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Ceramics and Polymers

CERAMICS

INTRODUCTION

What are Ceramics?

Ceramics are refractory , polycrystalline compounds , usually inorganic, including silicates, metallic oxides, carbides and various refractory hydrides, sulfides , and selenides.(2 marks)

What are the advantages of using Ceramics in dentistry?

Ceramics have been used in dentistry for dental crowns owing to their inertness to the body fluids , high compressive strength and good aesthetic appearance.

Good biocompatibilty and ease of fabrication.

Carbons have found use as implants especially for blood interfacing applications such as heart valves. Due to their high specific strength as fibers and their biocompatibility.

Ceramics are also being used as reinforcing components of composite implant materials and for tensile loading applications such as artificial tendon and ligaments

Desired Properties of Implantable

Bioceramics

1.

Should be nontoxic.

2.

Should be noncarcinogenic.

3.

Should be nonallergic.

4.

Should be noninflammatory.

5.

Should be biocompatible.

6.

Should be biofunctional for its lifetime in the

host.

Ceramics and its classification

How the difference in structures exist?

Ceramics are classified according to their structural compounds of which AmXn is an example. A,X are metals and non metals respectively.

The difference between these structures is due to

relative size of ions (min. radius ratio). If positive and

negative ions are about the same size the structure become a simple cubic.

Face centred cubic structure arises when relative sizes

of ions are different since positive ions can be fitted in

the tetragonal or octagonal spaces created among larger negative ions.

PROPERTIES OF CERAMICS

What are the properties of ceramics?

Unlike metals and polymers ,Ceramics are

difficult to shear plastically due to ionic nature of bonding.

In order to shear , the planes of atoms should

slip past each other. However , for ceramics

materials the ions of like electric charge repel

each other , moving the plane of atoms is thus

difficult. This makes the ceramics non ductile and creep at room temperature is almost zero.

PROPERTIES OF CERAMICS

Ceramics are also sensitive to cracks / notches

since instead of undergoing plastic

deformation they will fracture elastically once the crack propagates.

If the ceramics are flawless they are strong even in tension.

Glass fibers have tensile strength twice that of a high strength stainless steel.

CLASSES OF CERAMICS

The types of ceramic materials used in biomedical applications may

be divided into three classes according to their chemical reactivity

with the environment:

completely resorbable (Bio Resorbable)

surface reactive(Bio Active)

nearly inert (Bio Inert)

THREE CLASSES OF CERAMICS (according to their reactivity)

completely resorbable

More reactive (Calcium phosphate) over a span of times

Yielding mineralized bone growing from the implant surface

surface reactive

Bioglass ceramics ; Intermediate behavior

Soft tissues/cell membranes

nearly inert

Less reactive (alumina/carbons) even after thousands of hours

how minimal interfacial bonds with living tissues.

Resorbable Ceramics

Resorbable Ceramics (first resorbable implant material-Plaster of Paris).

Should not have variable resorption rates

Should not have poor mechanical properties.

rates • Should not have poor mechanical properties. Two types of orthophosphoric acid salt namely 
rates • Should not have poor mechanical properties. Two types of orthophosphoric acid salt namely 

Two types of orthophosphoric acid salt namely -tricalcium phosphate (TCP) and hydroxyapatite (HAP) (classified on the basis of Ca/P ratio). The apatite- [Ca 10 (PO 4 ) 6 (OH) 2 ] crystallizes into the hexagonal rhombic system. The unit cell has dimensions of a = 0.9432 mm and c = 0.6881 nm. The ideal Ca/P ratio of hydroxyapatite is 10/6 and the calculated density is 3.219 g/ml. The substitution of OH - with F - gives a greater structural stability due to the fact that F - has a closer coordination than the hydroxyl, to the nearest calcium.

Bio inert and active CERAMICS

Nearly inert ceramics e.g., alumina and carbons show

little chemical reactivity even after thousands of hours

or exposure to the physiological pH and therefore show minimal interfacial bonds with living tissues.

Surface reactive bioglass ceramics exhibit an

intermediate behaviour. In these ceramics, surface provides bonding sites for the proteinaceous constituents of soft tissues and cell membranes,

producing tissue adherence.

CERAMICS

The more reactive materials like calcium phosphate,CERAMICS release ions from the surface over a period of time as well as provide protein

release ions from the surface over a period of time as well

as provide protein bond sites.

The ions released, aid in promoting hydroxyapatiteover a period of time as well as provide protein bond sites. nucleation, yielding mineralized bone,

nucleation, yielding mineralized bone, growing from the

implant surface.

We will now see about the different classes of ceramicyielding mineralized bone, growing from the implant surface. materials 9/2/2012 Ceramics - V.Mythily,JCE 12

materials

BIO INERT CERAMICS

Uses of Bioinert Bioceramics

1. In reconstruction of acetabular cavities.

2. As bone plates and screws.

3. In the form of ceramic-ceramic composites.

4. In the form of ceramic-polymer composites.

5. As drug delivery devices.

6. As femoral heads.

7. As middle ear ossicles.

8. In the reconstruction of orbital rims.

9. As components of total and partial hips.

10. In the form of sterilization tubes.

11. As ventilation tubes.

12. In the repair of the cardiovascular area.

Bioinert PYROLYTIC CARBON

The carbons are inert ceramic materials.Carbon materials are widely used because it has good biocompatibility with bone and other tissues

Carbon materials are widely used because it hasThe carbons are inert ceramic materials. good biocompatibility with bone and other tissues high strength and

good biocompatibility with bone and other tissues

high strength and an elastic modulus close to that of boneit has good biocompatibility with bone and other tissues Unlike metals, polymers and some other ceramics

Unlike metals, polymers and some other ceramics carbonaceous materials do not suffer from fatigue.high strength and an elastic modulus close to that of bone Carbons can be made in

Carbons can be made in many allotropic forms: crystalline

diamond, graphite, noncrystalline glassy carbon, and quasicrystalline pyrolitic carbon. Among these, only pyrolitic carbon is widely utilized

for implant fabrication; it is normally used as a surface coating.

CARBON

Pyrolytic carbons are formed by deposition of the isotropic structure on a while in a fluidized bed, at controlled temperature between 1000 to isotropic structure on a while in a fluidized bed, at controlled temperature between 1000 to 2400 0 C.

Pyrolysis of a hydrocarbon gas at temperature of less than 1500 0 C has been most useful for applications in implants. than 1500 0 C has been most useful for applications in implants.

They are called as low-temperature isotropic (LTI)0 C has been most useful for applications in implants. Carbons. The increased mechanical properties are

Carbons.

The increased mechanical properties are directly related to increased density, which indicates that the properties of pyrolitic carbon depend mainly on the aggregate structure of the material.

CARBON

These thin films of LTI carbon have good bonding strength to a number of metals with value ranging from

(10Mpa to 35MPa) with the ultimate value being

dependent upon conditions of deposition.

The anisotropy, density, crystalline, size and structure of

the deposited carbon can be controlled by temperature,

composition of fluidizing gas, bed geometry and residence time of the gas molecules in the bed.

The inclusion of silicon with pyrolytic carbon makes it

very hard, so that its wear resistance increases.

CARBON

Vitreous carbon is a polycrystalline solid with a very

small grain size, formed by the controlled pyrolysis of a polymer such as phenol formaldehyde resin, rayon and

polyacrylonitrile.

A carbon residue remains after volatile residues are driven off.The resulting volume shrinkage is about 50%.

As with the LTI carbons, the structure is isotropic and the density is close to 1.5g/cm 3 .

Wear resistance and strength, however, are not as good

as the pyrolytic LTI carbons.

Carbons exhibit excellent compatibility with tissue. Compatibility of pyrolitic carbon-coated devices with blood have resulted in extensive use of these devices for repairing diseased heart valves and blood vessels

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CARBON

The third type of turbostratic carbon is vapor deposited at

a low temperature.

These carbons are called ultra low temperature isotropic carbons (ULTI). Carbon atoms are evaporated from heated carbon source and condensed into a cool substrate of ceramic, metal or polymer. The thickness of the coating is usually less than 1m . An advantage of this process is that the coating does not change the mechanical properties of the substrate while biocompatibility of carbon is conferred on the surface.

CARBON

Pyrolytic LTI carbon is used because it is highly biocompatible, especially when used as a blood interface.

Carbon coatings find wide applications in heart values, blood vessel grafts, percutaneous devices because of exceptional compatibility with soft tissues and blood.

Carbon does not provoke an inflammatory response in adjacent tissues and no foreign body reactions to the

materials have been observed.

Bone and soft tissues are much more tolerant to carbon than other materials.

DIFFERENT VARIETIES OF CARBON (NEARLY INERT CERAMICS)

Pyrolitic carbon;

Pyrolysis of hyrdocarbon gas (methane) 1500 0 degrees

Low temperature isotropic (LTI) phase

Good bonding strength to metals (10 Mpa 35 Mpa)

Inclusion of Si with C, wear resistance increases drastically

of Si with C, wear resistance increases drastically  Vitreous carbon (glassy carbon); • controlled

Vitreous carbon (glassy carbon);

increases drastically  Vitreous carbon (glassy carbon); • controlled pyrolysis of a polymer such as phenol

controlled pyrolysis of a polymer such as phenol formaldehyde

resin, rayon and polyacrylonitrile

as phenol formaldehyde resin, rayon and polyacrylonitrile • Low temperature isotropic phase • Good

Low temperature isotropic phase

Good biocompatibility, but strength and wear resistance are not good as

LTI carbons

Turbostratic carbon (Ultra low temperature isotropic carbons (ULTI))

Carbon atoms are evaporated from heated carbon source and condensed into a cool substrate of ceramic, metal or polymer.

Good biocompatibility

Bio Inert -ALUMINA

 Alumina is Aluminium oxide. Prepared by calcining aluminium trihydide . ASTM specification for alumina:
 Alumina is Aluminium oxide.
Prepared by calcining aluminium trihydide .
ASTM specification for alumina: Al 2 O 3 - 99.6%, SiO 2 – 0.12%, Fe 2 O 3 - 0.03%
and Na 2 O -0.04%.
 The main attraction for high purity alumina to orthopedic
surgeons for its use is its
high corrosion resistance
wear resistance
 The implant devices are prepared from purified alumina
powder by isostatic pressing and subsequent firing at
1500-1700 0 C.
The high hardness is accompanied by low friction and wear and inertness
to the in vivo environment. These properties make alumina an ideal material for
use in joint replacements.

Chemical Composition of Calcined Alumina

Chemicals Al 2 O 3 SiO 2 Fe 2 O 3 Na 2 O

Chemicals Al 2 O 3 SiO 2 Fe 2 O 3 Na 2 O
Chemicals Al 2 O 3 SiO 2 Fe 2 O 3 Na 2 O
Chemicals Al 2 O 3 SiO 2 Fe 2 O 3 Na 2 O
Chemicals Al 2 O 3 SiO 2 Fe 2 O 3 Na 2 O

Composition (Weight %)

99.6

0.12

0.03

0.04

Alumina (Aluminium oxide)

 Natural single crystal alumina known as sapphire  High-density alumina ; prepared from purified
 Natural single crystal alumina known as sapphire
 High-density alumina ; prepared from purified alumina powder by
isostatic pressing and subsequent firing at 1500-1700 0 C.
 -alumina has a hcp crystal structure (a=0.4758 nm and
c=1.2999nm)
 load bearing hip prostheses and dental implants, hip and knee
joints, tibial plate, femur shaft, shoulders, vertebra, and ankle joint
prostheses
•high corrosion resistance •wear resistance • Surface finishing •small grain size •biomechanically correct
•high corrosion resistance
•wear resistance
• Surface finishing
•small grain size
•biomechanically correct design
•exact implantation technique
correct design •exact implantation technique Alumina ceramic femoral component Porous network ; SEM
correct design •exact implantation technique Alumina ceramic femoral component Porous network ; SEM

Alumina ceramic femoral component

Porous network ; SEM

images

technique Alumina ceramic femoral component Porous network ; SEM images 9/2/2012 Ceramics - V.Mythily,JCE 25

ALUMINA

Natural single crystal alumina known as sapphire has

been successfully used to make implants.

High-density alumina is used in load bearing hip prostheses and dental implants because of its

combination of excellent corrosion resistance, good biocompatibility, high wear resistance and reasonable strength. Hardness varies from 2000 Kg/ mm 2 to 3000Kg/mm 2 .High hardness accompanied by low friction and wear makes it a

good candidate for joint replacements inspite of its brittleness.

Strength, fatigue resistance and fracture toughness of polycrystalline alumina are function of grain size and

purity.

The strength of alumina depends on the porosity also.

One of the most popular uses for aluminum oxide is in total hip protheses. Aluminum oxide hip protheses with an ultra-high molecular weight polyethylene (UHMWPE) socket have been claimed to be a better device than a metal prostheses with a UHMWPE

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ALUMINA

Orthopedic uses of alumina consist of hip and knee joints, tibial plate, femur shaft, shoulders,
Orthopedic uses of alumina consist of hip and knee joints, tibial
plate, femur shaft, shoulders, vertebra, and ankle joint
prostheses.
shaft, shoulders, vertebra, and ankle joint prostheses. Alumina ceramic femoral component (Kyocera Inc.; Japan)

Alumina ceramic femoral component (Kyocera Inc.; Japan)

ALUMINA

 The hip prostheses consist of a square or cylindrical shaped alumina socket, the latter
 The hip prostheses consist of a square or cylindrical
shaped alumina socket, the latter with an outer screw
profile, for cement free anchorage to the bone.
 An alumina ball is attached to a metal femoral stem by
aid of self locking tapers.
 The stem itself is implanted with PMMA cement, though
recently cement free prostheses have also been
developed.
 Different combinations of sockets, screws and balls
made of alumina are used.

ALUMINA

 Alumina finds applications in dentistry as well as in a reconstructive maxillofacial surgery to
 Alumina finds applications in dentistry as well as in a
reconstructive maxillofacial surgery to cover bone
defects.
 Alumina is not cytotoxic and there is no activation of
body’s immune response.
 Alumina implants do not show inflammatory or
progressive fibrotic reactions.
 However, worn out alumina particles are observed in the
interstitium of the lung, in reticuloendothelial cells of liver,
spleen and bone marrow after phagocytosis.

ALUMINA

The important prerequisites for success of alumina implants are, Surface finishing small grain size biomechanically
The important prerequisites for success of alumina implants are,
Surface finishing
small grain size
biomechanically correct design
exact implantation technique

Zirconia (ZrO 2 )

Pure zirconia can be obtained from chemical conversion of zircon (ZrSiO4 ), which is an abundant mineral deposit .Zirconia has a high melting temperature (Tm = 2953 K) and chemical stability with a = 5.145 Å, b= 0.521 Å,C = 5.311 Å, and β =

99°14.

It undergoes a large volume change during phase

changes at high temperature in pure form; therefore, a dopant oxide such as Y 2 O 3 is used to stabilize the high temperature (cubic) phase.

Zirconia has shown excellent biocompatibility and

good wear and friction when combined with ultra- high molecular weight polyethylene.

BIOACTIVE CERAMICS

GLASS CERAMICS

The main for the invention of this type of implant material is to achieve a
The main for the invention of this type of implant material
is to achieve a controlled surface reactivity that will induce
a direct chemical bond between the implant and the
surrounding tissues.
Glass ceramics are polycrystalline ceramics.
The glass ceramics serves this purpose.
Bioglass and Ceravital are two glass ceramics, having
fine-grained structure with excellent mechanical and
thermal properties, which are used in implants.
The composition of Ceravital is similar to bioglass in Sio 2
content but differ in CaO,MgO,Na 2 O.

Glass ceramics are polycrystalline ceramics

made by controlled crystallization of glasses ( photosensitive glasses), in which small

amounts of copper, silver, and gold are

precipitated by ultraviolet light irradiation.

These metallic precipitates help to nucleate

and crystallize the glass into a fine grained

ceramic which possesses excellent mechanical and thermal properties.

Both Bioglass and Ceravital glass ceramics

have been used as implants

The formation of glass ceramics is influenced by the nucleation and growth of small (<1 μm diameter) crystals as well as the size distribution of these crystals. It is estimated that about 1012 to 1015 nuclei per cubic centimeter are required to achieve such small crystals.

In addition to the metallic agents already mentioned, Pt groups, TiO 2 , ZrO 2 , and P 2 O 5 are widely used for nucleation and crystallization.

The nucleation of glass is carried out at temperatures much lower than the melting temperature. During processing the melt viscosity is kept in the range of 1011 and 1012 Poise for 1 to 2 h.

In order to obtain a larger fraction of the microcrystalline phase, the material is further heated to an appropriate temperature for maximum crystal growth. Deformation of the product, phase transformation within the crystalline phases, or redissolution of some of the phases should be avoided. The crystallization is usually more than 90% complete with grain sizes 0.1 to 1 μm. These grains are much smaller than those of conventional ceramics.

The glass ceramics developed for implantation are SiO 2 -CaO-Na 2 O-P 2 O 5 and Li 2 O- ZnO-SiO 2 systems.

Two major groups are experimenting with the SiO 2 -CaO-Na 2 O-P 2 O5 glass ceramic.

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Glass Ceramics To achieve a controlled surface reactivity that will induce a direct chemical bond
Glass Ceramics
To achieve a controlled surface reactivity that will induce a
direct chemical bond between the implant and the surrounding
tissues.
Bioglass
Also known as 45S5 glass. It is composed of SiO 2 , Na 2 O, CaO
and P 2 O 5.
45 wt.% of SiO 2
and 5:1 ratio
of
CaO to P 2 O 5 . Lower
Ca/P
ratios do not bond to bone.
Bioglass and Ceravital; fine-grained structure with excellent
mechanical and thermal properties
The composition of Ceravital is similar to bioglass in Sio 2
content but differ in CaO,MgO,Na 2 O.
Ceravital
Bioglass implants have several advantages like
• high mechanical properties
• surface biocompatible properties.

GLASS CERAMICS

Bioglass implants have several advantages like • high mechanical properties • surface biocompatible properties. •
Bioglass implants have several advantages like
• high mechanical properties
• surface biocompatible properties.
• The surface-reactive implants respond to the local pH
changes by releasing divalent ions.
• The surface reactivity can be controlled by the
composition of the implant.

Temperature-time cycle for a glass-

ceramic

Temperature-time cycle for a glass- ceramic 9/2/2012 Ceramics - V.Mythily,JCE 38

GLASS CERAMICS

The bioglass ceramics containing less reactive fluoride

acquire a fibrous capsule when implanted in rat femurs.

The major drawback of glass ceramic is its brittleness.

Therefore, they cannot be used for major load-bearing

implants such as joint implants.

However glass ceramics can be used as fillers for bone

cement, dental restorative composite and as coating

material.

Ceravital

The composition of Ceravital is similar to that of Bioglass in SiO2 content but differs somewhat in other components. In order to

control the dissolution rate, Al2O3, TiO2, and Ta2O5 are added

in Ceravital glass ceramic.

The mixtures, after melting in a platinum crucible at 1500°C for three h, are annealed and cooled. The nucleation and crystallization emperatures are 680°C and 750°C, respectively, each for 24 h.

When the size of crystallites reaches pproximately 4 Å and the

characteristic needle structure is not formed, the process is

stopped to obtain a fine grain structured glass ceramic

Desirable properties OF Glass ceramics

Glass ceramics have several desirable properties compared to glasses and ceramics. The thermal coefficient of expansion is very low, typically 10 7 to 10 5 °C 1 , and in some cases it can even be made negative.

Due to the controlled grain size and improved resistance to surface damage, the tensile strength of these materials can be increased by at least a factor of two, from about 100 to 200 MPa.

The resistance to scratching and abrasion of glass ceramics is similar

to that of sapphire .The mechanical strength of the interfacial bond between bone and Bioglass ceramic is on the same order of magnitude as the strength of the bulk glass ceramic (850 kg/cm2 or

83.3 MPa), which is about three-fourths that of the host bone

strength

A negative characteristic of the glass ceramic is its brittleness.

BIORESORBABLE CERAMICS

RESORBABLE CERAMICS

 One of the first resorbable implant substance uses was Plaster of Paris.  The
 One of the first resorbable implant substance uses was
Plaster of Paris.
 The reasons why Plaster of Paris is not widely used are
• variable resorption rates
• poor mechanical properties.
Two types of orthophosphoric acid salt namely -
tricalcium phosphate (TCP) and hydroxyapatite (HAP) find
widespread use as resorbable Ceramics

Uses of Biodegradable Bioceramics

1. As drug delivery devices.

2. For repairing damaged bone due to disease or

trauma.

3. For filling space vacated by bone screws, donor

bone, excised tumors, and diseased bone loss.

4. For repairing and fusion of spinal and lumbo-

sacral vertebrae

5. For repairing herniated discs.

6. For repairing maxillofacial and dental defects

7. Hydroxyapatite Ocular Implants.

RESORBABLE CERAMICS - APATITE

The apatite- [Ca 10 (PO 4 ) 6 (OH) 2 ] crystallizes into the hexagonal
The apatite- [Ca 10 (PO 4 ) 6 (OH) 2 ] crystallizes into the
hexagonal rhombic prism.
The unit cell has dimensions of a = 0.9432 mm and c =
0.6881 nm.
The ideal Ca/P ratio of hydroxyapatite is 10/6 and the
calculated density is 3.219 g/ml.
The substitution of OH- with F- gives a greater structural
stability due to the fact that F- has a closer coordination
than the hydroxyl, to the nearest calcium.

RESORBABLE CERAMICS

HYDROXYAPATITE The synthetic hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 is prepared by
HYDROXYAPATITE
The synthetic hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 is
prepared by the reaction of Ca(OH) 2 and H 3 PO 4 in an
aqueous solution.
The addition of fluorine to form fluoro-apatites may be
beneficial for the surrounding bone.
Fluoride treatments have been shown to cause a marked
increase in bone formation and comprehensive strength
of osteoporetic tissues.
It has a high modulus of elasticity (40-117 GPa).
The Poisson ‘s ratio is 0.27 which is close to natural bone (0.3)
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RESORBABLE CERAMICS

The Key properties of hydroxyapatite are,

The ability to integrate in bone structures and support bone ingrowth, without breaking down or dissolving

Hydroxyapatite is a thermally unstable compound,

decomposing at temperature from about 800-1200°C depending on its stoichiometry.

The wide variations in properties of polycrystalline calcium phosphates are due to the variations in the structure and manufacturing processes. Depending on the final firing conditions, the calcium phosphate can be calcium hydroxyapatite or β -whitlockite.

In many instances, both types of structures exist in the same final product Polycrystalline

hydroxyapatite has a high elastic modulus (40 to 117 GPa). Hard tissue such as bone, dentin, and dental enamel are natural composites which contain hydroxyapatite (or a similar mineral), as well as protein, other organic materials, and water. Enamel is the stiffest hard tissue, with an elastic

modulus of 74 GPa, and contains the most mineral. Dentin ( E = 21 GPa) and compact bone ( E = 12 to

18 GPa) contain comparatively less mineral. The Poisson’s ratio for the mineral or synthetic hydroxyapatite is about 0.27 which is close to that of bone ( ≈ 0.3)

Manufacturing of HAP

Ca (NO3)2 and NaH2PO4 precipitates Filtering- drying to fine particle powder.

Calcination /3 hours at 900 o C (to promote crystallization)

Pressing and sintering at 1050-1200 o C for 3 hours.

Grain boundary formation.

RESORBABLE CERAMICS

Can be crystallized into salts, hydroxy apatite

and B- whitlockite depending on the Ca/P

ratio, presence of impurities , water and temperature.

At low temperature (< 900 o C ) hydroxy apatite form and at high temperature the b- whitlockite will be formed.

The apatite form of calcium phosphate closely

mimics the mineral phase of bone and teeth.

Hydroxyapatite Synthesis Method

Prepare the following solutions:

Solution 1: Dissolve 157.6 g calcium nitrate tetrahydrate [Ca(NO3)24H2O] in 500 ml DI water. Bring the solution to a pH of 11 by adding ≈ 70 ml ammonium hydroxide *NH4OH+. Bring the solution to 800 ml with DI water. Solution 2: Dissolve 52.8 g ammonium phosphate dibasic [(NH4)2HPO4] in 500 ml DI water. Bring the solution to a pH of 11 by adding ≈ 150 ml ammonium hydroxide *NH4OH+. Add DI water until the precipitate is completely dissolved, 250350 ml.

1. Add one-half of Solution 1 to a 2 L separatory funnel.

2. Add one-half of Solution 2 to a 2 L separatory funnel.

3. Titrate both solutions into a 4 L beaker with heat and constant stirring.

4. Boil gently for 30 min.

5. Repeat steps 14 for the rest of Solutions 1 and 2.

6. Let cool completely allowing precipitate to settle to bottom of beaker.

7. Pour contents of beaker into 250 ml polypropylene bottles.

8. Centrifuge bottles for 10 min at (10,000 rpm) 16,000 g.

9. Collect precipitate from the six bottles into two and resuspend with DI water.

10. Fill the four empty bottles with the reaction mixture and centrifuge all six as before.

11. Collect precipitant from the two bottles that were resuspended with DI water.

12. Combine remaining four bottles into two bottles and resuspend with DI water.

13. Repeat steps 1012 as necessary.

14. Dry precipitate for 2448 h at 70°C.

15. Calcine the precipitate for one hour at 1140°C.

16. Grind and sieve product as desired.