Raw material and processing in general

Ceramics raw materials: 55% Quartz (sand) 35% Coke 5-10% Sawdust
(Sägemehl) 1-3% Salt

Temperature: 2000 - 2400°C Reaction time: around 40 h

Overall reaction: SiO2 (s) + 3 C (s) -SiC (s) + 2 CO (g) – 528 kJ/Mol (electrical
energy)

NOTE: 1 kcal = 4.184 J/Cal

Ceramic Processing

➢ The most common methods are:

dry pressing, slip casting, tape casting, and extrusion.

1
➢ The degree of complexity of the final component is relatively low (except for
slip casting).

➢ They might be considered “traditional” processes

➢ Ceramic Injection Moulding is also typical, but relatively recent. It leads

complex shapes.

➢ These processes leads to a green body. ➢ Then, sintering.

Problems with Ceramic Processing:

➢ Hardness makes difficult the milling process and will cause severe wear and
damage

➢ Milling process: (typically) high energy, high temperature, abrasion and

impacts

Dry pressing

➢ Simple geometries such as substrates, bricks or tiles

➢ Even dry pressing requires some organic additives to increase packing,

reduce friction and easier ejection

➢ Also to reduce the damage of the tools

➢ High stresses might cause huge defects in the green body

➢ It might lead to inhomogeneous densities

➢ The deformation of the ceramic particles is really limited (brittle) so maximal

green density ~ 60%
➢ Simple and relatively simple geometries can be produced

Slip casting

➢ Relative complex shapes!

➢ The thickness of the wall is constant! Typically, thin thickness

➢ Excess of the suspension can be reused

2
➢ To facilitate the drying process, water content as low as possible (25-35 wt.%)

➢ Low viscosity to increase the green density

➢ Green strength increases with increasing deflocculant content.

Alumina powder (>99.9%, D50: 170 µm), Ammomium salt of poly(methacrylic)

acid (to prevent agglomeration), and polyvinyl alcohol (PVA, as binder) to
enhance mechanical strength of green body.

Tape casting

➢ Just tapes with thickness 25 µm to 1.5 cm ➢ Highly used in industry for

SOCs, electronics, capacitors, protection, etc. ➢ Ceramic powders plus binders,
deflocculants and plasticizers. Then, degassed slip, control of thickness with
doctor blade, and continuous belt (protected with a carrier polymeric film). ➢
Evaporation of solvent during process ➢ More or less flexible depending on
binders

Extrusion

➢ Defined cross sections as tubes with different

Complexity.

➢ “long” products

➢ Plastic behavior, control of the rheology

➢ Feeding, metering screw and extrusion

Ceramic Injection Molding

➢ Highly used for polymers and metals, less for ceramics

➢ Highly used in industry due to large number of items
per time (one sample few seconds)
➢ Preparation of the feedstock (ceramic powder and
additives)

3
Cons

➢ Shrinkage during sintering; important to take into account when the

component is designed
➢ Good reproducibility and surface quality to produce components with relative
complex shapes

Powder preparation goals

➢ Material consistency: ▪ Hardness ▪ Plasticity

➢ Moisture: ▪ Wet: > 20 % humidity (i.e. suspension) ▪ Moisture: 3 – 20%

Humidity ▪ Dry: < 3% Humidity

➢ Operation: ▪ Continuous ▪ Discontinuous

➢ Crushing (obtaining powders)

➢ Homogeneous mixing

➢ Addition of organic / inorganic

4
Why Additives?

Change in surface quality

Dispersion of powders in suspensions
Deformation caused by wear
Mechanical alloying

5
Monomodal particle size ▪ Narrow and homogeneous powders ▪
Homogeneous features (i.e flowability) ▪ Higher green densities ▪ Moderate grain
growth ▪ Homogeneous microstructure

Bimodal or wide particle size distribution ▪ Inhomogeneous powder

features and packing ▪ Inhomogeneous microstructures ▪ Abnormal grain growth
▪ Higher porosity ▪ Larger defects and lower properties

Sources for Alumina:

Bauxite
Other natural sources for alumina:
Kaolinite Al4 [(OH)8Si4O10]
Leucite KAlSi2O6
Nepheline NaAlSi2O6
Anorthite CaAl2Si2O8

6
Sources for Zirconia

Heavy mineral sands („Seifen“) ZrSiO4 + Fe3O4 + FeTiO3 + TiO2 + CePO4 +...

Zircon Magnetite
Ilmenite
Rutile
Monazite ZrSiO4 HfSiO4
Hafnon ThSiO4
Thorianit (Zr,Hf,Th)SiO4,
Baddeleyite

Thermal decomposition of ZrSiO4 at 2000 ° C in an electric arc furnace

ZrSiO4 → ZrO2 + SiO2 ZrSiO4 + C → ZrO2 + SiO + CO

Purification by means of fractional distillation:

7
ZrO2 + PCl5 → 3 ZrCl4 x 2 POCl3 3 ZrCl4 x 2 POCl3 + H2O → ZrOCl2 x 8 H2O
+ H3PO4 or ZrO2 + 4 C + 2 N2 → Zr(CN)4 Zr(CN)4 + 4 HCl → ZrCl4 + 6 HCN

Implementation of ZrSiO4 in an oven at 800-1200oC:

ZrSiO4 + 3C + 4 Cl2 → ZrCl4 + SiCl4 + 4CO

Sublimation of ZrCl4 at 150 - 180oC,

Solve in water, Reprecipitation as ZrCl4 x 2H2O,

Calcination to ZrO2 or

Precipitation as Zr(OH)4 with ammonia from ZrOCl2 -solution,

Calcination to ZrO2
Co-precipitation with Y(OH)3 or Mg(OH)2

Silicon Carbide sources

occurs naturally in traces as a component of extraterrestrial celestial bodies

(e.g. in addition to diamond as a precipitate in iron-nickel meteorites)... also in
igneous rocks of the lower earth mantle (such as in Siberian kimberlites and
Bohemian breccias) And Natural moissanite in Mediterranean sands near
Izmir (Turkey) probably sedimentary residues from weathering of Fe-Ni
meteorites

8
Milling
Impact crusher - Hammerbrecher To improve the performance difference
possibilities

Impact milling Same concept as the impact crusher (in this figure hammer
crusher)

Ball-Milling Ball milling is one of the most used methods to reduce the particle
size; particularly for advanced ceramics. Impact of the grinding balls with the
particles to break them

powder to mill and some milling balls

Dry or using a liquid media (typically water or alcohol); dispersion and
reduction of energy and temperature
The atmosphere is also really important due to potential oxidation High
temperature due to the impact of particles, they can be melted and damaged

9
High Energy Ball Milling - Attritor

Different types and sizes; the type of balls is really important (composition and
size)

Limits of milling through agglomeration, Cold welding and "mechanical

alloying"

Jet Milling

Used in industry, Does not required any milling media reducing the wear,
impurities and cost Milling by impact with the same particles Narrow selection of
particle size

Classification and separation of fractions

Once the powder is milled, we need to separate the different fractions.

Basically all the processes are based on the same concept, a filter (the term is
“sieve” or “Sieb”) to separate the different fractions.

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Mogensen-Sizer

is highly used and is based in the same concept as sieving (but bigger) 1)
Arrangement of inclined sieve trays 2) Fine material 3) Excenter excitation 4)
Sieve trays

Advantages
Low energy requirement: just gravity.
Light maintenance High efficiency, High versatility in terms of materials and
classification, Quick and cheap

Luftstrahlsieb/air jet sieving

Same concept but assisted by pressurized air to move the particles Laboratory
scale; requirement to change the sieve

Windsichter/Air separator

At lab scale but also industrial Separation of fine and coarse grains depends on
distribution plate, rotation and gaps

parts
1) fan 2) Turntable 3) Centrifugal system 4) task 5) Inner container 6) Distribution
fan 7) Cone for coarse grain Mühle mit Windsichter

Cyclone separator

Creation of a vortex to separate course and fine powders. In fact, it is also used
to remove particles from air (such as ashes). The main vortex spirals downward
and carries the coarser particles. The inner vortex created near the bottom
carries the small (finer) particles Highly used in laboratory and industrial
equipments

Parts: 1) conical part 2) cylindrical part 3) Inlet nozzle 4) Outlet nozzle 5)

Overflow climbers 6) Overflow outlet

Colloidal Stability

Main concept: Homogeneous distribution of the ceramic particles

➢ Looking for the highest packing as possible

11
➢ The additives are “carriers” to “transport” the ceramic particle into a
complex shape, but not desired in the final product. They are eliminated
typically during a thermal process
➢ “just” particles will attract each other, forming aggregates and sedimentation.
➢ We need to add the organic binders for dispersion and control of the
suspension Briefly but important!

Zeta potential is an electrokinetic potential at the shear plane (the boundary

between the compact layer and the diffuse layer) near a solid-liquid interface
where the liquid velocity is zero. Measurable indicator of the stability of
colloidal dispersions. The magnitude of the zeta potential indicates the
degree of electrostatic repulsion between adjacent, similarly charged particles in
a dispersion. For molecules and particles that are small enough, a high zeta
potential will confer stability, resisting aggregation.

Factors affecting zeta potential

pH

If more alkali is added to this suspension, then the particles tend to acquire more
negative charge. If acid is added to this suspension, then a point will be reached
where the charge will be neutralized.

Conductivity

The thickness of the double layer (κ-1) depends upon the concentration of ions in
solution and can be calculated from the ionic strength of the medium. The higher
the ionic strength, the more compressed the double layer becomes. The valency
of the ions will also influence double layer thickness.

Colloidal stability and DVLO theory

Stability of a particle in solution depends on its total potential energy function VT.

VT = VA + VR + VS

VS is the potential energy due to the solvent (marginal contribution) VA and VR,
these are the attractive and repulsive contributions, and their balance is
determinant. VA = -A/(12 π D2) where A is the Hamaker constant and D is the

12
particle separation. VR = 2 π ε a ζ2 exp(-κD) where a is the particle radius, ε is
the solvent permeability, κ is a function of the ionic composition and ζ is the zeta
potential.

DVLO theory suggests that the stability of a colloidal system is determined

by the sum of these van der Waals attractive (VA) and electrical double
layer repulsive (VR) forces that exist between particles.

Therefore if the particles have a sufficiently high repulsion, the dispersion

will resist flocculation and the colloidal system will be stable.

Steric stabilization
Polymers added to the system are adsorbed onto the particle surface, preventing
the particle surfaces coming into close contact (van der Waals forces will be
weak due to distance).

Disadvantages
However it can be difficult to flocculate the system if required, the polymer can be
expensive and is undesirable (has to be 'burnt out’). This causes shrinkage and
can lead to defects

Electrostatic stabilization

Effect on particle interaction due to the distribution of charged species in the

system.

Electrostatic stabilization has the benefits of stabilizing a system by simply

altering the concentration of ions in the system. This is a reversible process and
is potentially inexpensive.

Surface Charges

Dissociation of acidic groups on the surface of a particle generates a

negatively charged surface. Conversely, a basic surface will take on a positive
charge. In both cases, the magnitude of the surface charge depends on the
acidic or basic strengths of the surface groups and on the pH of the solution

The surface charge can be reduced to zero by suppressing the surface

ionization by decreasing the pH in case of negatively charged particles or by
increasing the pH in the case of positively charged particles.

13
Surfactant ions are adsorbed on the surface of a particle, leading, in the case of
cationic surfactants, to a positively charged surface and, in the case of anionic
surfactants, to a negatively charged surface.

Advanced Ceramics

➢ Some of the applications required really complex shapes

➢ Additionally, to the previous processes, new processes are required
A great future is here but more progress in R&D is necessary to improve
materials and reduce costs.

Additive Manufacturing of Ceramics

➢ Considerable increase of complexity

➢ Some components impossible by other processes
➢ AM has opened another „world“ for ceramics
➢ But also, there is a hype, so think and evaluate!
➢ Several different types, names and classification

➢ Direct methods: deposition of a layer and immediately densification. No post-

treatment, quick, no shrinkage; however porosity, low purity and surface quality
➢ Indirect methods: first a green body, and then in a post-process the sintering.
High
densification, good surface quality, and control of microstructure.

Stereolithography is one of the most attractive methods due to the high quality
of the final components

➢ There are different approaches (top-down

and bottom-up)
➢ Based on a photopolymeric liquid that is
cured with a light (typically UV)
➢ Ceramics powders and photopolymers or
photopolymer and then ceramic conversion

Robocasting

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➢ Extrusion of a ceramic paste (or ink) through a small nozzle
(μm – mm)
➢ Rheology of the suspension is determinant, since it has to
flow when the pressure is applied and have good mechanical
stability to withstand the new layer on top
➢ Afterwards, sintering process

➢ As mentioned the ink preapration

is determinant
➢ Shear thinning behavior
(explained in other lecture)
➢ Briefly, low viscosity at relative
high shear rate and high viscosity
without any force.
➢ Drying and burning out avoiding oxidation
of the ceramic
➢ Followed by sintering at high temperature

Directed Energy Deposition (DED)

➢ Thermal energy by a laser, which melts the ceramic
powder while depositing onto the surface.
➢ Direct method even for ceramics > 3000 °C
➢ No slurries/inks; here powder flowability
➢ Feeding of the ceramic powder, melting and deposition.
➢ Critical: lasers pot width, laser scanning speed, and
powder feeding rate

15
Thermal Spray

Gas turbines – on site or mobile – needs thermal barrier coatings to protect the
metallic superalloys from the oxidation and to reduce the temperature (1400 –
1500 °C)

The TBC is a coating (around 500 μm) based on a ceramic compound. However,
for the adhesion to the metallic substrate a “Bond-coat” is necessary, which will
form during the high temperature process a thin and dense layer of (typically)
alumina to prevent oxidation.

Processing of these coatings is relatively complex and is performed by thermal

spray technologies

Atmospheric Plasma Spray (APS) is the most common process due to

economical reasons as well
as performance. The ceramic particles melt due to the high plasma, followed
by their impact to
the substrate. The solidify/crystallize forming a coating with porosity.

16
➢ Coatings for all gas temperatures, but lower defects at higher temperatures
➢ Higher temperature entails higher velocities and better cohesion between
Cr2AlC particles.

Pros:

➢ Thicker, denser and reduction of cracks (inter-splat cracks) with temperature

(higher velocities)
➢ Good adhesion between the coating and the substrate
➢ Detection of some impurities

Features:
➢ Some impurities, but below 1 vol.% by Image Analysis
➢ Cr2AlC purity > 97% (best in literature for Ti2AlC ~ 60%)
➢ Some orientation in the basal plane (pole figures)

➢ Cr2AlC as coating, but also as intermediate layer for bond-coat and/or joining
➢ Excellent adhesion steel substrate/Cr2AlC, as well as Cr2AlC/YSZ
➢ Potential of sprayed Cr2AlC as coating and as a bond-coat (or as joining
material)

Thermal spray technologies are competitive processing techniques to deposit

coatings

17
Sintering

(Mechanical) Sintering is a thermally activated transition of a

powder or porous system to thermodynamically more equilibrium
states through a decrease of the free surface energy.

(Physical) Sintering is a thermal treatment of bonding particles

into a coherent solid structure via mass transport that occurs on
the atomic scale. The bonding leads to improved strength and a
lower system energy.

Driving forces for sintering

- Decrease of the free energy of the system (Thermodynamic)

- Matter is transported by diffusion of atoms and ions (Kinetic)

𝑱 = −𝑫 𝛁 𝑪

J: Diffusion flux
D: Diffusion coefficient
C: Concentration gradient

18
Three kinds of diffusion rates depending on the area. D surface > D GB > D
lattice

3 mechanisms. They are not a densifying type, but they produce the coarsening
of the grains. (They do not close porosity)

It is a competition between them and all the mechanisms reduce the free energy
of the system.

last step is a competition between sintering (closing the porosity) and grain
growth.

19
Some pores are trapped inside the grains and will never be eliminated. It is
caused due to the mobility of the grain boundary migration

Once the grains growth they do not have enough energy for the
densification. Sintering during this step is reduced.

Conventional Ovens

low heating rate (up to 10-20 K/min).

• Large dwell times (isothermal holding time at

maximal temperature). It takes hours or even days.

20
• High temperatures (> 1000 °C) and typically around
1400°C.

• High consumption of energy, so new techniques are

demanded, although cost and number of items are
Determinant.

Spark Plasma Sintering

➢ DC pulse current process with low
voltage and high current)

➢ Assisted by uniaxial pressure

➢ Controlled atmosphere

➢ High heating rates (> 100 °C/min)

➢Max. temp. 2200 °C

➢ Short dwell time (min)

➢ Limited grain growth

➢ In principle samples with simple

geometries (different strategies)

Graphite for Dies and Punches

➢ Temperature-resistant up to max. 2,500°C (optional: oxidation-resistant)

➢ Good conductivity properties (heat and electricity)

➢ Mechanical resilience (pressure resistant up to at least 140MPa, but typically

50 MPa)

➢ Good wear resistance

➢ Chemical resistance

21
➢ Inexpensive to manufacture and good machinability

➢ Costs that are in reasonable relation to the expected service life

➢ The electrical current should flow so it is required that the dies are conductive
as well as sample and/or dies

Influences temperature distribution in the sample and thus the homogeneity of

the microstructure Finite element simulations help as a predictive optimization
tool

Cons of SPS

- Only samples with simple geometry

- (typically) just one sample per cycle, however, this is changed at industrial
level

Sinter complex shapes through the control of the graphite tools

Pros:

➢ Automatization
- Less manpower needed
- Increment of reproducibility
- Large number of samples
- Lower risk of damage (equipment & personnel)

Development of compositional Microstructures via SPS:

Stacking different layers (discontinuous)

Residual stresses at interfaces
Complex process to large scale manufacturing
High time and cost consuming

One-step continuous FGM

Reduction of residual stress
Simple and easier for scaling up
Cheap and fast processing (minutes)

22
Joining of metals and ceramics for oxygen separation membranes
NiCoCrAlY
Mechanical stability and ease joining
with membrane modules

Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)
Dense thin layer to increase
ionic conductivity

Requirements for oxygen separation membranes:

Dense/porous structures

➢ The porous supports have to be welded with the dense parts of the
membranes

➢ This process is complex and a solution is required

Flash sintering

➢ Sintering assisted by electric field/current. Increase of densification rate

by the electric field

➢ Temperature of the furnace is relatively low

➢ Electric fields between 0 and 103 V/cm. Determines the evolution of the
microstructure

➢ Furnace temperature and Joule heating

➢ Strong discussion about effect of current

➢ Sintering happens in seconds (flash)

➢ Field Assisted Sintering (softer) and flash sintering

(harder)

➢ Fine grains (< 1 μm) for low fields and large grains (> 1 μm) for high fields

23
➢ Grain growth is a thermally activated diffusional process (massive matter
transport)

➢ Flash of insulator ceramics (such as Al2O3) is not possible or required high

electric fields (103 V/cm)

Cold Sintering
- Sintering at low temps.
- Transient phase – typically water (< 10 vol.%)
- Pressure (< 500 MPa, although no limitation)

Effect of heating rate/evaporation of water

➢ Full densification takes place only for high heating rates in presence of water.

➢ High heating rate combined with a low water content triggers new sintering
behavior.

➢ Kinetics of water desorption play a significant role and limit the

temperature-time window in which the crystal interface is modified.

➢ „Dry“ powder requires double temperature than „aqueous“ to achieve high

density

➢ Consequently the grain size is larger, more than one order of magnitude
higher

Effect of Pressure

➢ Better packing and sintering for samples containing water (ZnO/H2O and
ZnO/Ac-H2O)
➢ Large influence by applied pessure
➢ Higher final densities for ZnO/Ac-H2O (up to 97.3 %)
➢ Large influence of pressure, also to the onset of the densification
➢ Densification starts at RT with low quantities of acetate
➢ Sintering mechanisms do not correspond with solution-
precipitation
➢ Massive formation of vacancies by diffusion of H+ and OH-

24
Features

➢ High densities and small grain size (nanometer)

➢ Strong effect of small addition of zinc acetate on grain growth
➢ Preferential grain growth in plane 001 (measured by XRD)

Kelvin Probe Force Microscopy (KPFM)

➢ Topography and surface potential → possibility to distinguish between grain
and grain boundary
➢ Homogeneous microstructures

25
GI
Compared to 2004/2017, total energy demand has decreased by 6% in 13
years

Compared 2004/2017, renewables have slightly more than tripled in 13

Years

• German power plants: Around 38% efficinecy

• Coal-fired power plants connected to the grid: 40 and 45%.

• Advanced Coal-fired power plants(Under research): 50% efficiency

• Combined cycle power plants using natural gas as a fuel: Around 63%
efficiency

Melting and holding of the casting alloys alone requires approx. 50% of
the total energy required for the production of cast components.

26
Al-parts have the largest share of non-ferrous cast products.

• High savings potential for the melting process, as this alone accounts
for approx. 50% of the total energy required.

• The potential savings in the future depend heavily on the current

efficiency and the optimization of the process that has already been
implemented.

• Development of different process variants with regard to the occurring

material and energy flows

Process variants differ with regard to the delivery of the Al.

Recycled material:

• Lumpy metal residues produced during casting production, which are

separated from the raw casting during fettling and remelted.

• Sprues, runners, gates and risers, as well as scrap castings originating

from the same foundry.

• Chips, flakes and other fine metal residues are not included
in the cycle, but can be melted down if the foundry is suitably
equipped. In most cases, however, they are sent to scrap

27
dealers or recycling plants for the production of secondary
Aluminum

Variation 1 of Al Smelters

In independent smelters, aluminum scrap, pure Al and other alloying

elements are melted down, with the proportion of scrap and pure aluminum
being variable.
• Casting of the aluminum into ingots (note: Al is traded globally as ingots
and ingots are therefore the standard form of solid Al for transport).
• Transport to the foundry, which is also independent.
• Melting of the ingots in the foundry.
• Mono-fractioned recycled material (sprues, scrap) is only used within the
foundry.

Variation 2 of Al Smelters
• Melting of scrap as well as mono-fractioned recycled material from foundry in
integrated melt shop (same location)
• Addition of pure Al and alloying elements
• Transport of liquid melt in ladle to the integrated foundry
• Holding of the melt until casting
• Return of the recycled material to the melting shop

Variation 3 of Al Smelters
Melting of scrap and recycled material in the independent melting shop
• Addition of pure aluminum and alloying elements
• Overheating up to 900°C and transport in special containers to external foundry:
other location, up to several 100km distance (external foundry, does not belong
to
the melting plant, but is a customer)
• Melting of the recycled material in the foundry and merging of the melts

Variation 4 of Al Smelters

28
• Melting of scrap and recycled material in the independent melting shop
• Addition of pure aluminum and alloying elements
• Overheating up to 900°C and transport in special containers to the
foundry: other location, up to several 100km away (external foundry, does
not belong to the melting plant, but is a customer)
• Keeping the melt warm until casting
• Return of the recycled material to the melting plant

• Solid metal delivery is economical if melting process (in foundry) approx.

< 800kWh/t
• In case of liquid metal transport, a higher superheating of the melt is
necessary in order to have sufficient superheating at delivery.
• Energy consumption for liquid metal delivery scaled with distance
• Approx. 75 kWh/Km

• Variant 1 (ingots, solid Al) highest energy demand as well as CO2 emissions
• Transport of raw material, remelting
• Variant 2 (liquid Al; internal foundry) lowest CO2 potential
• Low energy loss due to elimination of transport

• Worldwide, around 20 percent of aluminum demand can currently be met

from scrap
• If one product is manufactured 100 percent from scrap, 4 products must be
manufactured 100 percent from primary aluminum
• Statements on components with a high recycled content can therefore only be
made
selectively, since the amount of scrap available worldwide is not sufficient for all
components -> scrap availability is essential
• The above figures apply to Al consumption in general. For cast alloys, the
scrap content is higher, but exact global figures are currently not known.
• Sophisticated components made from secondary alloys are possible,

Choice of melting unit varies with choice of raw material

• Widely varying liquidus temperatures
• Electrically operated furnaces
• Induction furnaces, electric arc furnaces, electrically heated crucible furnaces
• Furnaces operated by fossil fuels (gas)
• (cupola furnace: only for cast iron), shaft melting furnace, crucible furnace,

29
tank melting furnace, rotary drum furnace

• Shaft melting furnaces are predominantly used for melting Al. Depending
on the application, induction, crucible and tank furnaces are also used.
• Crucible furnaces are mainly used for holding at the casting lines in die
casting, low-pressure die casting or gravity die casting
• Due to the low melting temperature and the usually high cost of electrical
energy, fuel-fired furnaces are therefore predominantly used for melting
aluminum alloys
• However, crucible furnaces are predestined for certain tasks in the aluminum
sector, e.g. for frequent alloy changes or for melting down small-sized
charge material and chips. Furthermore, crucible induction furnaces are
particularly suitable for the production of special alloys where good bath agitation
is required to introduce the alloying elements, or for melting down chips.
• The use of hydrogen for melting is possible, but presently under development

For a given task, the energy consumption for melting depends in particular on the
following factors:
• furnace design and plant layout.
• operating mode and.

30
• production organization.

As far as energy savings are concerned, any additional energy requirement

due to unfavorable operation and operating methods should therefore be
avoided as far as possible

Influence of bath temperature:

Increasing holding bath temperature leads
to 2 effects:

• Slightly higher ambient losses.

• A reduced heat transfer efficiency into the bath. However, the effect of
reduced heat transfer efficiency is minimal in this case, since the higher
temperature exhaust gasses are well utilized due to heat recovery.

• The alloy composition influences, among other things, the liquidus point and the
melting enthalpies.

31
• Depending on the alloy used, the required melting energy may therefore
vary

• Increase in heat of fusion for pure binary Al-Si alloys:

• 0% Si -> Δh = 100%
• 6% Si -> Δh = 105%
• 12% Si -> Δh = 110%

• The geometry of the charge material and its composition influence the
effectiveness of heat transfer.

• This influences the melting efficiency.

• Small charge material with a high surface-to-volume ratio is ideal for

optimum melting efficiency. However, the ratio should not be too low to obtain
a high metal yield.

Influence of batch material:

• The geometry of the charge material and its composition influence the
effectiveness of heat transfer.

• This influences the melting efficiency.

• Small charge material with a high surface-to-volume ratio is ideal for

optimum melting efficiency. However, the ratio should not be too low to
obtain a high metal yield.

Influence of furnace utilization:

• Energy efficiency depends very much on the furnace capacity utilization

• Operation management of particular importance for energy efficiency

• Resource savings through improved furnace operation

• The shaft filling level and the bulk density in the shaft are
• The higher the shaft filling level is, the better the shaft energy recovery is

• The lower the filling level, the more energy goes into waste heat, even if this
is used to preheat the ingots

32
• The continuity of the melting process plays an important role

• An interruption of the melting process leads to melting losses due to:

• A higher relative bath temperature holding consumption,

• Cooling of the shaft and the charge material, which must be reheated

• For optimum efficiency, the furnace is run at full load.

• Therefore, the furnace size should be well matched to the foundry

melting rate requirements.

Die casting most relevant production route for Al mold castings in

Germany

• Cold chamber die casting process. Materials: Al, Mg, Cu alloys

• Hot chamber die casting process. Materials: Zn, Mg, Pb, Sn alloys

33
Casting Cycle:
• Close the mold
• Dosing of the melt into the shot sleeve
• 1st Phase (pre-casting phase)
• 2nd Phase (Mold filling)
• 3rd Phase (Intensification)
• Open mold
• Eject Casting
• Spray the mold
• Close the mold

34
35
Melt preparation

Feed dried ingots to a central melting furnace. Pour the liquid AI melt into an exit
ladle. Clean the melt by means of an impeller or by feeding salts. Feed cleaned
melt to the metering furnace of the machine.

• Energy required to heat the crucible furnaces electrically is significantly lower

• Energy is directly induced in the molten material, no transmission losses
• Lower emission of pollutants

Influence of the furnace size

• The furnace size influences the total wall area and thus the ambient heat
loss
• Even if a larger furnace achieves better specific energy consumption per kg of
melt, the absolute energy consumption is higher
• Therefore, the furnace size should be chosen as small as possible from the
point of view of energy consumption, taking into account the required
production, temperature stability and charging cycles

36
Influence of melt bath temperature
• The higher the bath temperature, the more heat is dissipated to the
environment and the dosing gas

• Optimization of the furnace geometry and wall insulation can lead to an energy
reduction of ~10%.

• For optimum energy consumption, the bath temperature should be set as low
as possible, taking into account the melt cooling during the dosing process and
the temperature fluctuations of the batch melt.

Influence of the melt charging temperature

• Even if the bath temperature stability is very good, it can be negatively
influenced by the post-charging melt temperature

• A temperature deviation of the charge melt leads to a heating system reaction

in order to stabilize the bath temperature again

37
Die spraying unit
Since the aluminum and other molten metals would stick to the bare steel of
the inserts, a release agent is necessary.

Before the first casting, all surfaces that come into contact with molten metal
are coated with a special paste while the mold is preheated. The mold must
also be sprayed with a release agent before each casting operation.
Water-soluble release agents are commonly used, which are applied to the
mold by hand with a spray gun on smaller machines or for small batches.

Especially for larger machines, 2-axis sprayers are used. They move spray
heads with adjustable nozzles for release agent, water and air between the open
mold.

“Why spray at all”

Separating effect:

38
The release agent in the spray forms a thin film on the mold surface. This
prevents the castings from sticking

Lubricating effect:

Moving mold parts such as ejector pins and notchers are lubricated

Cooling effect:

Heat build-up and overheating in the die are prevented.

Mold cleaning:

Metal residues and flakes are washed or blown out of the mold.

39
Heat dissipation
Background

Removal of a large proportion of heat flow supplied by the melt via internal
cooling systems.

Release agent application only to achieve good demoldability and only in

exceptional cases mainly for cooling.

Low temperature fluctuations and thus low thermal cycling, especially of the
mold surface.

-> Advantage with low spray volumes or powdered release agents.

In practice, however, it may be necessary with complex geometries to also
actively cool the mold locally via spraying

Min 150°C for water-soluble release agents, since the water does not

40
evaporate completely below 150°C. Temperature control systems for the
molds are always required for heating and cooling with water or oil, for
maintaining the necessary temperatures and for measuring and monitoring

WHY TEMPER ???

• Increase the lifetime of the die casting mold
• Avoidance of stress cracks in the mold
• Shorter heating times
• Better quality of the parts
• More accurate dimensions
• constant reproducible quality
• clean surface
• uniform casting process
• Die casting of thin-walled parts

Error due to die temperature being too low

• Poor demoldability (increased shrinkage forces)

• Cold welding (material overlap)
• Incomplete mold filling
• Cold flow (pre-solidification)

Defects due to too high mold temperature

• Sticking of the casting material (insufficient spray film)

• Increased pore formation, due to excessive use of spraying agent

Preheating strategy Temperature control units Oil

Temperature control units with oil as heat transfer medium with a
possible temperature range from 60°C to 350°C
Advantage of oil unit:
Temperature range up to 350°C possible

Preheating strategy Temperature control units with water

Temperature control units with water as heat transfer medium with a possible
temperature range of 20°C to 160°C Advantage Water unit:
Due to the better heat transfer properties of water, a more efficient heat
exchange is possible

41
Ǭ = Aexchange * αFoWater * (Tcast – Twater)

42
Current: Utilization of process-related waste heat in
foundries
• Heating shop air
• Underfloor heating (for new buildings or conversions)
• Hot water for sanitary facilities
• Use in other foundry processes (e.g. annealing and drying furnaces)
• Use for drying raw materials and supplies
• e.g. scrap, chips, skives, molds, water-based paints
• Generate electrical energy
• (Power) heat-cooling cogeneration (cold generation for cooling processes)
• Steam generation (<2 kilometres economical)
• Storage of heat, e.g. in mobile thermal energy spokes
• Feeding into the district heating network
• External secondary use, e.g. in greenhouses, swimming pools or neighboring
companies

43
44
45
Conclusion: Die casting Aluminium

For the die casting process, the material and energy flows are complex
• In addition to providing the melt, energy is required at many other points,
such as:
• Operation of the die casting system
• Heating/cooling system for the die casting molds

• Due to the low energy level of the heat

generated in the process, it can only be
used further in operation to a very limited
extent, such as heating in winter or for hot
water.
• There are several possible solutions for
cleaning and using the exhaust air
• Overall, optimizations must be made in
detail at many points in the process in
order to minimize energy consumption
and the use of operating materials.

46
Melting area is by far the most energy-intensive division

47
48
• Large or small size of batch material

− the right mix influences the melting time up to 10 minutes and more ( >
100 kWh/t )

• Sandblasting of the return material

− If the return material is not sandblasted, it contains a lot of sand

adhesions (molding and
core sand)(often 10% of the return material is sand, which is brought into
the furnace).
− Additional 500 kWh/t, where the melted sand also forms additional slag
− For 10t feedstock with 5t return containing 10% sand, this is 250 kWh
additional needed to
melt the sand

49
50
51
Cupola Furnace: Melting cast iron in cupola
furnace
Introduction: Basic setup
• Shaft furnace for melting of ferrous alloys
• Batch materials are filled from the top:
− Steel scrap
− pig iron
− Return material
− Alloying additions
• coke
• Limestone (influencing the slag)
• Compressed combustion air (wind) is blown in from
below through the nozzles

52
Functionality

Heating of iron by coke (as well as hot blast)

and burning of other elements

∆HFe = (HC ∙ K + ∆HWind + ∆HAbbr.) ∙ ηges.

HC = Combustion heat of the coking coal

K = Carbon supply
ηges.= Overall efficiency

53
Material balance: throughput of the cupola furnace
Basic equation for the mass
balance of the cupola furnace
(without wind consumption for
exhaust gas and calcium carbide
addition):

54
Heat Balance: Cold Blast Cupola Furnace

30 % of the coke heat is used for melting the Iron.

57 % losses due to waste gas discharge

55
Heat balance: hot blast cupola furnace

• Generation of the hot blast by using the blast furnace gas heat to heat the
blast air to 400 to 600 °C

• Improvement in efficiency compared with cold blast cupola furnace

About 75% of the coke heat is used through secondary heat utilization

Heat of fusion: cupola vs. induction furnace

• Amount of heat required for melting in induction furnace lower than in

cupola furnace

• Theoretically app. 390 kWh are required for melting and heating up
cast iron to 1500 °C

56
57
58
Assembling a mold

Two piece mold with core

• Cores are inserted into the lower part of the mold

• upper and lower part of the mold are put together

• Transport to the casting equipment

Example clay bound sand

Raw materials

• New sand
• Regenerated used sand
• Bentonite
• Water
• Molding material additives (lustrous carbon, ...)
• Molding material cycle via recovery of the residual sand (processing)
• Separate core sand cycle, as cores are produced with other raw materials
(separate process)
• (regeneration)

Moulding material cycle of bentonite-bonded sand

• Used sand makes up the largest part of the "waste" produced in a foundry
despite the molding material cycle

• In Germany 460,000 t/year

• In the present example, 98% of the molding sand is reused (WESO-

Aurorahütte GmbH, 2017).

• Used sand can be used, for example, in road construction

59
60
Process steps of the molding material preparation

1. Casting sand separation

2. Removal of metal residues and lumps

3. Sieving and homogenization

4. Regeneration

− dry-mechanical: grinding off the sand particles with continuous dust

removal → Removal of binder shells and foreign particles from the sand
surface

− thermal-mechanical: burning of the binder components in rotary drum or

fluidized bed
furnaces at 700 - 800°C, subsequent mechanical post-treatment

61
5. Mixing of the different raw materials (new sand, used sand, bentonite,
water,
additives).

6. Homogenization of the mixture and adjustment of the properties.

Sand casting consists of a large number of process steps.

• In general, both clay-bonded sands and synthetic resin sands can be

recycled. Clay-bonded sands are always recirculated, synthetic resin sands
only partially.

• However, the demand for raw materials interacts with the demand for
energy.

More recycling means more energy.

• In the future, the focus will be on process optimization and the use of
regeneratively generated energy.

62
IME

I Intro and Basics:

Atomic Weight of Al: 13

Al is not found in pure form, which explains its late discovery.

Al is much less sensitive to oxygen and humidity than iron. The

corrosion resistance of Aluminum is based on a hard and extremely dense
oxide layer that is few molecules thick, which forms on freshly etched.

Hard and extremely dense oxide layer that is few molecules thick forms on
freshly etched Aluminum in air and water after only a few seconds. This
protective layer can be strengthened by electrochemical means (anodizing
process). Aluminum has no proven toxic effect on the human organism.

low density of Aluminum alloys (2.6 - 2.8 g/cm³). Frequently used in

Aerospace industry. Also leads to considerable fuel savings in Automobiles.

Low tensile strength of Aluminum can be significantly increased by adding

suitable alloying elements. Due to its comparatively low melting point, it
can only be used at high temperatures to a limited extent; its high thermal
conductivity nevertheless allows it to be used in engine construction,
especially with the use of ceramic or cast iron inlays.

Has high thermal conductivity (3x steel), therefore used in engine

construction.
Also has high electrical conductivity (two times higher than the same
weight of Cu)

Aluminum chips or powder are used as a deoxidizing agent in steel

production because Aluminum has a higher affinity to oxygen than iron

Has excellent forming properties. Used in all known casting pro-

cesses, although the melting point of the cast alloys is usually less than
630 °C

63
II Process chain of primary Aluminum production

Primary Aluminum is produced in a two-step process starting from

bauxite.

First step: Production of alumina (Aluminum oxide) from bauxite.

Second step: Production of primary Aluminum from alumina, usually at a

different site from the one where the first step is carried out; mainly for
logistical reasons and because of the availability of electricity.

***Primary Aluminum production is carried out exclusively by combining

a preceding refining of the raw material (separation of impurities) with a
subsequent reduction to metallic Aluminum in a fused-salt electrolysis. This
is because Aluminum is a very ignoble metal compared to other metals

The raw material for primary extraction is bauxite. Although

a simple process, Aluminum extraction from primary raw materials is more
energy-intensive than that of iron or copper because of the required
fused-salt Electrolysis

As a basic rule, the production of 1 t Al requires about twice the amount

of Al2O3 (2 t), corresponding to 4 t of bauxite. In reality, this factor
essentially depends on the quality of the bauxite and the efficiencies of the
processes. One reason for the high differences in worldwide production is
the use of lower-quality bauxite worldwide.

64
II a) Bauxite mining, transport and processing

Bauxite composition:

Aluminum hydroxides (Hydrargillite (-Al(OH)3), Boehmite (-AlOOH),

Diaspore (-AlOOH)), Aluminum oxides (Corundum (-Al2O3)), iron and
titanium oxides as well as silica. The chemical and mineralogical
composition as well as the physical properties of bauxite from different
deposits vary considerably.

65
Bauxite ores usually found near the surface in layers six to eight meters
thick, which are mined in open pits. Bauxite gets its rust-red color from the
iron present in the ore. European Bauxites are difficult to access and are
rarely mined.

Mining:

1. Before the actual valuable mineral extraction, the overlying surface

must be removed. To prepare the surface, the first step is clearing,
e.g. removing vegetation and, if necessary, loosening the surface
layer.

2. Next come processes of valuable mineral extraction and dumping

(depositing overburden around or on top of the surface mine) can be
carried out using continuous or discontinuous techniques (mostly
preferred).

3. For subsequent use, there is a need to create a planned post-mining

landscape. These include restoration of the original condition before
mining activity, another subsequent use such as agriculture is also
conceivable. The overburden layers that can be cultivated are
used for recultivation, the remaining overburden layers are
transported for dumping.

4. The valuable mineral is transported to the customer via transport

means.

5. In open pit bauxite, discontinuous conveyors such as haul trucks

dominate. Belt conveyors are used rather rarely. Integrated
generators can be used when transporting material from a higher to
a lower altitude level. The sub-processes of dewatering and periodic
work such as road construction or dust control are integrative
components of the mining process.

6. Even if the thick- ness of the overburden is the same, different ore deposits
have an impact on the amount of energy required for mining. For example,
the expenditure for removing the surface layers of the Venezuelan deposit
with seam-like bauxite is only about one third of that for the pocket-shaped
bauxite in Jamaica.

66
 Transportation

The choice of means of transport (ship, freight train, truck or conveyor belt)
depends first of all on the given infrastructure, then on the nature and
quantity of the goods to be transported and finally on economic and legal
constraints.

Mining: Further details

Objectives of the various process steps in bauxite processing are to separate
the iron content and other impurities from bauxite and to dissolve the
Aluminum hydroxide content as selectively as possible.

Mined bauxite hardly needs to be concentrated any further and is first

crushed to grain sizes of 20 - 50 mm. For this purpose, hammer or jaw
crushers are used first for pre-crushing, and ball or rod mills are used
afterwards to adjust the final grain sizes. The grain size spectrum achieved
has an influence on the digestibility of the bauxite, the settling behavior of
the red mud and the erosion of the process unit components. Overgrinding
should be avoided, on the one hand to keep the energy input low, and on the
other hand to prevent existing quartz from being ground so small that it can
dissolve in the leach. In many cases, washing follows, in order to remove the
kaolinite (Al4((OH)8|Si4O10)) that is finely distributed in the bauxite.

In addition to plant size, transport and energy costs, the decisive factors for the
profitability of a factory are personnel costs including social costs,
infrastructure and labor costs.

In the oxide factory, the bauxite is wet ground with part of the circulating
caustic soda intended for digestion. The required fineness depends on the
dissolving properties of the bauxite. The finely ground suspension is stored in
storage tanks. These are usually used at the same time for pre-desilication, in
which particularly silica-rich bauxites are subjected to SiO2 separation before
digestion.

Desilication

67
As the silica content in the bauxite increases, the maximum Aluminum
oxide yield decreases and the demand for caustic soda increases. Both are
disadvantageous for the economic process of the following digestion (Bayer
process). Silica-containing bauxites, together with red mud particles, form
crusts on the heating surfaces of the heat exchangers of autoclaves or
tubular reactors. The operating times of the reactors can be doubled in some
cases by pre- silica removal.

The bauxite mash is heated directly with exhaust steam in containers and stirred
for 6 to 10 hours. During this time, the silicic acid dissolves in the form of
sodium Aluminum silicate; the SiO2 content of the caustic soda increases. After
reaching the maximum saturation, silicate precipitates, so that reaching the
SiO2 content in the solution de- creases again. The silicate is insoluble in the
further course of the process and is dis- charged with the red mud. In this way,
the incrustation within the digestion aggregates can be reduced. This step is not
necessary for the process, but increases the service life of the reactors.

The rate of pre-desilication increases with increasing temperature, increasing

bauxite content and increasing dilution of the caustic soda. In practice, final
contents of up to 0.25 g/l SiO2 are achieved, depending on the type of bauxite.
The chemical process of desilication consists of two main reactions:

[Al2O3∙2SiO2∙2H2O](s) + 6 NaOH → 2 Na2SiO3 + 2 NaAlO2 + 5 H2O (1)

Na2SiO3 + NaAlO2 + H2O → 1 [Na2O∙Al2O3∙2SiO2](s) + 2 NaOH (2)

With the separation of silicon oxide (SiO2), Aluminum oxide (Al2O3) and
sodium hy- dioxide solution (NaOH) are also consumed in the
pre-desilication process. Bauxite types with a silica content of more than 6 to 8 %
are usually not processed due to the associated high losses of Aluminum oxide
and sodium hydroxide.

Bayer Process

68
In the digestion process, the ground and possibly pre-desilicified bauxite is
dissolved in hot sodium hydroxide solution (NaOH) with the addition of
lime (CaO) with the aim of dissolving the Aluminum contained in the form of
Aluminum hydroxide. The main reactions of the bauxite are given in equations
(3), (4) and (5).

Al2O3 (bauxite)+3H2O→2 Al(OH)3 (3)

(4) Total: Bauxite (Al2O3, Fe2O3)+ 2NaOH+3𝐻2O→ 2Na[Al(OH)4]+Fe2O3 (5)

The working conditions in bauxite digestion can be described by the

process variables: reaction temperature, NaOH leach concentration, mol ratio
and solubility of Al2O3. The rate of digestion is influenced in particular by:

Al(OH)3(bauxite)+Na OH →Na[Al(OH)4]

● the bauxite type;

● the particle size spectrum;

69
 ● the digestion temperature;
● the residence time of the caustic soda at the digestion temperature;
● the surface condition of the bauxite;
● the concentration of sodium hydroxide;
● the concentration of Al2O3 in the caustic soda; and
● the stirring speed in the autoclave, i.e. the turbulence.

In addition to the Aluminum being recovered, the bauxite also contains

accompanying elements and impurities that can either accumulate in the caustic
soda or be produced as solids (see Table 4), so that the caustic soda that is
circulated must be cleaned of both the dissolved and the solid impurities.
The removal of the dissolved accompanying elements takes place in a
separate caustic soda purification, so that a large part of these elements can
be recovered. The solid residue, on the other hand, must be separated from the
caustic soda and deposited. This residue has a red color because of the iron
content and is called red mud. The accumulation of large quantities of red
mud to be deposited is a major problem in bauxite processing.

Types of Bauxite Processing:

High-temperature and low-temperature processes with regard to the digestion

temperature. The Aluminum mineral gibbsite in bauxite requires digestion
temperatures of 110 - 150 °C, while the minerals boehmite and diaspore require
higher temperatures of 180 - 280 °C.

When processing diaspore, the addition of lime lowers the required

temperature to about 240 °C. This reduces the energy consumption and
influences the energy expenditure and energy loss in the autoclave.
low-temperature digestion for leaching gibbsite to high-temperature digestion for
leaching gibbsite and boehmite, the amount of leach decreases, but at the
same time the digestion temperature increases.

Both processes are almost exclusively carried out continuously in autoclave

cascades. Indirect heating was used in older alumina plants; the resulting
encrustation problems on heat exchanger surfaces are now circumvented
by direct introduction of heating steam into the autoclaves. The
disadvantage of this form of heating is that the condensate has to be removed
by evaporation, which requires additional energy. In addition, the caustic soda is
further diluted, which makes the dissolving process more difficult. With regard to
the caustic soda flow, the single-stream process, in which the entire

70
bauxite-caustic soda suspension is pumped through all the autoclaves, is
distinguished from the two-stream process, in which 80 - 85 % of the
caustic soda is preheated and compressed separately with heat recovery before
being combined with the rest of the caustic soda and the bauxite in one of the
last autoclaves. The advantage of less costly pumping for liquids compared to
suspensions is offset by increased material requirements based on greater
risk of corrosion due to the higher caustic soda concentration.

Tube reactor
in which the autoclave cascade is replaced by a tube. The main advantages
over the autoclave process are the increased turbulence and
temperature. The resulting almost ideal mass transfer and significantly
higher reaction rates lead to considerably shorter retention times. This also
reduces the specific plant volume of the tubular reactor by a factor of 5
compared to an autoclave cascade, which lowers the investment costs in terms
of space requirements accordingly. The high achievable process temperatures
allow such low digestion concentrations that no dilution of the caustic soda is
required for the preparation downstream of the tubular reactor. Consequently the
subsequent evaporation for regeneration of the sodium hydroxide solution
is not necessary. In addition, the specific amount of caustic soda required is
reduced from 13 - 17 m3/t(Al2O3) to 10 m3/t(Al2O3). Both effects are expressed in
a reduced energy requirement.

In the case of indirect heating during the digestion process, molten salt is
also available as an alternative to process steam as a heating medium in the
tubular reactor. Even with complete utilization of the condensation heat, which is
practically not achieved with steam heating, the heat exchanger efficiency of
salt heating at 85 - 90 % is significantly higher than that of steam heating at
60 - 70 %. This results in smaller heat exchanger dimensions required for the
salt medium, which in turn leads to reduced heat radiation losses of only 1
% compared to 5 % with steam heating.

In general, a temperature increase of 10 K improves the reaction rate by a

factor of 2.5. To achieve the higher process temperatures, higher operating
pressures are set to suppress boiling of the aqueous sodium hydroxide
solution. However, since the pressure itself has no direct effect on the bauxite
digestion.

Tube reactor digestion/ Piston Diaphragm Pumps

The bauxite suspension, which is relatively thin with the caustic soda
concentration of only 140 g Na2O/l used, is pumped into the reaction tube with

71
piston diaphragm pumps under a pressure of about 80 bar. Only the
invention of this type of pump, which uses a membrane to prevent the
suspension from coming into contact with the moving parts of the pumps,
made it possible to operate continuous reactors. The piston diaphragm pump is
the only moving part of the system. It ensures turbulent flow, favorable heat
exchange, high reaction rates and prevents back mixing.

In these flashers, the suspension boils up due to the pressure drop and high-
pressure steam ("vapor") is produced, which serves as a heating medium in the
middle section of the reactor. In the high-temperature section of the reactor, the
reaction temperature is reached by adding superheated steam. The suspension
leaves the digestion unit for red sludge separation.

Autoclave digestion/ Cascades, Al2O3 precipitation

For bauxite digestion in autoclaves, several autoclaves are connected in series.
Autoclave cascades have a number of shortcomings due to their
moving parts. They are increasingly prone to malfunction, incrustations and
costly process control. In addition, the autoclave cascade has poorer
residence time behavior than the tube reactor, i.e. parts of the reaction mixture
either leave the reactor before or beyond the average retention time. In the first
case, the digestion is incomplete, in the second case, volume is used
beyond the necessary time. Also, much higher turbulence in the tube reactor,
which also improves the solution behavior.

The tube reactor, on the other hand, where the residence time is about 5
minutes, requires only 0.1 m3/t(Al2O3).day. This makes the tube reactor,
although it only has a significantly smaller volume, much more efficient
than an autoclave cascade.

The (calculated) Al2O3 content is used as a parameter and comparative value in

order to have a constant reference value over the course of the entire Bayer
process. With a higher Al2O3 concentration after digestion precipitation of
Al2O3 is unavoidable, so that incrustations are a central issue in alumina
production.

Precipitation crystallization of Aluminum hydroxide

72
During crystallization, the precipitation of Aluminum hydroxide is achieved by
lowering the temperature and diluting the caustic soda. This shifts the chemical
equilibrium from the left-hand side of the leaching equation 6) back to the
right-hand side. [16]

The Aluminum hydroxide is present in the clarified solution, which is strongly

supersaturated by cooling from 90 to 55 - 75 °C, whereby Aluminum hydroxide is
dissolved in the caustic soda in the metastable range. The precipitation of
Al(OH)3 is chemically a hydrolysis.

[Al(OH)4] <--> Al(OH)3 + OH-

The precipitation crystallization takes place in stirred tanks in which the

settling of the Al(OH)3 is prevented by appropriate turbulence in order to
enable the discharge of the produced Al(OH)3 without clogging the reactor and
at the same time to be able to offer a maximum crystallization surface.
Stirring-out takes place in tanks with a capacity of 2,000 to 4,500 m3. Despite the
oversaturation in the metastable phase, the hydroxide precipitates only slowly.
To achieve a sufficient precipitation rate, solid Aluminum hydroxide is
used. An addition of 200 - 400 % hydroxide is made, i.e. 60 – 80 % of the
produced material is circulated (Figure 25). The effectiveness of the inoculation is
due to the active surface of the Aluminum hydroxide, which acts as a nucleating
agent. The hydroxide always precipitates from the alkali in the form of
hydrargillite.

The stirred-out Aluminum hydroxide is separated on drum filters (or

comparable filters such as plate filters or disc filters) and washed several
times (see Figure 27) in order to reduce the adhering alkalis to values of less
than 0.01 % as far as possible. These would destroy the lining of the calciner in
the subsequent calcination (separation of hydrate water for Al2O3 extraction, see
below) and deteriorate the quality of the Aluminum oxide. The Bayer process
is a closed-loop process in which sodium hydroxide is constantly
loaded and unloaded with Aluminum.

73
Overview of the Bayer process and possible sources of
loss in the system
In principle, on the one hand the raw material quality and on the other hand the
process technology used determine the amount of energy required for alumina
production. Theoretically, the enthalpy change for the overall reaction of the
Bayer process (without calcination) is low when using both hydrargillitic and
boehmitic bauxites. The process is even slightly exothermic, since the heat
deriving from the solution for the extraction is smaller than the generated heat
because of the crystallization of the hydroxide that has to be deducted
during stirring-out. The high energy input thus corresponds to the heat
losses in the overall process.

74
Energy losses through radiation and convection
insulation is practically impossible from a plant engineering point of view. The
values of energy losses are noticeably dependent on the climatic location of
the oxide plant. For example, the values for red mud separation in a European
alumina plant are 1,045 MJ/t Al2O3. In the tropics, this value is lower under
otherwise identical conditions, while it is higher in Canada or northern
Russia. In addition to the ambient temperatures, the wind speeds at the plant
components strongly influence the agitator. The real fluctuation of the heat
loss at the outer wall of the tank is attenuated by incrustations inside the
mixing tanks.

Heat loss through material discharge

The energy content of the outgoing material flows has a significant
influence on the total energy consumption. These material flows include the
red mud, the Aluminum oxide, the steam and the waste gas produced in the
calcination process. Thus, the goal of red mud washing is to discharge the
solids with as little adhering caustic as possible in order to remove as little
caustic soda as possible from the overall system. The amount of heat
discharged with the red mud is significantly influenced by the liquid
content. In fluidized bed calcination, the heat losses of the exiting waste gases,
the separated and evaporated water and the Aluminum oxide could already be
reduced by heat recovery. This is achieved by transferring the thermal energy
of the Aluminum oxide to the incoming combustion air and the preheating
and partial dehydration of the Aluminum hydroxide by the hot exhaust gases
from the calcining furnace.

Caustic soda circuit

Due to a change in the type or quality of the bauxite, it is often necessary to
increase the decomposition temperature. In this case, additional
stress-relieving stages and heat exchangers are necessary, but these are
often not available and thus lead to increased energy loss.

The yield of the process also has a significant influence on the

amount of specific energy required for digestion, as the specific mass of
the suspension to be reacted in- creases with increasing losses and thus also the
energy required for heating. In turn, valuable mineral losses are caused by too

75
low digestion temperatures or sodium hydroxide concentrations, at which
poorly soluble minerals (such as diaspore) do not dissolve and instead remain
in the red mud to be separated. Furthermore, already dissolved alumina that
crystallizes in the solution before the red mud separation is lost with the
red mud, as well as alumina that was not dissolved due to insufficient resi-
dence times in the autoclave and/or an insufficient degree of grinding. On the
other hand, too much fineness of grinding of bauxites with silica present in
quartz form leads to losses of sodium hydroxide and alumina due to the
reaction to sodalite. Reactive silica e.g. kaolinite (Al2O3 ∙ 2SiO2 ∙ 2H2O) is
soluble in sodium hydroxide solution and forms poorly soluble sodium silicates
such as hydroxysodalite (4Na2O ∙ 3Al2O3 ∙ 6SiO2 ∙ H2O), which contain Aluminum
oxide and sodium hydroxide solution in addition to silicon oxide. Average losses
are 2 t Al2O3 and 1.2 t sodium hydroxide per ton of SiO2, which is why bauxites
with reactive silica contents of more than 6-8 % are not usually processed.

Low concentrated by-elements such as chromium, vanadium,

zinc and gallium have no effect on the product quality of the
Bayer process. However, vanadium and gallium accumulate in the recycled
sodium hydroxide solution and must therefore be removed regularly.

Calcination of the Al-hydroxide to Al-oxide

The Al hydroxide obtained in the Bayer process still has a residual

moisture of 6 to 16 % and also contains water in hydrate groups. In this
form, it cannot be used in electrolysis, as the water introduced there
leads primarily to the increased formation of HF gas and therefore only
pure oxide may be used. For the separation of water and the conversion
into Aluminum oxide, the filter-moist hydroxide is therefore calcined at 1000
to 1300 °C:

2 Al(OH)3 + x H2O → Al2O3 + (2+x) H2O (8)

Two units are used for calcination today, the older rotary kiln and the
newer fluidized bed kiln. The rotary kilns consist of a refractory-lined,
inclined tube that rotates around its longitudinal axis. The hydroxide
charged at the upper end slowly moves to the lower end of the kiln
due to the inclination and rotation and is calcined in the process.

The Rotary kilns or fluidized bed furnaces are currently used for
calcination. In optimized plants, the high product temperature of 1200
°C is used for air preheating by means of recuperators. This reduces
the energy requirement from 5800 to 3500 MJ/t alumina. Better heat

76
utilization can be achieved with fluidized bed technology, which
reduces the thermal energy demand to up to 3000 MJ/t Al2O3. This
means that the heat utilization is more than 80 %, so that

Calcination in the rotary kiln is relatively uneconomical for several

reasons:

● comparatively low output of the ovens;

● high thermal load on the masonry;
● high maintenance and servicing costs;
● high space requirement;
● contamination of the product by SiO2 from the lining; and
● dust generation due to the fine-grained nature of the feed material
and the exhaust gas flowing in the opposite direction.

The energy consumption of the fluidized bed furnace is significantly lower

than that of the rotary kilns, even though their energy consumption has
been significantly reduced by the installation of heat exchangers.

Energy and material balance of alumina extraction

The calcined alumina is dry and in powder form. It has a purity of over
99 % and can be used directly for Aluminum reduction in electrolysis.
However, due to the high purity of this product, it is also used for
other purposes, such as gemstone synthesis, as an abrasive, in the
chemical industry or for the production of refractory material. It has a
density of 3.98 g/cm3 and a melting point of 2,053 °C.

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IME PAST EXAM THEORY QUESTIONS
A. There are a few reasons why silica must be removed before the Bayer Process

in alumina production, except: (1.0 P)

☐ To avoid incrustation in the subsequent digestion reactor.

☐ To avoid high temperature demand.

☐ To avoid the increase of caustic soda demand.

B. Which is the correct sequence of treatments that red mud is subjected before

being disposed of in landfills? (1.0 P)

☐ Dilution with weak leach flocculation in clarifying thickeners filtration

with wash water.

☐ Dilution with strong leach filtration with wash water flocculation in

clarifying thickeners.

☐ Dilution with weak leach filtration with wash water flocculation in

clarifying thickeners.

C. Which of the following statements about aluminium recycling is true? (1.0 P)

☐ Aluminium recycling saves 80% of the energy compared to the primary

process

☐ Aluminium products can be processed into recycled aluminium with only 15%

of the energy required for primary production.

☐ Aluminium can be remelted multiple times without any loss of properties if the

same quality can be achieved.

78
D. What are the consequences of the presence of organic components, such as

painted packaging material or chips containing oil, in the aluminium recycling?

(1.0 P)

☐ Increased efficiency of the recycling process and reduction quality of the

aluminium melt.

☐ Reduction in the efficiency of the recycling process and enhanced quality of

the aluminium melt.

☐ Reduction in the efficiency of the recycling process and reduction quality of

the aluminium melt.

E. Which of the following assumptions are made for the simplified energetic

balance of an electrolysis cell? (1.0 P)

☐ Neglect the heat loss distribution.

☐ Constant temperature in the electrolyte and aluminium.

☐ Variable anode life, cooling water temperature, and bath level.

Fill in the flowchart below with the correct bauxite digestion inputs and outputs in

terms of mass balance.

79
Clockwise: Bauxite, Red Mud, Alumina, NaOH

1.1. Order all the processes of aluminium production in terms of energy consumption

from the lowest to the highest.

(1) Bauxite mining and processing

(2) Bayer-process and calcination

(3) Casting

(4) Electrolysis

The energy consumption of an electrolysis cell consists of several components.

Name the two most energy consuming ones.

3.2. What would you do to decrease the direct and indirect CO2-footprint of an
electrolysis? Please name one solution each for direct and indirect footprint.

Direct: Adoption of Inert Anode

Indirect: Carbon Capturing

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How could a company use the energy stored in the organics containing scraps?

Please show how you can recover the energy and where you can use it.

4.4. Which advantages does a vortex smelter have in comparison to normal inserting

techniques? Name two.

A melting cyclone has been developed in order to take up fine particles via a
tangentially introduced melt flow. This prevents freezing of the bath surface and
enables optimum melting of the scrap and easy charging into the furnace. The
melting cyclone works in the same way as aero- or hydrocyclones: The tangential
introduction of the melt stream causes a rotation inside the reactor. As the diameter of
the reactor decreases, the velocity of the introduced melt increases downward. A
turbulent vortex is created on the surface, which picks up incoming scrap and melts it
downward in the downstream flow

Name a pyrometallurgical unit in which it is possible to melt red mud and carry

out slag treatment.

Q State and explain whether the pH of red mud is basic, neutral, or acidic.

Basic. the pH of red mud at the landfill is initially about 11.5, drops to 10.5 after
five years of storage, and reaches a value of 9.5 after another five years. It should
be mentioned here that the pH is a logarithmic relationship of concentration

Q The recovery of iron from red mud is possible through sintering and smelting
metallurgy. Which is the method used to recovery iron pyrometallurgically? Write one
possible chemical equation in which this method is based.

In carbothermic reduction, the reduction (electron absorption and thus reduction

of the

81
oxidation number) of a chemical element takes place by the addition of carbon,
which

is itself oxidized in the process (gives up its electrons and increases its oxidation num-

ber). Consequently, a redox reaction takes place, and depending on the temperature
and metal, metal carbides can also be formed:

xMeOy+ zC→(x-w)Me + wMeC(z-x∙y) + (x∙y)CO

MeOx + xCO→Me + xCO2

Q Briefly describe the processes pyrolysis and thermolysis (process objective and
temperature range). What is the main difference between these processes?

Pyrolysis is a process for the thermal decomposition of long-chain and

networked hydrocarbons at high temperatures of 500 to 800 °C in the absence of
oxygen and/or in an inert gas atmosphere. This is a feedstock recycling process in
which materials are destroyed and macromolecules are broken down. These
macromolecules, mostly organic compounds, are unstable at high temperatures and
break down into fission products. This is also called depolymerization or cracking.
The absence of oxygen prevents undesired oxidation (combustion) of the
feedstock. The goal is to obtain, on the one hand, a hydrogen-rich volatile
product in the form of waste gas or pyrolysis oil and, on the other hand, a solid
and usually carbon-rich residue. The advantage of pyrolysis over combustion is that
the feedstock can be qualitatively reused for the most part.

Combustion always takes place under stoichiometric or super stoichiometric conditions

(λ ≥ 1). In this process, all combustible components of a fuel are converted into
combustion products of the highest oxidation state and energy is released in the form of
heat. In complete combustion, the polymers are completely converted to water and
carbon dioxide, so that the following general equation (6) can be derived:

CxHy + nO2 → y

2 H2O + x CO2 (6)

If the reaction conditions are not precisely maintained, incomplete combustion occurs,
also known as thermolysis. The air number is between zero and one. Unsaturated
hydrocarbons and CO are formed as additional products. Taking into account the
Boudouard reaction, the remaining carbon particles can react with carbon dioxide to
form carbon monoxide according to equation (7):

C + CO2 ↔ 2 CO (7)

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The equilibrium of the reaction shifts to the product side with increasing temperatures.

By reducing the system pressure, the Boudouard reaction also takes place at lower
temperatures. At an atmospheric pressure of 1 bar, the equilibrium at
temperatures above 1000 °C is completely on the product side (CO side)

Q If an inert anode would be used instead of graphite, name three requirements

that this material should have to produce aluminium through an electrolysis

Process. (3/31)

In addition to the anode design, new cell designs are also possible which are not based
on the previous design. Therefore, geometries with a high surface area are aimed at
for inert anodes, so that no complete wetting of the anode can occur due to the gas
formation and the probability of the anode effect is reduced. Likewise, the current in-
tensity can be increased due to the larger surface area without changing the specific
current density.

It follows that with a higher current more aluminum can be produced per anode/cell.
Another alternative is the wetted cathode, which offers potential for improvement for
both inert and carbon-based electrolysis. In this variant, the cathode is provided with a
nitrogen-containing coating so that aluminum remains as a thin film on the layer. This
ensures electrical contact even at low metal bath heights and reduces the
anode-cathode distance.

Note: (4/20) means Skript 4 / Page 20

Consequence of Organic Components in Aluminum recycling (4/35)

Organic components are increasingly being introduced into the aluminum recycling
loop. The reason for this is the processing of painted packaging material or chips
containing oil. The consequences of recycling such secondary materials are a
reduction in the efficiency of the recycling process and the quality of the
aluminum melt. The organic components contained in the feedstock lead to aluminum
carbide formation and increased dross formation due to a reaction between liquid
aluminum and the carbon contained in the organic material. In consideration of the
described disadvantages, the necessity of a thermal treatment for the removal of the
organic coatings before the actual melting process becomes apparent.

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Such a process takes place during scrap preheating in the preheating shaft of a
hearth furnace or on the bridge of the scrap chamber of a two-chamber furnace
(see chapter 1.2.3.2). Here, in the case of aluminum beverage cans, the charged
material is present as scrap bales in an atmosphere with low oxygen content (<< 1 vol.
%). In this case, pyrolysis is the predominant decomposition mechanism of the adhering
organics. However, a significant variation in oxygen content may occur during charging
of the scrap in the preheating section of the furnaces, allowing combustion or
gasification to occur

Tube reactor vs Autoclave (4/27-29)

Autoclave plants, which are usually designed for average residence times of 3 to 5
hours, require a specific plant volume of about 2 m³/t(Al2O3).day. The tube reactor, on
the other hand, where the residence time is about 5 minutes, requires only 0.1
m³/t(Al2O3).day. This makes the tube reactor, although it only has a significantly smaller
volume, much more efficient than an autoclave cascade.
Volume of tube reactor can be optimally used for bauxite digestion and a very
homogeneous solution is produced. Furthermore, there is much higher turbulence in the
tube reactor, which also improves the solution behavior.
Why we remove silica before Bayer’s process (pre-desilication) (1/18)
The silicate is insoluble in the further course of the process and is discharged with the
red mud. In this way, the incrustation within the digestion aggregates can be
reduced. This step is not necessary for the process, but increases the service life
of the reactors
Pyrometallurgical unit in which it is possible to melt red mud and carry
out slag treatment (1/38)
Red mud treatment before going to landfill (2/4)
Diluted with weak leach from countercurrent washing -> Flocculation with clarifying
thickeners -> Filtration with wash water

Method to recover Iron Pyrometallurgy (2/26)

Name 3 metals found inside red mud and processes are used to
extract (2/18)
Red mud contains valuable metals, such as iron and aluminum, sometimes titanium
and rare earth elements (REE). Extraction may be economical in some circumstances
where some countries do not have their own deposits of iron ore, ilmenite (TiO2) or

84
REE. However, the latter two components are mentioned only for completeness. After
the separation of iron, a mineral residue is formed, which can serve as a source of
titanium with more than 20 wt.% TiO2. Titanium is then obtained classically by leaching
with sulfuric acid or by direct chlorination. Similarly, the Orbite process can be used to
separate red mud into its components by careful digestion in hydrochloric acid
and subsequent solvent extraction, so that products ranging from high-purity iron and
aluminum hydroxide to rare earths can be obtained

Interaction when unpyrolysed aluminium packages are added to the

molten aluminium bath
Interactions of pyrolytic gases and oxygen within the aluminum melt occur during the
immersion of incompletely pyrolysed aluminum packages, in whose interstices air is
enclosed. Due to a high reaction surface of these gases, the gas-liquid reactions that
take place have a strong influence on dross formation.

Why electrolyte should not come in direct contact with ceramic

refractory? (3/7)
The aggressive electrolyte consisting of Na-Al-Ca fluorides (main component cryolite
Na3AlF6) is kept in a so-called "freeze lining" via sufficient cooling on the side walls. This
consists of a solidified edge layer of the species' own material, in this case the
electrolyte. This circumstance is used specifically so that the insulation ceramic is not in
direct contact with the liquid electrolyte. Without such an edge layer, the electrolyte
would dissolve the ceramic. Furthermore, fluorides in the form of HF or CxF
compounds are emitted from the electrolyte into the exhaust gas. Due to the
possible fluorine emissions, post-cleaning of the exhaust gas is indispensable

Electrolysis cell (3/8)

the carbon lining of the electrolytic cell must be completely renewed about every
2,000 operating days (5.5 years). The reason for this is the erosion of the carbon
cathode due to permanent contact with the molten aluminum.
Cryolite (Na3AlF6) is used as the (molten) electrolyte because it has a high ionic
conductivity and solubility for aluminum oxide. Electrolysis is operated at a
temperature between 950 - 990 °C, excess of AlF3 of up to 10% is used to lower the
liquidus temperature
Electrolyte additive requirements (3/12):

85
• Reduction of the density of the electrolyte to ensure better separation from the
liquid metal
• Lowering the solubility for metallic aluminum to reduce the likelihood of a reverse
reaction of the aluminum with the melt
• Lowering the melting temperature to reduce energy consumption
• Reducing the solubility of alumina as little as possible, otherwise the working
range would be restricted
• Increase of the conductivity of the melt to minimize the loss due to the electrical
resistance of the melt
• Reduction of the vapor pressure of the melt in order to reduce the formation of
gaseous substances and the discharge of material via the gas phase
Energy balance in electrolysis cell (3/24)
Assumption
• Constant anode life, cooling water temperature, bath level
• No consumption of the electrolyte
• Neglect of the anode effect and transient reactions
• Complete conversion of Al2O3 and anode carbon
• A period without starting and shutting down the cell is selected
• Constant temperature in the electrolyte and aluminum
• Linear temperature curve in the anode
• Heat loss distribution according to Figure 17
• Constant heat capacity

86