparticle dispersion infiltration

To improve the dimensional accuracy, surface quality, and mechanical properties of binder jet additive manufactured ceramic parts, in this work, nanozirconia dispersion and binder were used to prepare a jet solution to investigate the effect of nanozirconia content of the jet solution on the properties of zirconia ceramic green and sintered bodies. When the nanozirconia content of the jet solution increased from 0 to 20 wt%, the forming precision of the zirconia ceramic green bodies improved, the surface roughness decreased, and the density increased. After sintering at 1400 °C for 2 h, linear shrinkage along the height, width, and length of the zirconia ceramics decreased by 6.27%, 10.20%, and 5.45%, respectively, while the surface roughness decreased by 42.87%, and the bending strength increased by 145.60%. With increasing nanozirconia content of the jet solution, the spreading and infiltration distance of the jetted solution in the powder layer decreased, the thickness of the deposition layer of nanozirconia on the surface of the zirconia particles in the powder layer increased, and the pore size of the powder layer decreased significantly. This increased the density of the green bodies; thus, improving the sintering properties of the zirconia ceramics.     

Development and mechanical characterization of novel ceramic foams fabricated by gel-casting

Porous ceramic materials are of considerable interest for a variety of chemical and industrial applications in extremely harsh conditions, particularly at very high temperatures for long time periods. A combined gel-casting-fugitive phase process employing agar as a natural gelling agent and polyethylene spheres as pore formers was exploited to produce porous ceramic bodies. Alumina and alumina–zirconia powders were used to prepare samples having a porosity of about 65–70–75 vol%. The composite powder was produced by a surface modification route, i.e. by coating a well-dispersed alpha-alumina powder with a zirconium chloride aqueous solution. On thermal treatment, ultra-fine tetragonal zirconia grains were formed on the surface of the alumina particles. SEM observations and image analysis were used to characterize the microstructure of porous samples and uniaxial compressive tests were carried out to measure their mechanical behavior.     

Fabrication of a material with composition gradient for metal/ceramic assembly

This study presents a method and an apparatus for fabricating graded materials with powders. The application is about making some transition interlayer components when assembling metal to ceramic by brazing for example. The chosen applicative couple is inco600 with zirconia. The densification technique is hot isostatic pressing. After calibration of the equipment designed to make some bi-constituent powder gradients, a cylindrical component with a symmetrical axial gradient has been manufactured. Phase volume fraction composition determined through image analysis and micro-hardness study has demonstrated that the obtained composition and properties vary continuously along the gradient direction. The fabricated material also exhibits some cracks probably due to low sinterability of zirconia used (50 μm balls). Other tests should be done with a finer zirconia powder. This technique should then be employed to fabricate ceramic metal assemblies through the manufacture of intermediated graded parts between the metal and ceramic components.     

Ink-Jet Printing of Binders for Ceramic Components

Layered manufacturing methods for fabricating ceramic components can involve selective deposition of binder using ink-jet printing. Selection of a proper binder plays a critical role in fabricating parts with good surface finish, dimensional accuracy, and high resolution. Several polymeric solution-phase binders were investigated in terms of their physical properties, printing performance, and binder-powder bed interaction. It was observed that the molecular weight should be <15 000 for the binder to be penetrated into dense powder compacts. Binder infiltration kinetics and printed line width were also significantly influenced by powder-bed characteristics, such as surface roughness and pore size, as well as the physical properties of the binder, such as viscosity and surface tension.     

UV Curable Systems for Tape Casting

The substitution of solvents by photopolymerizable binders in the tape casting process allows to achieve high ceramic loading and to eliminate the drying stage which is a critical step of the tape casting process. After the rapid UV polymerization of the resin, the high strength green tapes can be debinded and sintered. Ceramic suspensions containing alumina or zirconia powder, dispersant, UV curable binder and photoinitiator have been prepared. The use of a low viscosity organic vehicle allows to prepare low viscosity ceramic suspensions, containing about 50 vol% powder, which have a shear thinning behaviour. Because of the rapid attenuation of the incident light in UV curing systems containing ceramic particles it is important to estimate the thickness of the tape that can be treated. The effect of incident energy, of photoinitiator concentration and of powder volume fraction was studied. There is an optimal photoinitiator concentration which maximizes the cured depth and which depends on the volume fraction of solid. A theoretical model based on the Beer–Lambert’s law enables the prediction of cured depth for any volume fraction of solid. To prove the ability to manufacture ceramic sheets by tape casting, some suspensions were tape cast.     

Strength of Green Ceramics with Low Binder Content

Acrylic-based polymers are common binders that impart high green strength (>2 MPa) at low concentrations (<5.0 vol%). Strength at low binder concentrations may be determined by chemical bonding at the ceramic–polymer interface. We have studied the binding mechanisms as a function of ceramic surface chemistry using a cross-linkable binder, which is based on a soluble poly(acrylic acid) (PAA, MW = 60 000) and glycerol. The cross-linked PAA binder system has been integrated into a solid freeform fabrication process, which provides a means of fabricating very reproducible green bodies, including SiO₂, TiO₂, Al₂O₃, multicomponent oxides, and non-oxides, with uniform density and composition. The ceramic parts contain only 2.5 vol% binder (solids basis), which increases the strength of the ceramic systems by at least a factor of 8 while the strength of Al₂O₃ components increases by a factor of ∼24 (0.3 to 7.6 MPa). Addition of the binder improves the toughness of the ceramic bodies by an order of magnitude with SiO₂ representing the largest relative increase (2.8 × 10⁻³ to 4.4 × 10⁻² MPa·m^1/2). The mechanical properties are dictated by two binding mechanisms: binder adsorption and mechanical interlocking. High green strengths result from adsorption of the binder onto the ceramic surface whereas toughness is enhanced by poor adhesion of the binder to the ceramic surface.     

Aqueous Emulsion Acrylic Binders for Low-Foaming Ceramic Slips

Experiments are reported to fundamentally understand foaming in ceramic slips. Adsorption of two different types of surfactants, one anionic and another nonionic, onto alumina powders was studied. The most significant observation was that while the anionic surfactant strongly adsorbed onto alumina powders, the nonionic surfactant had essentially no adsorption. A model polymer based on the anionic surfactant was synthesized and compared with a similar polymer prepared with the nonionic surfactant. The comparison demonstrated that while the model polymer foamed severely in its neat form, it produced a very low-foaming ceramic slip when formulated with alumina powder because the surface-active agents in the binder strongly adsorbed onto the powder. Based on these fundamental understandings, a series of aqueous emulsion acrylic Duramax binders were developed. The influence of these binders on foaming in alumina slips is reported.     

Binder removal via a two-stage debinding process for ceramic injection molding parts

Debinding binders in two stages is critical to maintaining the shape of injected parts; the resulting decomposition affects the strength and rigidity of a structure. This study determines the optimal debinding process on the basis of a higher binder removal rate and the production of defect-free parts. The feedstock used was a combination of alumina–zirconia powder with a binder that consists of high-density polyethylene (HDPE), paraffin wax (PW), and stearic acid (SA). During the first stage, the injected parts were immersed in an n-heptane solution at 50 °C, 60 °C, 65 °C, and 70 °C to remove PW and SA. Binder weight loss was evaluated as a function of time. In the second stage, HDPE was removed by using thermal debinding. The results show that the optimum solvent debinding process runs for 16 h at 60 °C. The weight loss of the binder reaches 41.1% and results in the formation of defect-free parts. The binders are degraded at approximately 550 °C during thermal debinding. This degradation resulted in decomposition of nearly 96.9% of the binders. Low heating rates (1 °C/min to 2 °C/min) prevent defects from forming in the injected parts.     

Environmentally-harmless polylactic acid-polyethylene glycol binder for deformable ceramic green body

We report a polylactic acid (PLA)-polyethylene glycol (PEG) mixture as a thermoplastic binder to prepare shape-machinable ceramic green bodies. During the mixing process, the high viscosity of the PLA binder impedes effective mixing with ceramic powders. To address this issue, PEG was introduced as a plasticizer into ceramic/PLA composites to diminish the overall viscosity of the feedstock, which resulted in effective mixing with ceramic powders. After sintering green bodies composed of PLA-PEG binders and ceramic compounds, the mechanical properties (flexural strength and porosity) of the sintered specimens were investigated and compared with those of sintered specimens made from wax-based green bodies. The sintered specimens made from ceramic/PLA-PEG composites showed comparable mechanical properties and porosities with the sintered specimens made from ceramic/wax composites. In addition, the shape-machinable characteristic of the green bodies made from ceramic/PLA-PEG composites was demonstrated by deforming the entire structure of the green bodies via simple heat treatment.