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ZINC OXIDE (zingk OX ide) is used to treat or prevent minor skin irritations such as burns, cuts, and diaper rash. Some products may be used
as a sunscreen.
What should I tell my health care provider before I take this medicine?
They need to know if you have any of these conditions:
an unusual or allergic reaction to zinc oxide, other medicines, foods, dyes, or preservatives
breast-feeding
Syllabus
Questions:
1.
Define and differentiate between Ointment and creams, lotion and liniment. (98) [4+4]
2.
3.
4.
Write a note on different types of raw materials that are used in the manufacture of semisolid
dosage forms. What are the factors that affect skin penetration of drugs from semisolids (96)[16]
5.
6.
How do you select the ointment base for a water soluble and insoluble drug to be incorporated
for a medicinal preparation. Discuss on the selection of ointment base
(94) [16]
7.
Discuss on the importance of packing materials for ointments. What is the influence of packing
materials for ointment storage? (94) [16]
8.
Write in brief the factors governing the selection of ointment bases. (93) [6]
9.
[8]
INTRODUCTION
Pharmaceutical semisolid dosage preparations include ointments, pastes, cream, emulsions, gels
and rigid foams.
Ointments are soft semisolid preparations meant for external application to the skin or mucous
membrane. They usually contain medicament, which is either dissolved or suspended in the base.
They have emollient and protective action.
Creams are semisolid emulsions for external application and are generally of softer consistency
and lighter than ointments.
They are less greasy and are easy to apply.
Pastes are semisolid preparations for external application that differs from similar products in
containing a high proportion of finely powdered medicaments. They are stiffer and are usually
employed for their protective action and for their ability to absorb serous discharges from skin
lesions.
Thus when protective, rather than therapeutic action is desired, the formulation
pharmacists will favor a paste, but when therapeutic action is required, he will prefer ointments
and creams.
Jellies are transparent or translucent, non-greasy, semisolid preparation mainly used externally.
In these systems the liquid phase is entrapped within a three-dimensional polymeric matrix in
which a high degree of physical cross-linking has been introduced.
The polymers (gelling agents) used include:
Natural Polymers :
gelatin.
nthetic polymers:
STRUCTURE OF SKIN
The skin has three main layers: the epidermis, dermis and hypodermis.
Epidermis is the outermost layer. It consists of:
(a) The basal layer (innermost) is one cell thick layer. Its cells divide constantly and the daughter
cells are steadily pushed towards the surface.
(b) The prickle cell layer: The cells in this region are linked by tiny bridges or prickles.
(c) The granular layer: When they reach this region, the upwardly moving cells become granules and
begin to synthesize the inert protein keratin.
(d) The horny layer (stratum corneum). This is the outermost layer and the cells are heavily
keratinized and dead. The dead cells sloughs off gradually.
Dermis is the middle and the main part of the skin. The dermis is made up of protein collagen and
elastin. The collagen is in the form of gel that is reinforced by a framework of elastin.
Dermis contains the following structures:
(a) Blood vessels, lymphatics and nerves.
(b) Epidermal appendages e.g. hair follicles, sebaceous glands and sweat glands.
Hypodermis, the innermost layer, consists of adipose tissues. It gives physical protection and
thermal insulation to underlying structures.
N.B.
Epidermis is non-granular but is penetrated by hair follicles, sebaceous glands and sweat glands.
Sebum is the secretion of sebaceous glands. Sebum is a mixture of fatty substances and emulsifiers; it
mixes with water producing a fluid of pH 5.5 that covers the skin surface and permeates the upper layer of
keratinized cells this is called the acid-mantle of skin.
Keratin is hydrophillic, the stratum corneum normally contains about 20% w/w of water, the amount varying
with atmospheric humidity. This moisture keeps the skin supple and if its level falls below about 12% the
cells becomes dry and brittle and then shrink and curl at the edges, making the skin feel rough.
Cracking may follow, causing discomfort. Loss of water may be the result of excessive evaporation, overusage of detergents (which removes sebum) and cold weather (which inhibits sebum production).
The horny layer is thickest on palms and soles and thinnest on the face; penetration rate increases with decreased
thickness of horny layer.
Creams are easier to apply and remove. Oil in water (o/w) creams mix with sebum and are more
suitable for weeping or wounded surface.
(b) Hydration of stratum corneum
An occlusive layer reduces evaporation of water from skin, increasing hydration of the horny layer
and, therefore, promotes penetration of medicament.
e.g. hydrocarbons, wool fat and isopropyl myristate containing ointments produce occlusive films
on the skin. Water in oil (o/w) type creams have some occlusive effects.
Humectants like glycerols are not good for retaining water because at low atmospheric
humidities, because they tend to increase loss of water by absorbing it from the skin.
(c) Penetration of the epidermis
Bases miscible with the sebum penetrate into the regions of the skin in which sebum is found.
e.g. Woolfat (originating from sebaceous glands of sheep) penetrates into the skin.
Vegetable oils penetrate more slowly and liquid paraffin does not penetrate at all.
(d) Alteration of skin permeability
Penetration can be improved by dissolving the medicament in an organic liquid such as ethanol,
dimethylformamide(DMF), dimethyl acetamide, dimethylsulfoxide (DMSO) and propylene glycol.
They increases the hydration of skin.
OINTMENT
Definition: Ointments are semisolid preparations for application to the skin or mucosae. The
ointment bases are almost always anhydrous and generally contains one or more medicaments in
suspension or solution.
2.
3.
4.
5.
The medicament should be finely divided and uniformly distributed throughout the base.
Classification of ointments
According to their therapeutic properties based on penetration of skin.
NT BASES
The ointment base is that substance or part of an ointment preparation which serves as carrier or
vehicle for the medicament.
An ideal ointment base should be inert, stable, smooth, compatible with the skin, non-irritating
and should release the incorporated medicaments readily.
Classification of ointment bases:
1.
Oleaginous bases
2.
Absorption bases
3.
Water-miscible bases
4.
OLEAGINOUS BASES
These bases consists of oils and fats. The most important are the
Hydrocarbons i.e. petrolatum, paraffins and mineral oils.
The animal fat includes lard.
The combination of these materials can produce a product of desired melting point and viscosity.
(a) Petrolatum (Soft paraffin)
This is a purified mixture of semi-solid hydrocarbons obtained from petroleum or heavy
lubricating oil.
Yellow soft paraffin (Petrolatum; Petroleum jelly)
This a purified mixture of semisolid hydrocarbons obtained from petroleum. It may contain
suitable stabilizers like, antioxidants e.g. -tocopherol (Vitamin E), butylated hydroxy toluene
(BHT) etc.
Melting range : 38 to 560C.
White soft paraffin (White petroleum jelly, White petrolatum)
This a purified mixture of semisolid hydrocarbons obtained from petroleum, and wholly or
partially decolorized by percolating the yellow soft paraffin through freshly burned bone black or
adsorptive clays.
Melting range : 38 to 560C.
Use: The white form is used when the medicament is colourless, white or a pastel shade. This
base is used in
Dithranol ointment B.P.
Ammoniated Mercury and Coal tar ointment B.P.C.
Zinc ointment B.P.C.
(b) Hard paraffin (Paraffin)
This is a mixture of solid hydrocarbons obtained from petroleum.
It is colourless or white, odorless, translucent, wax-like substance. It solidifies between 50 and
570C and is used to stiffen ointment bases.
(c) Liquid paraffin (Liquid petrolatum,; White mineral oil)
It is a mixture of liquid , hydrocarbons obtained from petroleum. It is transparent, colourless,
odourless, viscous liquid.
On long storage it may oxidize to produce peroxides and therefore, it may contain tocopherol or
BHT as antioxidants.
It is used along with hard paraffin and soft paraffin to get a desired consistency of the ointment.
Tubes for eye, rectal and nasal ointments have nozzles with narrow orifices through which it is
difficult to expel very viscous ointments without the risk of bursting the tube. To facilitate the
extrusion upto 25% of the base may be replaced by liquid paraffins.
Advantages of hydrocarbons bases:
(i) They are not absorbed by the skin. They remain on the surface as an occlusive layer that restricts
the loss of moisture hence, keeps the skin soft.
(ii) They are sticky hence ensures prolonged contact between skin and medicament.
(iii) They are almost inert. They consist largely of saturated hydrocarbons, therefore, very few
incompatibilities and little tendency of rancidity are there.
(iv) They can withstand heat sterilization, hence, sterile ophthalmic ointments can be prepared with it.
(v) They are readily available and cheap.
Disadvantages of hydrocarbon bases;
(i) It may lead to water logging followed by maceration of the skin if applied for a prolonged period.
(ii) It retains body heat, which may produce an uncomfortable feeling of warmth.
(iii) They are immiscible with water; as a result rubbing onto the surface and removal after treatment
both are difficult.
(iv) they are sticky, hence makes application unpleasant and leads to contamination of clothes.
(v) Water absorption capacity is very low, hence, these bases are poor in absorbing exudate from
moist lesions.
ABSORPTION BASE
The term absorption base is used to denote the water absorbing or emulsifying property of these
bases and not to describe their action on the skin.
These bases (some times called emulsifiable ointment bases) are generally anhydrous
substances which have the property of absorbing (emulsifying) considerable quantity of water yet
retaining its ointment-like consistency.
Preparations of this type do not contain water as a component of their basic formula but
if water is incorporated a W/O emulsion results.
Wool Fat (anhydrous lanolin)
It is the purified anhydrous fat like substance obtained from the wool of sheep.
It is practically insoluble in water but can absorb water upto 50% of its own weight. Therefore it
is used in ointments the proportion of water or aqueous liquids to be incorporated in hydrocarbon
base is too large.
Due to its sticky nature it is not used alone but is used along with other bases in the preparation
of a number of ointments.
e.g. Simple ointment B.P. contains 5% and the B.P. eye ointment base contains 10% woolfat.
Hydrous Wool Fat (Lanolin)
It is a mixture of 70 % w/w wool fat and 30 % w/w purified water. It is a w/o emulsion. Aqueous
liquids can be emulsified with it.
Example:- Hydrous Wool Fat Ointment B.P.C., Calamine Coal Tar Ointment.
Wool Alcohol
It is the emulsifying fraction of wool fat. Wool alcohol is obtained from wool fat by treating it with
alkali and separating the fraction containing cholesterol and other alcohols. It contains not less
than 30% of cholesterol.
Use:-
It is used as an emulsifying agent for the preparation of w/o emulsions and is used to absorb
water in ointment bases.
It is also used to improve the texture, stability and emollient properties of o/w emulsions.
Examples :- Wool alcohol ointment B.P. contains 6% wool alcohol and hard, liquid and soft
paraffin.
Beeswax
It is purified wax, obtained from honey comb of bees.
It contains small amount of cholesterol. It is of two types: (a) yellow beeswax and (b) white
beeswax.
Use:Beeswax is used as a stiffening agent in ointment preparations.
Examples:-Paraffin ointment B.P.C. contains beeswax.
Cholesterol
It is widely distributed in animal organisms. Wool fat is also used as a source of cholesterol.
Use:- It is used to increase the water absorbing power of an ointment base.
Example:- Hydrophilic petroleum U.S.P. contains:
Cholesterol
Stearyl alcohol
3%
3%
White beeswax
White soft paraffin
8%
86%
Uses: they are used to prepare o/w creams and are easily removable ointment bases
e.g. Compound Benzoic Acid Ointment (Whitfields Ointment) used as antifungal ointment.
Advantages of water miscible bases:
(i) Readily miscible with the exudates from lesions.
(ii) Reduced interference with normal skin function.
(iii) Good contact with the skin, because of their surfactant content.
(iv) High cosmetic acceptability, hence there is less likelihood of the patients discontinuing treatment.
(v) Easy removal from the hair.
viscous liquids
Macrogols 1500
Macrogols 1540, 3000, 4000, 6000
greasy semi-solids
waxy solids.
Certain other substances which are used as water soluble ointment bases include tragacanth,
gelatin, pectin, silica gel, sodium alginate, cellulose derivatives, etc.
Medicaments which are both soluble in oil and water are most readily absorbed though the skin.
Whereas animal and vegetable fats and oils normally penetrate the skin.
Animals fats, e.g. lard and wool fat when combined with water, penetrates the skin.
o/w emulsion bases release the medicament more readily than greasy bases or w/o emulsion
bases.
(b) Effect on the skin
Greasy bases interfere with normal skin functions i.e. heat radiation and sweating. They are
irritant to the skin.
o/w emulsion bases and other water miscible bases produce a cooling effect due to the
evaporation of water.
(c) Miscibility with skin secretion and sebum
Skin secretions are more readily miscible with emulsion bases than with greasy bases. Due to this the drug is more rapidly
and completely released to the skin.
(e) Non-irritant
All bases should be highly pure and bases specially for eye ointments should be non-irritant and free from foreign particle.
The ointment bases should be easily applicable as well as easily removable from the skin by simple washing with water.
Stiff and sticky ointment bases require much force to spread on the skin and during rubbing newly formed tissues on the
skin may be damaged.
2. Pharmaceutical factors
(a) Stability
Fats and oils obtained from animal and plant sources are prone to oxidation unless they are
suitably preserved. Due to oxidation odour comes out. This type of reactions are
called rancidification. Lard, from animal origin, rancidify rapidly. Soft paraffin, simple ointment
and paraffin ointment are inert and stable. Liquid paraffin is also stable but after prolonged
storage it gets oxidized. Therefore, an antioxidant liketocopherol (Vit -E) may be incorporated.
Other antioxidants those may be used are butylated hydroxy toluene (BHT) or butylated hydroxy
hydroxy anisole (BHA).
(b) Solvent properties
Most of the medicaments used in the preparation of ointments are insoluble in the ointment bases therefore, they are
finely powdered and are distributed uniformly throughout the base.
(d) Consistency
The ointments produced should be of suitable consistency. They should neither be hard nor too soft. They should
withstand climatic conditions. Thus in summer they should not become too soft and in winter not too hard to be difficult to
remove from the container and spread on the skin.
The consistency of an ointment base can be controlled by varying the ratio of hard and liquid paraffin.
PREPARATION OF OINTMENTS
A well-made ointment is
(a) Uniform throughout i.e. it contains no lumps of separated high melting point ingredients of the
base, there is no tendency for liquid constituents to separate and insoluble powders are evenly
dispersed.
(b) Free from grittiness, i.e. insoluble powders are finely subdivided and large lumps of particles
are absent. Methods of preparation must satisfy this criteria.
Two mixing techniques are frequently used in making ointments:
1. Fusion, in which ingredients are melted together and stirred to ensure homogeneity.
Cautions:
(i) Melting time is shortened by grating waxy components (i.e. beeswax, wool alcohols, hardparaffin, higher fatty alcohols and emulsifying waxes) by stirring during melting and by lowering
the dish as far as possible into the water bath so that the maximum surface area is heated.
(ii) The surface of some ingredients discolors due to oxidation e.g. wool fats and wool alcohols and
this discolored layers should be removed before use.
(iii) After melting, the ingredients should be stirred until the ointment is cool, taking care not to cause
localized cooling, e.g. by using a cold spatula or stirrer, placing the dish on a cold surface (e.g. a
plastic bench top) or transferring to a cold container before the ointment has fully set. If these
precautions are ignored, hard lumps may separate.
(iv) Vigorous-stirring, after the ointment has begun to thicken, causes excessive aeration and should
be avoided.
(v) Because of their greasy nature, many constituents of ointment bases pickup dirt during storage,
which can be seen after melting. This is removed from the melt by allowing it to sediment and
decanting the supernatant, or by passage through muslin supported by a warm strainer. In both
instances the clarified liquid is collected in another hot basin.
(vi) If the product is granular after cooling, due to separation of high m.p. constituents, it should be
remelted, using the minimum of heat, and again stirred and cooled.
Example:
(i) Simple ointment B.P. contains
Type of preparation:
Wool fat
50g
Hard paraffin
50g
Cetostearyl alcohol
50g
850g
Procedure:
Hard paraffin and cetostearyl alcohol on water-bath. Wool fat and white soft paraffin are mixed
and stirred until all the ingredients are melted. If required decanted or strained and stirred until
cold and packed in suitable container.
(ii) Paraffin ointment base
Type of preparation: Hydrocarbon ointment base
(iii) Wool alcohols ointment B.P.
Type of preparation: Absorption base
(iv) Emulsifying ointment B.P.
Type of preparation: Water-miscible ointment base.
(v) Macrogol ointment B.P.C
Type of preparation: Water soluble ointment base
Formula:
Macrogol 4000
Liquid Macrogol 300
Method: Macrogol 4000 is melted and previously warmed liquid macrogol 300 is added. Stirred
until cool.
(iii) Finally liquid ingredients are incorporated. To avoid loss from splashing, a small volume of liquid
is poured into a depression in the ointment an thoroughly incorporated before more is added in
the same way. Splashing is more easily controlled in a mortar than on a tile.
Example:
(i) Whitfield ointment (Compound benzoic acid ointment B.P.C.)
Formula:
6gm
3gm
91gm
Method: Benzoic acid and salicylic acid are sieved through No. 180 sieves. They are mixed on the
tile with small amount of base and levigated until smooth and dilute gradually.
(ii) Salicylic acid sulphur ointment B.P.C.
Water
Procedure:
(i) KI is dissolved in water. I2 is dissolved in it.
(ii) Woolfat and yellow soft paraffin are melted together over water bath. Melted mass is cooled to
about 400C.
(iii) I2 solution is added to the melted mass in small quantities at a time with continuos stirring until a
uniform mass is obtained.
(iv) It is cooled to room temperature and packed.
Use: - Ringworm in cattle.
(b) Ointment containing combined iodine
Fixed oils and many vegetable and animal fats absorb iodine which combines with the double
bonds of the unsaturated constituents, e.g.
CH3.(CH2) 2.CH = CH.(CH2) 7.COOH + I2 CH3.(CH2) 2.CHI CHI.(CH2) 7.COOH
Oleic acid
di-iodostearic acid
For o/w emulsion systems the following emulsifying agents are used:
(i) water soluble soap
(ii) cetyl alcohol
(iii)glyceryl monostearate
(iv) combination of emulsifiers: triethanolamine stearate + cetyl alcohol
(v) non-ionic emulsifiers: glyceryl monostearate, glyceryl monooelate, propylene glycol
stearate
For w/o emulsion creams the following emulsifiers are used:
(i) polyvalent ions e.g magnesium, calcium and aluminium are used.
(ii) combination of emulsifiers: beeswax + divalent calcium ion
The viscosity of this type of creams prevent coalescence of the emulsified phases and helps in
stabilizing the emulsion.
Example:
Cold cream:
Procedure:
(i) Water immiscible components e.g. oils, fats, waxes are melted together over water bath (70 0C).
(ii) Aqueous solution of all heat stable, water soluble components are heated (70 0C).
(iii) Aqueous solution is slowly added to the melted bases with continuous stirring until the product
cools down and a semi-solid mass is obtained.
N.B. The aqueous phase is heated otherwise high melting point fats and waxes will immediately
solidify on addition of cold aqueous solution.
Steam
jacketed
Equipment:
kettle
Dissolved
Filtered
(A) Simultaneou
s blending
Batch sizes are on weight basis. For weighing a hydraulic load cell is fitted under one of the leg
of the mixing kettle.
Cooled to 43 to 450C
Addition of perfume
Dispersed or dissolved
4. Homogenization
Creams or ointments
5. Storage of semisolids
Stored before packaging. In the mean time Q.C. report comes. Stored in a tight-fitting
stainless steel (SS#316) container.
STABILITY OF OINTMENTS
The ointments should remain stable from the time of preparation to the time when the whole of it
is consumed by the user.
(i) To stop microbial growth preservatives are added. Preservatives for ointment includes : phydroxy benzoates, phenol, benzoic acid, sorbic acid, methyl paraben, propyl paraben, quaternary
ammonium compounds, mercury compounds etc.
(ii) The preservatives should not react with any of the component of the formulation. Plastic
containers may absorb the preservative and thereby decreasing the concentration of preservative
available for killing the bacteria.
(iii) Some ingredients like wool fat and wool alcohols are susceptible to oxidation. Therefore, a
suitable antioxidant may be incorporated to protect the active ingredients from oxidation.
(iv) Incompatible drugs, emulsifying agents and preservatives must be avoided. The drugs which are
likely to hydrolyze must be dispensed in an anhydrous base.
(v) Humectants such as, glycerin, propylene glycol and sorbitol may be added to prevent the loss of
moisture from the preparation.
(vi) Ointment must be stored at an optimum temperature otherwise separation of phases may take
place in the emulsified products which may be very difficult to remix to get a uniform product.
Preservatives in ointments
FOR
PHARMACEUTICS
THEORY
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well,here is some details:
1-Pastes:paste is a substance that behaves as a solid until a sufficiently large load or stress is applied,at which point it flows like a fluid,paste typically
consists of a suspension of small particles in a background fluid,the small particles are jammed together like grains of sand on a beach,forming a
disordered,glassy or amorphous structure, and giving pastes their solid-like character,in pharmacology,paste is basic pharmaceutical form,it consists of
fatty base (e.g. petroleum jelly) and at least 25% solid substance (e.g. zinc oxide).
2-Ointments:an ointment is a viscous semisolid preparation used topically on a variety of body surfaces.these include the skin and the mucus
membranes of the eye (an eye ointment),vagina,glans and nose,an ointment may or may not be medicated.
3-creams:Cream is semi-solid emulsion,that is mixtures of oil and water,they are divided into two types:oil-in-water (O/W) creams which are composed
of small droplets of oil dispersed in a continuous aqueous phase,and water-in-oil (W/O) creams which are composed of small droplets of water
dispersed in a continuous oily phase.
Viscosity?
Paste - Thick, almost solid form.
Ointment - Not as thick, like grease
Cream - Even less thick, like a thick oil.
sunblock.
definition (more)
definition of Wikipedia
Advertizing
analogical dictionary
Inorganic Chemicals - Anions - Oxygen Compounds[Hyper.]
Zinc Compounds - Oxides[Hyper.]
oxide; hydroxide[ClasseHyper.]
compos d'oxygne (fr)[Classe]
(enamel)[termes
lis]
chemistry[Domaine]
CompoundSubstance[Domaine]
chemical compound, compound - pigment[Hyper.]
oxidate, oxidise, oxidize[Driv]
oxide[Hyper.]
Chinese white, cover white, zinc white[Element]
Wikipedia
Zinc oxideupdate
Zinc oxide
Other names
Zinc white, Calamine, philosopher's wool, Chinese white, flowers of zinc
Identifiers
CAS number
PubChem
ChemSpider
EC number
ChEBI
ChEMBL
RTECS number
ATCvet code
1314-13-2
14806
14122
215-222-5
CHEBI:36560
CHEMBL1201128
ZH4810000
QA07XA91
InChI
InChI=1S/O.Zn
Key: XLOMVQKBTHCTTD-UHFFFAOYSA-N
Properties
Molecular formula
Molar mass
Appearance
Odor
Density
Melting point
Boiling point
Solubility inwater
Band gap
Refractive index(nD)
ZnO
81.408 g/mol
White solid
odorless
5.606 g/cm3
1975 C (decomposes)[1]
2360 C
0.16 mg/100 mL (30 C)
3.3 eV (direct)
2.0041
Std enthalpy of
formationfHo298
Standard molar
entropy So298
-348.0 kJ/mol
MSDS
EU Index
EU classification
R-phrases
S-phrases
NFPA 704
ICSC 0208
030-013-00-7
Dangerous for the environment (N)
R50/53
S60, S61
Thermochemistry
43.9 JK1mol1
Hazards
1
2
0
W
Flash point
1436 C
Other anions
Zinc sulfide
Zinc selenide
Zinc telluride
Cadmium oxide
Mercury(II) oxide
Related compounds
Other cations
Zinc oxide is an inorganic compound with the formula ZnO. ZnO is a white powder that is insoluble in water, which is widely used as an additive in numerous
materials and products including plastics, ceramics, glass, cement, lubricants [2], paints, ointments, adhesives, sealants, pigments, foods (source of
Zn nutrient), batteries, ferrites, fire retardants, and first aid tapes. It occurs naturally as the mineral zincite but most zinc oxide is produced synthetically.[3]
In materials science, ZnO is a wide-bandgap semiconductor of the II-VI semiconductor group (since oxygen was classed as an element of VIA group (the 6th
main group, now referred to as 16th) of the periodic table and zinc, a transition metal, as a member of the IIB (2nd B), now 12th, group). The native doping of
the semiconductor (due to oxygen vacancies) is n-type. This semiconductor has several favorable properties, including good transparency, high electron
mobility, wide bandgap, and strong room-temperatureluminescence. Those properties are used in emerging applications for transparent electrodes in liquid
crystal displays, in energy-saving or heat-protecting windows, and in electronics as thin-film transistors and light-emitting diodes.
Contents
1 Chemical properties
2 Physical properties
2.1 Structure
3 Production
4 Applications
4.3 Medical
4.6 Pigment
4.7 Coatings
5 Potential applications
5.1 Electronics
5.3 Spintronics
5.4 Piezoelectricity
6 History
7 Safety
8 In popular culture
9 See also
10 References
11 Reviews
12 External links
Chemical properties
ZnO occurs as a white powder. The mineral zincite usually contains manganese and other impurities that confer a yellow to red color.[4] Crystalline zinc oxide
is thermochromic, changing from white to yellow when heated and in air reverting to white on cooling. [5] This color change is caused by a small loss of oxygen
to the environment at high temperatures to form the non-stoichiometric Zn 1+xO, where at 800 C, x = 0.00007.[5]
Zinc oxide is an amphoteric oxide. It is nearly insoluble in water, but it is soluble in (degraded by) most acids, such as hydrochloricacid:[6][7]
ZnO + 2 HCl ZnCl2 + H2O
Bases also degrade the solid to give soluble zincates:
ZnO + 2 NaOH + H2O Na2[Zn(OH)4]
ZnO reacts slowly with fatty acids in oils to produce the corresponding carboxylates, such as oleate or stearate. ZnO forms cement-like products when mixed
with a strong aqueous solution of zinc chloride and these are best described as zinc hydroxy chlorides.[8] This cement was used in dentistry.[9]
Hopeite
ZnO also forms cement-like products when treated with phosphoric acid; related materials are used in dentistry.[9] A major component of zinc phosphate
cement produced by this reaction is hopeite, Zn3(PO4)24H2O.[10]
ZnO decomposes into zinc vapor and oxygen only at around 1975 C, reflecting its considerable stability. Heating with carbon converts the oxide into the
metal, which is more volatile than the oxide. [11]
ZnO + C Zn + CO
Zinc oxide can react violently with aluminium and magnesium powders, with chlorinated rubber and linseed oil on heating causing fire and explosion hazard. [12]
[13]
It reacts with hydrogen sulfide to give the sulfide. This reaction is used commercially in removing H2S using ZnO powder (e.g., as deodorant).
ZnO + H2S ZnS + H2O
When ointments containing ZnO and water are melted and exposed to ultraviolet light, hydrogen peroxide is produced.[7]
Physical properties
Wurtzite structure
Structure
Zinc oxide crystallizes in two main forms, hexagonal wurtzite[14] and cubic zincblende. The wurtzite structure is most stable at ambient conditions and thus
most common. The zincblende form can be stabilized by growing ZnO on substrates with cubic lattice structure. In both cases, the zinc and oxide centers
are tetrahedral, the most characteristic geometry for Zn(II).
In addition to the wurtzite and zincblende polymorphs, ZnO can be crystallized in the rocksalt motif at relatively high pressures about 10 GPa.[15]
Hexagonal and zincblende polymorphs have no inversion symmetry (reflection of a crystal relative to any given point does not transform it into itself). This and
other lattice symmetry properties result in piezoelectricity of the hexagonal and zincblende ZnO, and pyroelectricityof hexagonal ZnO.
The hexagonal structure has a point group 6 mm (Hermann-Mauguin notation) or C6v (Schoenflies notation), and the space group is P63mc or C6v4. The lattice
constants are a = 3.25 and c = 5.2 ; their ratio c/a ~ 1.60 is close to the ideal value for hexagonal cell c/a = 1.633.[16] As in most group II-VI materials, the
bonding in ZnO is largely ionic (Zn2+O2) with the corresponding radii of 0.074 nm for Zn 2+ and 0.140 nm for O2. This property accounts for the preferential
formation of wurtzite rather than zinc blende structure, [17] as well as the strong piezoelectricity of ZnO. Because of the polar Zn-O bonds, zinc and oxygen
planes are electrically charged. To maintain electrical neutrality, those planes reconstruct at atomic level in most relative materials, but not in ZnO its
surfaces are atomically flat, stable and exhibit no reconstruction. This anomaly of ZnO is not fully explained yet. [18]
Mechanical properties
ZnO is a relatively soft material with approximate hardness of 4.5 on the Mohs scale.[2] Its elastic constants are smaller than those of relevant III-V
semiconductors, such as GaN. The high heat capacity and heat conductivity, low thermal expansion and high melting temperature of ZnO are beneficial for
ceramics.[19] ZnO's most stable phase being wurtzite, ZnO exhibits a very long lived optical phonon E2(low) with a lifetime as high as 133 ps at 10 K [20]
Among the tetrahedrally bonded semiconductors, it has been stated that ZnO has the highest piezoelectric tensor, or at least one comparable to that
of GaN and AlN.[21] This property makes it a technologically important material for many piezoelectrical applications, which require a large electromechanical
coupling.
Electrical properties
ZnO has a relatively large direct band gap of ~3.3 eV at room temperature. Advantages associated with a large band gap include higher breakdown voltages,
ability to sustain large electric fields, lower electronic noise, and high-temperature and high-power operation. The bandgap of ZnO can further be tuned to ~3
4 eV by its alloying withmagnesium oxide or cadmium oxide.[15]
Most ZnO has n-type character, even in the absence of intentional doping. Nonstoichiometry is typically the origin of n-type character, but the subject remains
controversial.[22] An alternative explanation has been proposed, based on theoretical calculations, that unintentional substitutional hydrogen impurities are
responsible.[23] Controllable n-type doping is easily achieved by substituting Zn with group-III elements such as Al, Ga, In or by substituting oxygen with groupVII elements chlorine or iodine.[24]
Reliable p-type doping of ZnO remains difficult. This problem originates from low solubility of p-type dopants and their compensation by abundant n-type
impurities. This problem is observed with GaN and ZnSe. Measurement of p-type in "intrinsically" n-type material is complicated by the inhomogeneity of
samples.[25]
Current limitations to p-doping does not limit electronic and optoelectronic applications of ZnO, which usually require junctions of n-type and p-type material.
Known p-type dopants include group-I elements Li, Na, K; group-V elements N, P and As; as well as copper and silver. However, many of these form deep
acceptors and do not produce significant p-type conduction at room temperature. [15]
Electron mobility of ZnO strongly varies with temperature and has a maximum of ~2000 cm2/(Vs) at 80 K.[26] Data on hole mobility are scarce with values in the
range 530 cm2/(Vs).[27]
Production
See also: Zinc smelting
For industrial use, ZnO is produced at levels of 105 tons per year[4] by three main processes:[19]
Laboratory synthesis
Synthetic ZnO crystals. Red and green color are associated with different concentrations of oxygen vacancies. [28]
A large number of specialised methods exist for producing ZnO for scientific studies and niche applications. These methods can be classified by the resulting
ZnO form (bulk, thin film, nanowire), temperature ("low", that is close to room temperature or "high", that is T ~ 1000 C), process type (vapor deposition or
growth from solution) and other parameters.
Large single crystals (many cubic centimeters) are usually grown by the gas transport (vapor-phase deposition), hydrothermal synthesis,[18][28][29] or melt growth.
[1]
However, because of high vapor pressure of ZnO, growth from the melt is problematic. Growth by gas transport is difficult to control, leaving the
hydrothermal method as a preference.[1] Thin films can be produced by chemical vapor deposition, metalorganic vapour phase
epitaxy, electrodeposition, pulsed laser deposition, sputtering, sol-gel synthesis, atomic layer deposition, spray pyrolysis, etc.
Ordinary white powdered zinc oxide can be produced in the laboratory by electrolyzing a solution of sodium bicarbonate with a zinc anode. Zinc hydroxide and
hydrogen gas are produced. The zinc hydroxide upon heating decomposes to zinc oxide.
Zn + 2 H2O Zn(OH)2 + H2
Zn(OH)2 ZnO + H2O
Nanophase ZnO
Nanophase ZnO can be synthesized into a variety of morphologies including nanowires, nanorods, tetrapods, nanobelts, nanoflowers, nanoparticles etc.
Nanostructures can be obtained with most above-mentioned techniques, at certain conditions, and also with the vapor-liquid-solid method.[18][30]
Rodlike nanostructures of ZnO can be produced via aqueous methods, which are attractive for the following reasons: They are low cost, less hazardous [citation
needed]
, and thus capable of easy scaling up; the growth occurs at a relatively low temperature, compatible with flexible organic substrates; there is no need for
the use of metal catalysts, and thus it can be integrated with well-developed silicon technologies. In addition, there are a variety of parameters that can be
tuned to effectively control the morphology and properties of the final product. Wet chemical methods have been demonstrated as a very powerful and
versatile technique for growing one dimensional ZnO nanostructures. [31]The synthesis is typically carried out at temperatures of about 90 C, in an equimolar
aqueous solution of zinc nitrate and hexamine, the latter providing the basic environment. Certain additives, such as polyethylene glycol or polyethylenimine,
can improve the aspect ratio of the ZnO nanowires. [32] Doping of the ZnO nanowires has been achieved by adding other metal nitrates to the growth solution.
[33]
The morphology of the resulting nanostructures can be tuned by changing the parameters relating to the precursor composition (such as the zinc
concentration and pH) or to the thermal treatment (such as the temperature and heating rate). [34]
Aligned ZnO nanowires on pre-seeded silicon, glass and gallium nitride substrates have been grown in aqueous solutions using aqueous zinc salts such as Zinc
nitrate and Zinc acetate in basic environments.[35] Pre-seeding substrates with ZnO creates sites for homogeneous nucleation of ZnO crystal during the
synthesis. Common pre-seeding methods include in-situ thermal decomposition of zinc acetate crystallites, spincoating of ZnO nanoparticles and the use
of physical vapor deposition methods to deposit ZnO thin films.[36][37] Pre-seeding can be performed in conjunction with top down patterning methods such
as electron beam lithography and nanosphere lithography to designate nucleation sites prior to growth. Aligned ZnO nanowires can be used in dye-sensitized
solar cells and field emission devices.[38][39]
Applications
The applications of zinc oxide powder are numerous, and the principal ones are summarized below. Most applications exploit the reactivity of the oxide as a
precursor to other zinc compounds. For material science applications, zinc oxide has high refractive index, high thermal conductivity, binding, antibacterial
and UV-protection properties. Consequently, it is added into materials and products including plastics, ceramics, glass, cement, rubber, lubricants, [2] paints,
ointments, adhesive, sealants, pigments, foods, batteries, ferrites, fire retardants, etc. [40]
Rubber manufacture
About 50% of ZnO use is in the rubber industry. Zinc oxide along with stearic acid is used in the vulcanization of rubber[19][41][42] ZnO additive also protect rubber
from fungi (see medical applications) and UV light.
Concrete industry
Zinc oxide is widely used for concrete manufacturing. Addition of ZnO improves the processing time and the resistance of concrete against water.[41]
Medical
Zinc oxide as a mixture with about 0.5% iron(III) oxide (Fe2O3) is called calamine and is used in calamine lotion. There are also two
minerals, zincite and hemimorphite, which have been historically called calamine. When mixed with eugenol, a ligand, zinc oxide eugenol is formed, which has
applications as a restorative and prosthodontic in dentistry.[9][43]
Reflecting the basic properties of ZnO, fine particles of the oxide have deodorizing and antibacterial [44] properties and for that reason are added into materials
including cotton fabric, rubber, and food packaging.[45][46] Enhanced antibacterial action of fine particles compared to bulk material is not intrinsic to ZnO and is
observed for other materials, such as silver.[47] This property is due to the increased surface area of the fine particles.
Zinc oxide is widely used to treat a variety of other skin conditions, in products such as baby powder and barrier creams to treat diaper
rashes, calamine cream, anti-dandruffshampoos, and antiseptic ointments.[48][49] It is also a component in tape (called "zinc oxide tape") used by athletes as a
bandage to prevent soft tissue damage during workouts. [50]
Zinc oxide can be used in ointments, creams, and lotions to protect against sunburn and other damage to the skin caused by ultraviolet light (see sunscreen). It
is the broadest spectrum UVA and UVB reflector that is approved for use as a sunscreen by the FDA, [51] and is completely photostable.[52] When used as an
ingredient in sunscreen, zinc oxide sits on the skins surface and is not absorbed into the skin, and blocks both UVA (320400 nm) and UVB (280320 nm) rays
of ultraviolet light. Because zinc oxide (and the other most common physical sunscreen, titanium dioxide) are not absorbed into the skin, they are
nonirritating, nonallergenic, and non-comedogenic.[53]
Many sunscreens use nanoparticles of zinc oxide (along with nanoparticles of titanium dioxide) because such small particles do not scatter light and therefore
do not appear white. Although there has been concern that they might be absorbed into the skin, [54][55] comprehensive reviews of the medical literature have
not uncovered any risk.[56]
Cigarette filters
Zinc oxide is a constituent of cigarette filters for removal of selected components from tobacco smoke. A filter consisting of charcoal impregnated with zinc
oxide and iron oxide removes significant amounts of HCN and H2S from tobacco smoke without affecting its flavor.[40]
Food additive
Zinc oxide is added to many food products, including breakfast cereals, as a source of zinc,[57] a necessary nutrient. (Zinc sulfate is also used for the same
purpose.) Some prepackaged foods also include trace amounts of ZnO even if it is not intended as a nutrient.
Pigment
Zinc white is used as a pigment[58] in paints and is more opaque than lithopone, but less opaque than titanium dioxide. It is also used in coatings for paper.
Chinese white is a special grade of zinc white used in artists' pigments. It is also a main ingredient of mineral makeup.[59]
Coatings
Paints containing zinc oxide powder have long been utilized as anticorrosive coatings for metals. They are especially effective for galvanized iron. Iron is
difficult to protect because its reactivity with organic coatings leads to brittleness and lack of adhesion. Zinc oxide paints retain their flexibility and adherence
on such surfaces for many years.[40]
ZnO highly n-type doped with Al, Ga, or In is transparent and conductive (transparency ~90%, lowest resistivity ~104 cm[60]). ZnO:Al coatings are used for
energy-saving or heat-protecting windows. The coating lets the visible part of the spectrum in but either reflects the infrared (IR) radiation back into the room
(energy saving) or does not let the IR radiation into the room (heat protection), depending on which side of the window has the coating. [4]
Plastics, such as polyethylene naphthalate (PEN), can be protected by applying zinc oxide coating. The coating reduces the diffusion of oxygen with PEN.
[61]
Zinc oxide layers can also be used on polycarbonate (PC) in outdoor applications. The coating protects PC form solar radiation and decreases the oxidation
rate and photo-yellowing of PC.[62]
Potential applications
Electronics
ZnO has wide direct band gap (3.37 eV or 375 nm at room temperature). Therefore, its most common potential applications are in laser diodes and light
emitting diodes (LEDs).[64] Some optoelectronic applications of ZnO overlap with that of GaN, which has a similar bandgap (~3.4 eV at room temperature).
Compared to GaN, ZnO has a larger exciton binding energy (~60 meV, 2.4 times of the room-temperature thermal energy), which results in bright roomtemperature emission from ZnO. ZnO can be combined with GaN for LED-applications. For instance as TCO layer and ZnO nanostructures provide better light
outcoupling.[65] Other properties of ZnO favorable for electronic applications include its stability to high-energy radiation and to wet chemical etching.
[66]
Radiation resistance[67] makes ZnO a suitable candidate for space applications. ZnO is the most promising candidate in the field of random lasers to produce
an electronically pumped UV laser source.
The pointed tips of ZnO nanorods result in a strong enhancement of an electric field. Therefore, they can be used as field emitters.[68]
Aluminium-doped ZnO layers are used as a transparent electrodes. The constituents Zn and Al are much cheaper and less poisonous compared to the generally
used indium tin oxide (ITO). One application which has begun to be commercially available is the use of ZnO as the front contact for solar cells or of liquid
crystal displays.[69]
Transparent thin-film transistors (TTFT) can be produced with ZnO. As field-effect transistors, they even may not need a pn junction, [70] thus avoiding the ptype doping problem of ZnO. Some of the field-effect transistors even use ZnO nanorods as conducting channels. [71]
Spintronics
ZnO has also been considered for spintronics applications: if doped with 110% of magnetic ions (Mn, Fe, Co, V, etc.), ZnO could become ferromagnetic, even at
room temperature. Such room temperature ferromagnetism in ZnO:Mn has been observed,[74] but it is not clear yet whether it originates from the matrix itself
or from secondary oxide phases.
Piezoelectricity
The piezoelectricity in textile fibers coated in ZnO have been shown capable of fabricating "self-powered nanosystems" with everyday mechanical stress from
wind or body movements.[75][76]
In 2008 the Center for Nanostructure Characterization at the Georgia Institute of Technology reported producing an electricity generating device (called
flexible charge pump generator) delivering alternating current by stretching and releasing zinc oxide nanowires. This mini-generator creates an oscillating
voltage up to 45 millivolts, converting close to seven percent of the applied mechanical energy into electricity. Researchers used wires with lengths of 0.2
0.3 mm and diameters of three to five micrometers, but the device could be scaled down to smaller size. [77]
History
It is hardly possible to trace the first usage of zinc oxide zinc compounds were used by early humans, in processed and unprocessed forms, as a paint or
medicinal ointment, but their composition is uncertain.
The use of pushpanjan, probably zinc oxide, as a salve for eyes and open wounds, is mentioned in the Indian medical text the Charaka Samhita, thought to
date from 500 BC or before.[78] Zinc oxide ointment is also mentioned by the Greek physician Dioscorides (1st century AD.)[79] Avicenna mentions zinc oxide
in The Canon of Medicine (1025 AD), which mentioned it as a preferred treatment for a variety of skin conditions, including skin cancer. Though it is no longer
used for treating skin cancer, it is still widely used to treat a variety of other skin conditions, in products such as baby powder and creams against diaper
rashes, calamine cream, anti-dandruff shampoos, and antiseptic ointments.[48]
The Romans produced considerable quantities of brass (an alloy of zinc and copper) as early as 200 BC by a cementation process where copper was reacted
with zinc oxide.[80]The zinc oxide is thought to have been produced by heating zinc ore in a shaft furnace. This liberated metallic zinc as a vapor, which then
ascended the flue and condensed as the oxide. This process was described by Dioscorides in the 1st century AD.[81] Zinc oxide has also been recovered from zinc
mines at Zawar in India, dating from the second half of the first millennium BC. This was presumably also made in the same way and used to produce brass. [79]
From the 12th to the 16th century zinc and zinc oxide were recognized and produced in India using a primitive form of the direct synthesis process. From India,
zinc manufacture moved to China in the 17th century. In 1743, the first European zinc smelter was established in Bristol, United Kingdom.[82]
The main usage of zinc oxide (zinc white) was again paints and additive to ointments. Zinc white was accepted as a watercolor by 1834 but it did not mix well
with oil. This problem was quickly solved by optimizing the synthesis of ZnO. In 1845, LeClaire in Paris was producing the oil paint on a large scale, and by
1850, zinc white was being manufactured throughout Europe. The success of zinc white paint was due to its advantages over the traditional white lead: zinc
white is essentially permanent in sunlight, it is not blackened by sulfur-bearing air, it is non-toxic and more economical. Because zinc white is so "clean" it is
very valuable for making tints with other colors; however, it makes a rather brittle dry film when unmixed with other colors. For example, during the late
1890s and early 1900s, some artists used zinc white as a ground for their oil paintings. All those paintings developed cracks over the years. [83]
In the recent times, most zinc oxide was used in the rubber industry (see applications above). In the 1970s, the second largest application of ZnO was
photocopying. High-quality ZnO produced by the "French process" was added into the photocopying paper as a filler. This application was however soon
displaced.[19]
Safety
As a food additive, zinc oxide is on the U.S. FDA's list of generally recognized as safe, or GRAS, substances.[84]
Zinc oxide itself is non-toxic; however it is hazardous to inhale zinc oxide fumes, as generated when zinc or zinc alloys are melted and oxidized at high
temperature. This problem occurs while melting brass because the melting point of brass is close to the boiling point of zinc. [85] Exposure to zinc oxide in the
air, which also occurs while welding galvanized (zinc plated) steel, can result in a nervous malady called metal fume fever. For this reason, typically galvanized
steel is not welded, or the zinc is removed first. [86]
A recent study has also raised a concern that zinc oxide nano-particles may cause cancer.[87]
In popular culture
Reflecting its many varied but relatively unobtrusive and unglamorous uses, zinc oxide was the theme of a spoof in The Kentucky Fried Movie as a
short educational filmZinc Oxide and You.
In SpongeBob SquarePants, the lifeguards in Goo Lagoon use zinc oxide to make their noses white to show that they're a lifeguard.
zinc oxide
n a white insoluble powder used as a pigment in paints (zinc white or Chinese white), cosmetics, glass, and printing inks. It is an
antiseptic and astringent and is used in making zinc ointment. Formula: ZnO , (Also called) flowers of zinc, philosophers wool
Starch or amylum is a carbohydrate consisting of a large number of glucose units joined by glycosidic bonds. This polysaccharide is produced by
most green plants as an energy store. It is the most common carbohydrate in human diets and is contained in large amounts in such staple
foods aspotatoes, wheat, maize (corn), rice, and cassava.
Pure starch is a white, tasteless and odorless powder that is insoluble in cold water or alcohol. It consists of two types of molecules: the linear
andhelical amylose and the branched amylopectin. Depending on the plant, starch generally contains 20 to 25% amylose and 75 to 80% amylopectin
by weight.[1] Glycogen, the glucose store of animals, is a more branched version of amylopectin.
Starch is processed to produce many of the sugars in processed foods. Dissolving starch in warm water gives wheatpaste, which can be used as a
thickening, stiffening or gluing agent. The biggest industrial non-food use of starch is as adhesive in the papermaking process. Starch can be applied to
parts of some garments before ironing, to stiffen them.
Petroleum jelly, petrolatum, white petrolatum, soft paraffin or multi-hydrocarbon, CAS number 8009-03-8, is a semi-solid mixture
ofhydrocarbons (with carbon numbers mainly higher than 25),[1] originally promoted as a topical ointment for its healing properties.
After petroleum jelly became a medicine chest staple, consumers began to use it for myriad ailments and cosmetic purposes, including toenail fungus,
male genital rashes (non-STD), nosebleeds, diaper rash, and chest colds. Its folkloric medicinal value as a "cure-all" has since been limited by better
scientific understanding of appropriate and inappropriate uses (see uses below). It is recognized by the U.S. Food and Drug Administration (FDA) as
an approved over-the-counter (OTC) skin protectant, and remains widely used in cosmetic skin care.