Binders
1. Compaction behaviour of organic binders in alumina
ceramics(PVA & PEG)
General facts
Mean grain size of raw material alumina is 1.3μm
The mean grain size of the spray dried agglomerates are typically between 100-200μm
Stages of compaction involves rearrangement of granules, then elimination of inter-granular
porosity and third stage is reduction of intra-granular porosity through rearrangement of
elementary ceramic particles
They exhibit plastic behaviour over a significant range of deformation
Property PVA PEG
T 79°C -60°C
g
Mol Wt. 31000 20000
Manufacturer/Product ID Hoescht 4-88 D PEG20M(union carbide)
Chain Straight chain -OH on chain Straight chain di-ol
The Experiment
Aqueous suspensions of 60 wt% alumina with 3 wt% binder was taken
Particle size 200 μm approx
Residual moisture after spray drying 0.6wt%
3 samples: PEG (powder 1), PVA (2) & dried PVA (3) compacted @4mm/min
Green samples analysed with the help of Hg porosimetry
The moisture content of 0.6wt% corresponds to 20wt% moisture if only absorbed in the organic
phase. Tg of water plasticized-PVA should thus be located close to room temperature.
Results
PEG PVA Dried PVA
No intergranular porosity Marginal porosity Higher porosity
Densification due to intergranular & intragranular compression analysed for powder 2
Penetration of Hg through pore sizes greater than 1.3μm is intergranular pore else
intragranular
Densification is enhanced if Tg is below ambient temperatures
Intragranular porosity drops more sharply for powder3 than powder2 upon applying
pressures of 10-100MPa
Intergranular porosity drops more sharply for powder2 when compared to powder3
Powder1 shows the best results
2. US patent – Ethylene acrylic acid co-polymer
General Facts
Used as binder for ceramics particularly alumina ceramics
Organic binders tend to require extended times during the 'burnoff' stage
Large % of organics tend to produce cracks or blemishes
Higher boiling point organics require a longer sintering step & length of the polymer hinders
escape which eventually results in cracks
This composition exhibits excellent wettability characteristics
• Co polymer of ethylene and alpha-beta unsaturated carboxylic acid
• The high concentration of oxides of many polymers are polar and attracted to the carboxylic
groups in the co-polymer, increasing wettability.
• DEAE (diethyl amine ethanol) acts as a surfactant and good dispesing agent for thw
copolymer
• Polyethylene ionomer containing Mg maybe used as a binding agent in injection moulding
machinery. It has a low melting point of 90°C.
• Methyl cellulose is another good ceramic binder and is marketed as Methocel 20-231.
• Hydroxyethyl cellulose may be added about 6wt% organic binder along with the new
invention. It has a trade name HEC15000H.
• A gelation agent(3-25%) may be used to improve preform retention. It may be PEG, methyl
cellulose etc.
• An important aspect of the invention is that a major portion of the aqueous organic portion
consists of water. When the binder is driven off from the preform , the water vaporizes first,
increasing porosity thus helping the homogeneous burnoff of the binder.
Commonly used configurations of today:
3. Carboxymethyl Cellulose
General Properties
Tg = 135°C (dry state) .This drops to -85°C on adding 0.2 to 0.5(g/g) water.
Cellulose ethers are binders designed to improve water retention.
Mol. Wt. Is of the order of 17000
Different grades of CMC are available in the market with varying viscosity, degree of
substitution, pharma/food grade and coarse/fine particle size
Online detailed product specifications requires special request
Viscosity of CMC is found to drop significantly upon addition of certain cations like Na+,
Ca++ and H+
The viscosity is found to drop linearly with temperature(°C)
It is pseudoplastic whose viscosity drops with shear rate
Merits
Ensures uniform, controlled drying
Prevents thermogelling cellulose ethers from migrating to the surface during drying
Prevents formation of cracks or blisters
The gelation temperature, the temperature above which the viscosity starts increasing can be
adjusted by adding suitable additives for best results in the case of methyl celluloses. No
references for gelation occuring in CMCs.
4.Polyurethane binder
In 1995, a polyacrylic binder, Duramax B-1031, (Rohm & Haas) was developed. The binder
provided sufficient green strength to allow shaping of unfired ceramic parts from alumina & SiC by
drilling, lathing and grinding. Today, Dow chemicals has Duramax B-1022 with the same
applications.
Polyurethane emulsions are often obtained without low-molecular emulsifiers and therefore
the burnout residue is low
Polyurethane chains could adsorb easily on the surface of ceramic powders due to the
presence of hydrophobic groups, those could be coordination centres, creating strong
interparticle interactions. Hydrogen bonding bridges between the polymer molecules and the
ceramic particles further increases green strength
Experimentation
• Alumina powder of size 0.7μm
• Aqueous polyurethene dispersion 35wt% solid particles [polycarbonatediol (cyclohexane di-
methanediol dimethyl propane derivative & cycloaliphatoc isocyanates)]
• Quantity of binder added was 1-5wt% in steps of 1wt%
• Mean size of spray dried granules was 200μm
• Pressed at 150MPa
• Moisture in binder granules was 2.7 -2.9 wt% (sample1) & this was dried for 4hrs @ 80°C
to get 0.5-0.7 wt% moisture (sample2)
Properties measured:
1. Tensile strength (using diametral compression method called 'Brazilian test')
2. Flexural strength (using 3 point bending method)
3. Glass transition temperature (differential scanning calorimetry)
4. Polymer Ceramic interactions are studied using IR spectroscopy
5. The thermal decomposition of polyurethane binder is studied by thermogravimetric analysis
(TGA) and differential thermal analysis (DTA)
Results & Discussions:
Tg of binder was 28°C, several degrees higher than the pressing temperature it required
plasticization for obtaining a good compaction. The moisture content of alumina provided
this reduction in Tg
Depending on binder concentration (1–5 wt.%), the green density varied between 59 and
57%of the theoretical density of corundum(3.98 g/cm3)
The green density decreases with increasing of a polyurethane binder concentration &
moisture helped increase green density
Variation of green strength with binder wt%
Tensile strength for the dried powder is greater and increases with binder wt% concentration
Because Tg of polyurethane binder is 28 °C, it ought to be plasticized by water to
achieve high green density, but then dried to yield high strength.
Molecular interactions:
Binder Burnout Characteristics:
Thermal decomposition takes place by two mechanisms depending upon the medium
used is air(oxidation reaction) or nitrogen(depolymerization reaction).
In air, the poly-urethane binder starts losing its weight at approximately 120 °C. Upon
reaching 200 °C, the polymer loses about 10% of its weight. This pattern continues to
approximately 470°C where the weight loss reaches 90%.
At 600°C it reaches a plateau,leaving 0.4% residue.
In nitrogen, the poly-urethane binder starts losing weight at approximately180°C. Upon
reaching 300°C, the polymer has lost approximately 20wt%. At 475 °C the weight loss
reaches a plateau, leaving 0.1% residue.
Conclusions:
1. The polyurethane binder provided high green strength of dry-pressed alumina compacts.
Depending on binder concentration (1–5 wt.%)the tensile and flexural strengths varied
between1.6–7.0 and 2.0–12.7 MPa, respectively.
2. IR study revealed that the high green strength was controlled by hydrogen bonding between
oxygen atoms of alumina oxide and urethane groups of binder phase.
3. The glass transition temperature of polymer influenced the binder behaviour in the ceramic
processing. For decreasing Tg the binder had to be plasticized by water to achieve high
green density, but then dried to achieve high green strength.
4. The polyurethane binder had a gradual burnout with a low char residue in both air and
nitrogen.
5. US patent - Polyalkylene Carbonate
If the binder is in the form of an emulsion either with water or an organic like alcohol, then
the ceramic binder must be dried to produce a free flowing powder prior to shaping the
mixture into a green body
The process is particularly suited for ceramic powders which should not be exposed to an
oxidising atmosphere, because the binder composition of the present invention can be
burned out in a non-oxidising atmosphere
Polypropylene carbonate and polyethylene carbonate are preferred
They decompose cleanly to produce cyclic carbonates, hence they dont require oxygen for
removal.
Ash content after burn out is 0.058wt% in air & 0.13wt% in nitrogen
Green density increase is shown below:
Density of the sintered product expressed as % of theoretical alumina density:
This binder decomposes completely even in inert atmospheres. Hence, the volume of gas
produced during sintering is reduced thus reducing the possibility of cracks to form.
