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ce-
ments, water being classified as "non-evaporable" and "evaporable". The ratio of these two types of water was found to vary greatly among dif-
ferent cement types, being lesser in zinc oxide and ionic polymer cements and greater in ion-leachable glass and phosphoric acid cements. The cement with the least "non-evaporable" water, i.e., showing least hydration (the zinc polycarboxylate cement), had the lowest strength and modulus and the greatest deformation at failure. A linear relationship was found to exist between strength and the degree of hydration of dental cements. All the cements were found to become more highly hydrated and stronger as they aged. J Dent Res 58(3):1065-1071, March 1979
The general mechanism of cement formation in dental cements can be represented as an acid-base reaction between a proton donating liquid and a powder which acts as a base. A salt hydrogel is formed which binds the unreacted powder particlles together into a cementitious mass. The generic setting reaction may simply be repre :sented thus: MO + H2A = MA + H20 powder liquid salt hlydrogel For convenience of rep] resnttin,the oxide cation and the liquid anion are taken as being divalent. In fact, F ioA may repret sent phosphoric or polyacrrylic acids, and Can M can represent Al as well a~slicM Ca. Zn, Mg (The silica, sodium and fluc)rine content of cements based on ion-leachLable glasses are ignored, since they do not aaffect the essenOne tial features of the reactioner One may ren gard the powder as a provide and the liquid as an accept(or of these ions (Fig. 1). These acid-base reaction cements appear to be far removed from Pc:)rtland cement which sets by complex hydra Ition reactions1 However, it is known thattin ss9&L"L, , the setting time and compre: ssive strength of ssive phosphate-bonded cements zare critically afor
fected by the water content of the liquid2'3. Again, although dental cements develop their strength rapidly after mixing, strength continues to be slowly developed for several months. 4-6 These observations suggest that the initial acid-base reaction is followed by a slower process, such as the hydration of reaction products. In order to ascertain if there was a hydration phenomenon, a study was made of the condition of water in four different dental cements: zinc phosphate, zinc polycarboxylate, silicate and glass-ionomer. Water was classified into "evaporable" and "non-evaporable", and the effect of aging on the amounts contained in dental cements was studied.
prepared
under
standard
of 23
5%
ce-
ment
Lf)
essre-
mixed using the standard technique appropriate to each as described in the International Standards Organization's specifications (ISO/R 1565 and ISO/R 1566, respectively). The other cements were mixed using the
dental
silicate
cement
technique.
The
were
L,
L..,
eartionlsr starticuharf
M". 16.
performed (in duplicate) on cement discs (20 mm diameter x 1.5 mm thick) which had been stored at 37C in sealed containers
for various times: 30
min,
4 h and 340 h.
Received for publication November 28, 1977. Accepted for publication June 5, 1978.
*Amalgamated Dental Company, London, England **Laboratory of the Government Chemist, London, England. 1065
1066
WILSONETAL.
* MA
( displaced cations
powder partide basic/amphoteric metal oxide
M 2+
(proton acceptor)
Fig. l.-Schematic representation of the setting reaction in dental cements.
These cement discs were formed by placing the freshly mixed paste in a brass ring (internal dimensions 20 mm diameter x 1.5 mm high), held in a restraining former, placed on a sheet of polyethylene backed by a stainless steel plate. The mould was closed by a similar polyethylene covered stainless steel plate, and the whole assembly was clamped together. In order to obtain figures
for zero time, cement liquids were mixed with finely ground quartz powder to form a simulated cement paste. Evaporable water was removed by placing a weighed cement disc in a desiccator containing anhydrous magnesium perchlorate, which was continuously evacuated to 10 mm Hg pressure. This process was continued until the cement disc attained constant
TABLE 1 COMPOSITION (% m/m) OF DENTAL CEMENT LIQUIDS Silicate Cement Super Syntrex 48.8
1.6
Total phosphate
(as H3PO4)
A13+
3.1
33.4 27.9 35.5
Zinc Polycarboxylate Cement Poly F
Zn2+
H2P04- (calc) free H3PO4 (caic) H20 (calc)
6.1 35.3
13.1 43.9
Glass-lonomer Cement
ASPA IV
Polyacid
47.5*
5.0 47.5
42.6**
57.4
Tartaric acid H20 (calc) *2:1 poly(acrylic acid/itaconic acid) **poly(acrylic acid)
Vol. 58 No. 3
1067
E_opbWA
E
0l;w
'.1 Eila1W 1 F ]
'.
Fig. 2.-Non-evaporable and evaporable water present in dental cements of various ages.
Zinc
Carboxylate Poly F
2.4
Silicate
3.4
3.0
1.18 1.55 Liquid density 1.69 1.10 2.00 2.72 Powder/Liquid 2.00 2.58 ratio g/g 19.2 12.7 13.8+ Water content* 11.9 (excluding reaction water) 1.7 Reaction water** 4.6 1.8 2.8 Total Water 20.9 16.5 14.5 16.6 *Calculated from the chemical composition of the components of the cement, but not including reaction water. **Calculated assuming completion of the reaction with the formation of neutral salts. +Allowing for 2.2% water in the powder.
1068
WILSON ET AL.
Zinc Phosphate Zinc Polycarboxylate Glass - Ionomer Silicate - De Trey's Zinc Poly F ASPA IV Super Syntrex 0 30 340 0 30 340 0 30 340 0 30 340 min min 4 h h min min 4 h h min min 4 h h min min 4 h h
Nonevaporable: Evaporable water
Compressive strength
0.0 0.54 0.60 0.72 0.09 0.05 0.07 0.22 0.0 0.42 0.54 1.20 0.0 0.68 0.89 1.08
-
(N/mm2)
Yield strength
93
43
40 18
62
75
71
146
92
275
(N/mm2)
Modulus of elasticity, E
30
45
24
225 -
55 190 230
(103 x
N/mm2)
Plastic Strain at fracture, a (x 10-3)
-
3.5
5.1
7.3
5.1
8.8
18.0
weight. At all times the cement disc was contained in a weighing bottle so that it could be isolated from ambient conditions during weighing and transfer to and from the desiccator. The percentage of evaporable water is given by the equation:
Wi
Wf
x
100
W.
Where, Wi is the initial weight of the cementdisc, and Wf is the final weight after desiccation. The total water content of each dental cement was calculated from its chemical composition (Table 1). In addition to the water contained in the liquid, due allowance was made for water generated during the course of the reaction except in the cases of the unreactive quartz/liquids pastes. Reaction water was calculated from the anionic content of the liquid,. assuming that all anions in the liquid combined with metal ions from the powder to form a neutral salt. Results of these calculations are presented in Table 2. Mechanical properties were determined
*Instron Model TTCM, Instron, Ltd., High Wycombe, Bucks, England
Vol. 58 No. 3
1069
drawn. Most of the hydration reaction takes place in the first 30 min, and the salt matrices of these cements probably precipitates as hydrated forms. In general, zinc oxide cements are less hydrated than those cements based on ion-leachable glasses, while the degree of hydration of phosphate-bonded cements tends to be higher than that of cements containing hardly any non-evaporable water. The effect of temperature on the hydration of one type of dental cement, the glassionomer cement, is shown in Figure 3. Increase in temperature is seen to accelerate the rate of hydration. The ratio of non-evaporable water to evaporable water present in a cement is related to various mechanical properties in Table 3. This table shows that the degree of hydration of a cement correlates with compressive strength, yield strength, modulus of elasticity and with the inverse of plastic strain at failure. These trends are exemplified by
the results obtained for the zinc polycarboxylate cement. This is the weakest cement, having the lowest yield strength, compressive strength and modulus, and it contains the least amount of non-evaporable water. Also, of all the cements, it has by far the highest plastic strain at failure, an observation which can be explained by the plasticizing effect of the evaporable water - the loose water - which is greatest in this cement. In all cases, as the cements become hydrated, their strength and modulus of elasticity increase and their plasticity decreases. (Fig. 4)
Conclusions.
The hydration of dental cements, defined as the ratio of "non-evaporable" water to "evaporable" water, is an important parameter which controls the mechanical properties of dental cements. The most highly hydrated cements are the strongest, have
1.0 _
230 23 C
.0
z
10 100 hours Fig. 3.-The progressive hydration of a glass-ionomer cement at various temperatures.
1070
WILSON ET AL.
STRENGTH
Nlmm2 30 r
+
2001
x 0u0 0* x
1001
Xm
050
1-0
1-5
Fig. 4. -The relationship between non-evaporable water: evaporable water and compressive strength: Cement Temperature (OC) Age(h) Zinc polycarboxylate 37 0.5, 4, 340 A Zinc phosphate 37 0.5, 4, 340 37 Silicate 0.5, 4, 340 37 Glass-ionomer 0.5,4,28,96, 340 x 23 various Glass-ionomer 65 Glass-ionomer various
Vol. 58 No. 3
1071
the greatest modulus and show the least sion of the Controller of Her Britannic Madeformation at fracture. In general, zinc jesty's Stationery Office. oxide cements are weaker and less hydrated REFERENCES than ion-leachable glass cements, and cements based on polycarboxylic acid are 1. LEA, F. M.: The Chemistry of Cement and weaker and less hydrated than those based Concrete, 3rd ed., Edward Arnold, London, on phosphoric acid. The weakest and least 1970. hydrated cement is, thus, the zinc polycar- 2. WORNER, H. K. and DOCKING, A. R.: Denboxylate cement. "Evaporable" water aptal Materials in the Tropics. Aust. Dent. J. pears to act as a plasticizer, for the zinc 3:215-229, 1958. polycarboxylate cement is the most plastic 3. WILSON, A. D.; KENT, B. E.; BATCHELOR, R. F.; SCOTT, B. G.; and LEWIS, B. G.: Dental of all the cements. The strengths of dental Silicate Cements: XII. The Role of Water: cements are directly related to the ratio of J. Dent. Res. 49:307-314, 1970. "non-evaporable" water to "evaporable" C.; SCHOONOVER, I. C. water. The hydration of dental cements, 4. PAFFENBARGER, G.Dental Silicate Cements: and SOUDER, W.: and thus their strength, increases as they Physical and Chemical Properties and a Specifiage. cation,J. Am. Dent. Assoc. 25:31-87, 1938.
Acknowledgments.
The authors thank the Government Chemist, Dr. H. Egan, for permission to contribute this paper. Reproduced by permis-
5. CRISP, S.; LEWIS, B. G.; and WILSON, A. D.: Characterization of glass-ionomer cements. 1. Long term hardness and compressive strength, J. Dent. 4:162-166, 1976. 6. PADDON, J. M; and WILSON, A. D.: Stress Relaxation Studies on Dental Materials. 1. Dental Cements J. Dent. 4:183-189, 1976.