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A04 515 PDF
A04 515 PDF
A further vacuum distillation step is required The result is a fundamental quality improve-
to obtain high-purity calcium metal, used in ment, especially in castability and the mechani-
more specialized refining applications such as cal properties: formability, drawing, impact, ten-
the production of neodymium for magnetic al- sile, machinability, resistance to cracking and
loys. This second operation reduces the level tearing, and improved surface and internal clean-
of contaminants. Commercial-grade calcium is liness. Calcium also improves resistance to hy-
placed at the bottom of a large vertical retort drogen-induced cracking in line pipe associated
made of heat-resistant steel; the vessel has a with high-sulfur oil and gas pipelines.
water-cooled condenser at the top. The retort is In the early 1970s, calcium wire feeding tech-
sealed and evacuated to a pressure of less than nology was introduced. A steel-clad calcium
6.6 Pa; the bottom is heated to 900 – 925 ◦ C. wire is fed through a delivery system which pro-
Calcium distills to the condensing section and pels the wire well below the surface of the molten
leaves behind less volatile impurities. Table 3 steel. The steel cladding protects the calcium un-
shows the purity after the first and second pu- til it reaches a depth where the ferrostatic pres-
rification steps. sure suppresses vaporization.
Table 3. Chemical analysis of typical commercial and redistilled The use of metallic calcium to refine steel
calcium became common in Japan and the USA in the
Element Commercial Redistilled 1980s. Cored-wire injection technology was ap-
grade, wt % grade, wt % plied in ladle metallurgy, tundish, and mold
Mg 0.50 0.50 injection for continuous casting. This led to
N 0.08 0.02 the adoption of calcium injection for improved
Al 0.30 0.001 castability and superior product quality in thin
Fe 0.008 0.001
Mn 0.01 0.002 slab casting. This casting technology, which can
Co n.a. 0.0002 produce continuous 50 – 70 mm steel slabs, was
Li n.a. 0.0001 developed by SMS and MDH in Germany dur-
Be n.a. 0.0001
Cr n.a. 0.0002
ing the mid-1980. Nucor, USA, established the
B n.a. 0.0001 first commercial-scale thin-slab caster in 1989.
Ca and Mg 99.5 99.9 Thin-slab casting employs a specially de-
signed nozzle that is susceptible to alumina
buildup, develops progressive blockage, serious
clogging, and leads to termination of the cast-
4. Uses ing process. Calcium has proved the most ef-
Steelmaking. The major use of calcium is fective method to prevent these problems. With
to improve the quality of steel (→ Steel). For appropriate sequential process steps, treatment
decades, calcium-containing ferroalloys have with calcium allows inclusion-shape control and
been used as tap-stream additions to the molten gives much cleaner steel.
metal, or calcium compounds were injected For large-tonnage use and ladle treatment, a
through a refractory lance by using argon as car- wire-lance system combines the advantages of
rier gas. Although the benefits of using pure cal- wire feeding, gas control of fluid dynamics, and
cium metal were known, they were difficult to treatment with pure calcium. This has resulted
obtain; calcium is highly volatile, boiling well in the efficient production of improved-quality
below steelmaking temperatures. ultraclean steels.
Calcium is important in steel chemistry be-
cause it is a strong oxide and sulfide former; Maintenance-Free Automotive Battery. In
furthermore, it has the uncommon ability to al- the maintenance-free automotive battery (→
ter the oxides and sulfides to give liquid lime Batteries, Chap. 4.2.2), calcium improves elec-
aluminates and underformed sulfides. Treatment trical performance and battery life. The anti-
with calcium modifies the melting point of in- mony – lead alloy used in the conventional lead
clusions, which rapidly float out of the steel; – acid battery is replaced with a 0.1 % Ca – Pb
in addition, treatment alters the morphology of grid alloy. The calcium in “calcium batteries”
any remaining inclusions, rendering them spher- refers to the lead alloy used in the production
ical in shape, very small, and finely dispersed. of the grids for plate making. The alloy is typ-
4 Calcium and Calcium Alloys
ically still 99 % lead with alloying metals. Cal- as a reductant. This is an important development
cium alloy grids afford low water loss and low because these magnets have energy products ap-
self-discharge. proaching 40 × 104 T·A/m, over twice that of
Calcium improves the conductivity and cur- samarium – cobalt. In addition, the availabil-
rent capability of the cell; it significantly reduces ity of the raw materials is significantly greater
gassing, permitting the cell to be closed, thus than for samarium – cobalt; both the quantity
preventing water loss and extending life. The and stability of raw material supply limited the
hydrogen overvoltage increases with calcium – growth of samarium – cobalt magnets. There-
lead alloy grids, so at a given rate of overcharge fore, neodymium – iron – boron magnet mate-
at the same temperature, an antimonial battery rials are less expensive to produce.
will consume more water than a calcium battery. The energy density is sufficient to permit
The resulting battery will not require water addi- the replacement of armature windings in mo-
tion, i.e., maintenance, during its operating life tors, transducers, and generators with permanent
under normal operating conditions. Their lower magnets. The weight of an automotive starting
internal resistance provides a higher charge-rate motor was reduced from 3.6 to 1.8 kg; the size
acceptance and a small increase in performance. and cost of the motor were commensurately re-
The life and performance of calcium – lead bat- duced as well. This technology is finding exten-
teries is enhanced by tight control of the man- sive applications in automotive, computer pe-
ufacturing process and the specifications of the ripheral, medical, home appliance, and military
grid alloy for the positive plate. markets.
Calcium – lead alloy grids were prone to ex- There are two methods of producing
pansion and cracking that lead to premature bat- the neodymium – iron – boron raw material, a
tery failure. The use of calcium alloys and roll- neodymium – iron alloy. One is the calcium
hardening the positive grid reduced the problem. thermal reduction method:
A calcium – aluminum alloy forms a eutectic
NdF3 or NdCl3 +Ca+Fe→NdFe+byproducts
with lead, and rapid solidification of the alloy
makes continuous grid making possible. or
Lead – calcium alloys have replaced lead –
antimony alloys in a number of casting appli- Nd2 O3 +Ca+Fe→NdFe+byproducts
cations. These alloys contain 0.03 – 0.15 % Ca. The second method is by electrolysis:
Aluminum is added to calcium – lead and cal-
cium – tin – lead alloys as a stabilizer for cal- NdCl2 +electricity→Nd2 +Cl2(v)
cium. Adding tin to lead or lead alloys increases or
hardness and strength, but lead – tin alloys are
more commonly used in type metals and sol- NdF3 +Nd2 O3 +electricity→Nd+byproducts
ders for their good melting, casting, and wetting
The calcium thermal reduction process is pre-
properties. Tin gives the alloy the ability to wet
ferred. It has the greatest flexibility in produc-
and bond with metals such as steel and copper;
ing the basic neodymium – iron and alloy varia-
unalloyed lead has poor wetting characteristics.
tions. The byproducts are not toxic as they are in
Magnet Materials. High-energy-density the electrolytic process. The calcium process is
magnetic materials are produced using calcium less capital intensive and readily scaled in pro-
(→ Magnetic Materials). Samarium – cobalt duction volume to meet market demands.
magnets with energy products of between 8 Iron Making. Injection of calcium wire has
and 16 × 104 T·A/m have found applications been adopted by many foundries for iron treat-
in miniature transducers and other devices re- ment. Again, the calcium is used for desulfur-
quiring high energy or volume restrictions. The ization, inoculation spherodizing, and alloying.
reaction is: Calcium ferroalloys are used in the produc-
3 Sm2 O3 +10 Co3 O4 +49 Ca (g) →6 SmCo5 +49 CaO tion of nodular iron castings. In magnesium
ferrosilicon, calcium reduces the reactivity, en-
The production of neodymium – iron – hances nucleation, and improves morphology.
boron magnets involves the use of calcium metal The ratio of calcium to magnesium varies from
Calcium and Calcium Alloys 5
0.15 to 0.50. Pieces of the ferroalloy are placed Precipitated calcium carbonate is used to re-
in a protected pocket cut in the refractory lin- place wood pulp in paper and as an antacid.
ing of the ladle prior to tap. The molten iron is Many calcium compounds are used in
then poured into the ladle where it reacts with the foodstuffs, pharmaceuticals and medi-
the alloy. The treated, nodularized iron is then cal industries. Calcium lactate Ca(C3 H5 O3 )2 ·
cast into molds. 5 H2 O, calcium diphosphate (phosphate of
In the in-mold process, granularized ferroal- lime), CaHPO4 · H2 O, and tricalcium phosphate
loy is placed in a special reaction chamber Ca3 (PO4 )2 are used to supply calcium and phos-
formed in the channels of the mold. This per- phorus to foods. The last-named also finds appli-
mits the reaction to occur when the iron is cast; cation as a polishing agent in dentifrices and as
it enhances the effectivity of the ferroalloy and an antacid. Calcium lactobionate, a white pow-
results in improved castings. The process can be der, provides a suspending agent in pharmaceu-
automated for high productivity. ticals.
Other Applications of Calcium and Cal- Calcium monophosphate, CaH4 P2 O8 ·H2 O is
cium Compounds. Alloys of calcium also are used as a leavening agent in baking. Anhydrous
used to deoxidize magnesium, to strengthen lead monocalcium phosphate CaH4 (PO4 )2 is used in
electrodes, and to produce special aluminum pre-mixed flour mixes.
alloys. Calcium is also used to improve the Calcium sulfite CaSO3 · 2 H2 O provides a
mechanical properties of lead (→ Lead Alloys). bleach for paper pulp and textiles. As a bleach,
A proprietary process for improving the integrity it is a disinfectant.
and formability of the lead used in yacht keels Calcium silicate CaO · SiO2 is used as a re-
was developed in Australia. inforcing agent in rubber. This compound also
In the debismuthizing of lead by the Kroll- helps manipulate the viscosity of liquids, com-
Betterton process, calcium metal is combined mercially as a filler in paints and coatings. In
with bismuth which then floats out in a dross: coatings it modifies the reflectivity resulting in
reduce sheen, a matte surface. Calcium metasili-
3 Pb3 Ca+2 Bi→Bi2 Ca3 +9 Pb
cate CaO·SiO3 (wollastonite) is used as a bright-
Lead ores are thus refined to commercial soft ener for paints and paper coatings, a filler for
lead with 0.02 % or less Bi (→ Lead). plastics, a coating for welding rods, and for elec-
Calcium metal is reacted with zirconium fluo- trical insulators, tile, and ceramics.
ride to refine zirconium; the high heat of reaction Calcium acetate Ca(C2 H3 O2 ) · 2 H2 O,
melts the zirconium. The zirconium ingot pro- (known as lime acetate and vinegar salts) is
duced by this method is remelted under vacuum employed in liming rosin and the manufacture
for purification. The resulting metal is leached of metallic soaps and synthetic resins.
with acetic acid to remove the lime produced as Limestone is an essential element in Portland
a byproduct of the reaction. cements. Oyster shells (CaCO3 ) are a commer-
Uranium fluoride or oxide can be reduced cially important source of calcium for animal
with calcium. To produce thorium and uranium, feeds.
the oxides are mixed with a stoichiometric ex-
cess of calcium and reduced under an atmo-
sphere of argon. Auergesellschaft during World 5. Occupational Health and Safety
War II made the uranium metal for the atomic
bomb project by using metallic calcium to re- Calcium metal reacts with water and acids to
duce uranium oxide to uranium metal. In 1945 form hydrogen gas, calcium oxide and calcium
the Russians dismantled and took the calcium hydroxide; the reaction is exothermic. If calcium
plant to Russia for refining uranium. Calcium metal contacts moisture in the eyes, on the skin,
produced in China was used in obtaining nuclear or in the respiratory tract, severe corrosive irrita-
materials as well. tion may result. Inhalation of dust or fume may
Calcium metal is readily hydrided for use as cause severe respiratory irritation, cough, diffi-
a portable source of hydrogen gas. It also is used culty in breathing, and chemical pneumonitis.
in the production of the B-complex vitamin cal- Contact with skin causes irritation and possible
cium pantothenate [137-08-6]. corrosion damage.
6 Calcium and Calcium Alloys
The substance is severely irritating to the eyes mended as an extinguishing agent for fires that
and may injure eye tissue if not promptly re- involve it. If water must be used, prevent it from
moved. coming into direct contact with calcium metal. If
Ingestion may cause acute irritation or burns contact is unavoidable, apply the water in flood-
to the mouth, throat, and stomach; calcium may ing amounts to safely absorb the heat that will
cause vomiting. Pre-existing chronic respiratory, be generated.
skin, or eye diseases may be aggravated. Hazard: Calcium metal is extremely danger-
The symptoms of inhalation include severe ous when wet. Calcium metal forms calcium
irritation of respiratory tract. Skin and eye con- hydroxide and hydrogen gas resulting in an ex-
tact symptoms are severe irritation. plosion hazard when wet. Calcium metal forms
There are no known adverse health effects CaO, quicklime, when it burns. It reacts with
resulting from long-term exposure to calcium wet extinguishing agents such as water, halo-
metal gens, and possibly carbon dioxide.
First Aid. Inhalation: Remove to fresh air. If Accidental Release Measures. Do not
breathing is difficult, give oxygen. Seek imme- touch spilled calcium metal. Wear protective
diate medical attention. apparel. Do not smoke or place flame or igni-
Skin contact: Remove calcium metal imme- tion sources near spill area. Do not allow water
diately with a dry cloth. Wash the area with large to touch spilled calcium metal or to get inside
amounts of water until all the chemical is re- containers. Use a cover, a plastic sheet for ex-
moved. ample, to prevent water or rain from dissolving
Eye contact: Immediately flush eyes with spilled calcium metal or to prevent its spread-
running water for 15 min. Lift upper and lower ing. Isolate hazard area and keep nonessential
eyelids occasionally. Get immediately medical personnel away from spill or leak site. Shovel
attention. small dry spills into a dry container and cover
Ingestion: If victim is conscious, give large it tightly. Move containers away from spill to a
amounts of water to dilute the alkali. Do not in- safe area. Take up small spills with sand or an
duce vomiting. Never give anything by mouth to absorbent and contain as described above. Dike
an unconscious person. the flow of large calcium metal and water spills
Note to physician: All treatment should be with soil, sandbags, or concrete. Keep the waste
based on observed signs and symptoms of dis- from entering drains and open sewers. Wear full
tress in the patient. Consideration should be protective gear.
given to the possibility that overexposure to ma-
Handling and Storage. Storage: Store cal-
terials other than calcium metal may have oc-
cium metal in a sealed container away from wa-
curred.
ter, acids, or organic compounds. Protect con-
Firefighting Measures. Extinguishing tainers against physical damage. Calcium metal
method: Do not use water, foam, or halogenated will generate heat upon contacting water.
hydrocarbons such as Halon or carbon tetrachlo- Handling: Avoid damaging container.
ride to extinguish fire. Use only graphite powder,
Exposure Controls and Personal Protec-
soda ash, powdered sodium chloride, or an ap-
tion. Ventilation: Provide adequate exhaust ven-
propriate metal-fire-extinguishing dry powder,
tilation to meet exposure limit requirements. An
such as Met-L-X. For large fires, withdraw from
exhaust filter system may be required to avoid
the area and let the fire burn.
environmental contamination.
Firefighting procedures: Firefighters should
Respiratory protection: Calcium metal does
wear self-contained breathing apparatus with
not have established exposure limits. Wear a
full face piece operated in the pressure-demand
positive pressure air-supplied respirator in situa-
or positive-pressure mode. Firefighters should
tions where there may be a potential for airborne
move containers from the fire area if this can be
exposure.
done without risk. Do not use water or foam. Use
Hand protection: Impervious gloves.
dry powder only.
Eye protection: Chemical goggles and/or face
Fire and explosion hazards: Water reacts dan-
shield.
gerously with calcium metal and is not recom-
Calcium and Calcium Alloys 7
Other protection: Wear rubber apron or other the digestive protein trypsin has a locus of glu-
impervious clothing to prevent contact with skin. tamic and aspartic residues that bind Ca, and
this changes the conformation of the enzyme to
enhance its activity [11, 12]. Osteocalcin (a bone
6. Biological Relevance matrix protein) possesses a sequence with three
γ-carboxyglutamic acid residues that enable it to
6.1. Introduction bind Ca minerals [13]. The bone matrix proteins
osteopontin and bone sialoprotein are rich in as-
Calcium is indispensable for life; it is required partic acid, glutamic acid, and phosphorylated
for maintenance of structure and metabolism. serine and/or threonine residues, which per-
Examples of the structural role of calcium in- mit them to bind calcium phosphate crystals
clude the elaborate structure of coral [8], the se- [14 – 18]. Calcium-dependent enzymes can be
creted shells of mollusks, and the internal skele- activated by two principal mechanisms. Many
tons of vertebrates. Calcium is also necessary enzymes are activated by binding Ca directly.
for many biological functions, the most promi- Other calcium-dependent enzymes do not bind
nent being muscle contraction, nerve conduc- Ca, but are activated by noncovalent associa-
tion, and regulation of blood clotting. To control tion with calcium-binding proteins. Calcium-
these functions, all organisms have mechanisms binding proteins which fulfill this co-enzyme
for maintaining critical intracellular calcium lev- function include calmodulin, annexin, and cal-
els. Organisms with a circulatory system also cineurin.
have mechanisms to control extra-cellular cal- To optimize the ability of proteins to bind
cium levels as well as calcium uptake and ex- calcium, the relevant amino acid residues are lo-
cretion. The role of calcium in biological sys- calized in specific domains which may be con-
tems has been the subject of a number of books served between species and throughout evolu-
[9, 10]. This chapter focuses on the molecular, tion. An example domain is known as “EF-
metabolic and structural aspects of calcium in hand”, which is a single helix – loop – helix
vertebrate biology. structure that binds Ca within the 12-amino acid
loop [19]. The proteins possessing EF hand mo-
tifs have undergone significant and turbulent
6.2. Chemical Properties of Ca molecular evolution. Starting as an archety-
pal protein containing one EF hand, the genes
Important in Biological Functions
coding these proteins have undergone dupli-
Calcium has two properties that render it indis- cations, deletions, and retroversions to yield a
pensable for life. First, Ca ions complex with or- family of calcium-binding proteins with a wide
ganic compounds, particularly proteins, thereby array of functions and a variable number of
affecting their function. Second, Ca salts display EF hands [19 – 25]. A representative calcium-
a wide range of solubility, making it possible for binding protein of this type is calmodulin, which
vertebrates to possess a skeleton. has four EF hands that recapitulate the canoni-
cal EF hand sequence observed in slime molds,
Calcium – Protein/Lipid Interactions. paramecium, plants, and mammals, including
Calcium mediates many biological functions humans [22, 26]. Calcium also complexes with
through its ability to bind specifically to pro- cell membrane phospholipids, which can anchor
teins and lipids. Calcium binds to proteins by cell surface-associated proteins on the basis of
three principal mechanisms. First, it can directly electrostatic interaction between Ca ion and the
bind the carboxyl groups of glutamic and aspar- negatively charged head groups of cell mem-
tic acid residues to alter enzyme function. Sec- brane phospholipids.
ond, it can interact with specific phosphorylated
serine, tyrosine, or threonine residues. Third, Solubility Range of Calcium Salts. Primary
specific amino acids that have undergone vi- calcium phosphate Ca(H2 PO4 )2 is extremely
tamin K-dependent γ-carboxylation effectively soluble. Secondary calcium phosphate CaHPO4
chelate Ca. Proteins may use one or more of has a solubility of about 2.0 mM and makes up
these mechanisms to bind Ca. For example,
8 Calcium and Calcium Alloys
light [34]. Vitamin D undergoes hydroxylation ond, passive flux between intestinal cells, known
in the liver to form 25-(OH)-D and then by the as paracellular flux (Fig. 2).
kidney to 1, 25-(OH)2 -D, which is the major ac- The kidneys are the principal regulators of
tive metabolite regulating Ca homeostasis. Cir- plasma calcium level, and filter about 10 g of
culating vitamin D2 has a half-life of about 1.5 Ca per day. In the renal glomeruli, Ca is fil-
d. The major target organs of vitamin D2 include tered out of the blood into the proximal tubule;
the gut, kidney, and bone [35]. however, 70 % is reabsorbed in this portion of
Calcitonin is a short 32 amino acid peptide the kidney by paracellular transport. In addi-
secreted by specialized cells in the thyroid gland. tion, about 20 % of the filtered Ca is reabsorbed
Calcitonin secretion is stimulated (or inhibited) in the thick ascending limb of Henle by para-
by acute increases (or decreases) in plasma cal- cellular transport and calcitonin-induced active
cium concentration. Its plasma half-life is about transport. The remaining Ca is absorbed by the
10 min. Calcitonin inhibits bone resorption, thus distal convoluted tubes in a PTH- and vitamin D-
antagonizing the effect of PTH. The role of cal- dependent manner due to enhanced expression
citonin in regulating plasma calcium levels is of calbindin-D28K . The urinary filtrate thus con-
minor relative to PTH and vitamin D [36]. tains approximately 1 % of the filtered Ca load
[39].
Bone contributes to the steady-state plasma
6.5. Control of Plasma Calcium by calcium level, which is regulated by PTH and vi-
Target Organs tamin D. PTH promotes bone resorption by acti-
vating cells within the bone matrix (osteoclasts)
In the intestine, Ca is absorbed as the free ion committed to matrix destruction, allowing Ca
with an efficiency of approximately 30 – 32 %. access to plasma [29]. However, PTH also pro-
Calcium traverses the intestinal lining either by motes bone formation, probably due to its action
transcellular flux, which is mediated by calcium- on cells lining bone (osteocytes). Vitamin D has
transport proteins or vesicular transport, or a sec- multiple effects on Ca trafficking: it enhances
10 Calcium and Calcium Alloys
deposition of Ca into bone by stimulating the which is collagen type I, is flexible and tension
maturation of primitive bone cells (osteoblasts) resistant. Thus, bone has the tensile strength of
to osteocytes, but also acts in concert with PTH cast iron, but has only one-third the weight and
to stimulate osteoclast activity. Thus, PTH and is ten times as flexible. Bone is organized into
vitamin D act together to increase the rate of two general types of structures. Compact bone
bone and mineral turnover without altering net which forms the shafts of the long bones and the
bone mineral content or mass [40]. outer surface of nearly all other bones, is highly
calcified (80 – 90 %). Trabecular bone forms the
ends of the shafts of the long bones and most of
6.6. Physiology of Intracellular Calcium the bones in the spine, and is 15 – 20 % calcified
Trafficking [44].
Cellular Basis of Bone Formation and
The optimum intracellular calcium concentra- Turnover. Bone undergoes continuous remod-
tion is 0.1 µM, which is 10 000 times less than eling due to the activity of bone-forming cells
the extracellular calcium level. Accordingly, (osteoblasts, osteocytes), and bone-resorbing
cells developed mechanisms to control Ca flux cells (osteoclasts). Osteoblasts secrete connec-
between the extra- and intracellular pools. The tive tissue proteins to form unmineralized bone
major restriction of extracellular Ca to the intra- matrix. Mature osteoblasts, known as osteo-
cellular milieu is the plasma membrane which cytes, lie within small cavities that are com-
has a low passive permeability to Ca. How- pletely surrounded by bone, and are responsible
ever, the plasma membrane also has Ca chan- for bone deposition. These cells are activated by
nels which allow Ca entry in response to changes vitamin D, calcitonin, platelet-derived growth
in voltage, stretching, or hormonal stimulation factor, transforming growth factor- β, insulin-
[41]. At least one type of channel is tonically ac- like growth factor, androgens, and low physio-
tive and permits Ca to the extracellular milieu, as logical amounts of glucocorticoids [45]. In con-
described above [42]. In addition, an intracellu- trast, osteoclasts degrade bone, and are activated
lar tubular structure known as the smooth endo- by PTH, vitamin D, interleukin-1, tumor necro-
plasmic reticulum (SER) serves as a source of in- sis factor, and prostaglandin E1 . Conversely, os-
tracellular Ca. A membrane-bound Ca/ATPase teoclast activity is inhibited by estrogens [46].
transports cytoplasmic Ca into the SER, which There are two general mechanisms by which
lowers cytoplasmic calcium level. In contrast, bone is laid down. In the first, bone formation
release of calcium from the SER is mediated by occurs in the absence of a pre-existing structure.
two receptors, one of which is responsive to hor- Primordial cells differentiate directly into os-
monal stimulation, while the other is activated teoblasts, which secrete soluble collagen into the
by the Ca itself [43]. The cytoplasmic calcium extracellular space. The soluble collagen then
level is thus a reflection of the state of activa- self-assembles to form fibrils, which are stabi-
tion of the cell. Collectively, calcium-dependent lized by extensive intermolecular cross-linking.
enzymes control nearly every aspect of cell func- Initially, the bone matrix is randomly oriented
tion, including nucleotide metabolism, glycogen (or woven), and hydroxyapatite deposition oc-
metabolism, electrolyte balance, neuromuscular curs in irregular patches by the formation of
irritability, neural function, muscle contraction, matrix vesicles as a result of exocytosis from
and proliferation. the plasma membrane of osteoblasts. Mineral-
ization occurs on these vesicles. and as the crys-
tals grow, the vesicle is subsequently destroyed.
6.7. Physiology of Bone Bones which are formed by this method include
Bone is a connective tissue that has the ability to flat bones, such as the skull, jaw, and ribs. The
become calcified. Structurally, bone consists of second method of bone formation occurs on a
hydroxyapatite deposited within an organic ma- previously existing cartilaginous structure as an
trix. Hydroxyapatite is hard, rigid, and brittle, initial supporting structure which undergoes ini-
and is effective mainly in resistance to compres- tial calcification. Remodeling of this calcified
sion. However, the organic matrix, over 90 % of matrix by osteoclasts and osteoblasts eventually
Calcium and Calcium Alloys 11
replace the calcified cartilage in the formation 6.8. Disturbances in Plasma Calcium
first of woven bone, and then compact bone. Homeostasis
Mineralization in compact bone occurs within
Hypercalcemia. Excessive calcium intake
the tightly spaced organic matrix within vesicle
may cause increased calcium levels. However,
formation. This process occurs in the develop-
this is rare, since intestinal paracellular Ca trans-
ment of the long bones of the legs and arms [47].
port is rather inefficient, and at least 2 – 3 grams
Remodeling of bone occurs throughout life.
of additional Ca must be consumed to cause
During growth, the midshaft of long bones un-
toxicity. Hypercalcemia is usually due to exces-
dergoes growth on the outer surface, and resorp-
sive intake of vitamin D, increased PTH secre-
tion at the inner surface to maintain net bone
tion (primary hyperparathyroidism), or a conse-
thickness. At puberty, the growth plates present
quence of bone destruction secondary to tumor
on both ends of long bone close and prevent fur-
metastasis to bone. Hypercalcemia is manifested
ther bone lengthening. As bone ages, the organic
by deposition of Ca salts into the heart, blood
matrix becomes brittle and weak, and undergoes
vessels, kidneys, and skeletal muscles, anorexia,
microfractures. Bone remodeling continuously
nausea, vomiting, memory loss, confusion, mus-
replaces old matrix with new matrix in a steady-
cle weakness, increased urine excression, and
state process of osteoclastic destruction of dam-
dehydration, and metabolic bone disease (see
aged bone and generation of new bone by os-
below).
teoblasts. This aspect of bone physiology is the
subject of numerous books [44, 48]. Hypocalcemia. may be due to inadequate di-
etary intake of Ca, vitamin D, or insufficient
Mineralization of Bone. The mineral in
sunlight. The most common endocrine cause
bone is hydroxyapatite, and makes approxi-
is inadequate or nonexistent secretion of PTH
mately 60 – 65 wt % of bone. For the hexag-
(primary hypoparathyroidism). Hypocalcemia
onal form of hydroxyapatite, the content of
is also caused by defects of the PTH receptor
the unit cell is Ca10 (PO4 )6 (OH)2 . In vitro, hy-
in the target cells and is characterized by a resis-
droxyapatite can be generated by mixing CaCl2
tance to peripheral tissue to PTH rather than by
with KPO4 . An unstable amorphous phase
a low amount of active hormone (pseudohypor-
(ACP1) is initially formed, followed by the ap-
parathyroidism). The features of hypocalcemia
pearance of a second amorphous phase (ACP2),
include neuromuscular excitability, which may
which is less soluble than ACP1. ACP2 then
result in tetany and cardiac conduction defects.
transforms to Ca4 H(PO4 )3 , which polymerizes
into deficient hydroxyapatite [49, 50]. Other ions
can influence hydroxyapatite formation. Fluo-
ride generates two crystal forms: hydroxyapatite 6.9. Diseases of Bone
covered with fluorapatite, and fluorapatite co-
vered with hydroxyapatite [51]. In contrast, The strength of bone depends in part on the
magnesium, carbonate, and cadmium inhibit molecular structure and organization of its con-
hydroxyapatite formation by substitution into stituent mineral crystals in their organic matrix
the apatite crystals, preventing further crystal- [61]. Most common diseases of bone cause in-
lization. The inhibition of crystal growth by creased propensity for fracture, and are due to a
magnesium can be attenuated by fluoride ion failure in the ability to generate adequate matrix
[52, 53]. In vivo, hydroxyapatite crystal for- or hydroxyapatite.
mation and attachment to collagen is regulated Osteoporosis is characterized by a reduc-
by calcium-binding proteins. Osteopontin and tion in mineral content per unit volume of bone
bone sialoprotein initiate and regulate crystal and is caused by reduced 17- β-estradiol secre-
growth and mediate the turnover of bone in tion (Type I) or a variety of mechanisms includ-
areas of growth [54, 55]. In compact bone, hy- ing deficiencies in calcium, vitamins C, D or
droxyapatite is maintained by osteocalcin [14, K, hypogonadism, hyperthyroidism, glucocorti-
56, 57] and osteonectin [58 – 60]. coid excess, rheumatoid arthritis, and immobi-
lization (Type II) [62]. Treatment of osteoporo-
sis includes Ca supplements, vitamin D and bis-
12 Calcium and Calcium Alloys