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The Hydration of Dental Cements

ALAN D. WILSON, JOHN M. PADDON and STEPHEN CRISP

Laboratory of the Government Chemist, Cornwall House, London SE1, England

A study was made of the hydration of dental 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-

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., show- ing least hydration (the zinc polycarboxylate cement), had the lowest strength and modulus and the greatest deformation at failure. A linear rela- tionship was found to exist between strength and the degree of hydration of dental cements. All the cements were found to become more highly hy- drated 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

ferent cement

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 hy- dration phenomenon, a study was made of the condition of water in four different dental cements: zinc phosphate, zinc poly- carboxylate, silicate and glass-ionomer. Wa- ter was classified into "evaporable" and "non-evaporable", and the effect of aging on the amounts contained in dental cements was studied.

acid-base reaction between a proton donat- ing liquid and a powder which acts as a base. A salt hydrogel is formed which binds

the unreacted powder particl les together into Four brands of dental cement, each of a

a cementitious mass. The reaction may simply be repre MO + H2A =

Materials and methods.

generic setting different type, were selected for this study:

:sented thus:

MA

+ H20

a dental silicate cement (Super Syntrex*),

a zinc phosphate cement (De Trey's

Zinc*),

a glass-ionomer cement (ASPA IV**), and

powder

For convenience of rep]

liquid

salt h

lydrogel

resnttin,the

a zinc polycarboxylate cement (Poly F*).

Cements were prepared under standard

oxide cation and the liquid anion

as

being divalent. In fact, F sent phosphoric or polyacr

are taken

repret

ISO conditions of

23 ±

I C and 50 ± 5%

ioAmay

relative humidity. The dental silicate ce-

ment and the zinc phosphate cement were

mixed using the standard technique appro-

priate to each as described in the Interna-

tional Standards Organization's specifications

rylic acids, and

licM

Can

~s Zn, Mg or Ca.

)rine content

of

Lable glasses are

affect

Lf)

er

One

the essen-

essre-

ren

One may

M can represent Al as well a

(The silica, sodium and fluc cements based on ion-leach

ignored, since they do not a tial features of the reaction

gard the powder as a provide

and the liquid as an accept( (Fig. 1). These acid-base reaction to be far removed from Pc

which sets by complex hydra However, it is known that the setting time and compre:

(ISO/R

1565 and ISO/R

1566,

respectively).

using

the

The

The other cements were

mixed

dental silicate cement technique.

or of these ions powder/liquid ratio used was recorded.

cements appear

:)rtland cement

Ition

reactions1

eartionlsr

ssivestarticuharf

L,

,

L

,

ssive

M".

16. ss9&L"L,

strength

of

tin

Evaporable

water determinations were

performed (in duplicate) on cement discs

(20 mm diameter x

had been stored at

1.5

37C in

mm thick)

sealed

which

containers

for various times: 30 min, 4 h and 340 h.

phosphate-bonded cements z

are critically af- *Amalgamated Dental Company, London, En- gland

**Laboratory of the Government Chemist, London, England.

Received for publication November 28, 1977. Accepted for publication June 5, 1978.

1065

1066

WILSONETAL.

acid liquid (proton

, IA donor)

4

( displaced cations M 2+

powder partide basic/amphoteric metal oxide

(proton acceptor)

JDent ResMarch 1979

* MA

matrix

salt gel

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 (in- ternal 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 con-

taining 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

ZincPhosphate Cement

De Trey's

Zinc

Total phosphate

48.8

61.7

(asH3PO4)

A13+

1.6

3.1

Zn2+

6.1

H2P04- (calc)

35.3

33.4

free H3PO4 (caic)

13.1

27.9

H20 (calc)

43.9

35.5

Glass-lonomerCement

ASPA IV

Zinc Polycarboxylate Cement Poly F

Polyacid

47.5*

42.6**

Tartaric acid

5.0

H20 (calc)

47.5

57.4

*2:1 poly(acrylic acid/itaconic acid)

**poly(acrylicacid)

Vol. 58 No. 3

HYDRA TION OF DENTAL CEMENTS

1067

E

0l;w

Water in Dental Cements

o L

UL[L.AL" mmE."-,':,

?

Nu E_opbW A

U 1 '.1Eila1W] 1 F '.

Fig. 2.-Non-evaporable and evaporable water present in dental cements of various ages.

TABLE 2

WATER CONTENT OF DENTAL CEMENTS

Zinc Phosphate

De Trey's Zinc

Zinc

Carboxylate

Poly F

Glass

Ion

nomer

AS

'PA IV

Silicate

Super Syntrex

Powder/Liquid

3.4

2.4

3.0

4.0

ratio g/ml

Liquid density

1.69

1.18

1.10

1.55

Powder/Liquid

2.00

2.00

2.72

2.58

ratio g/g

Water content*

11.9

19.2

12.7

13.8+

(excluding reaction

water)

Reaction water**

4.6

1.7

1.8

2.8

Total Water

16.5

20.9

14.5

16.6

*Calculated from the chemical composition of the components of the cement, but not including reac-

tion 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.

JDent Res March 1979

TABLE 3 EFFECT OF CEMENT AGE ON HYDRATION STATE* AND PROPERTIES

 

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

Non-

evaporable:

Evaporable

water

Compressive

strength

min min 4 h

h

min min 4 h

h

min min

4 h

h

min min

4 h

h

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

-

93

141 150

 

40

62

75

 

71

146

275 -

117 201

252

-

 

-

strength

(N/mm2)

Modulus of

-

43

108 120 -

18

30

45

-

24

92

225 -

55 190 230

   

elasticity, E

(103 x

N/mm2)

-

11.7 13.5 13.0

-

3.5

5.1

7.3

-

5.1

8.8

18.0 -

11.2 20.4 21.3

Plastic Strain

at fracture, a

(x 10-3)

-

2.3 0.78 0.22

-

10.1 6.67 2.87

-

23

5.86 0.95 -

0.88 0.16 0.20

*Under sealed conditions at 37 C

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 cement- disc, and Wf is the final weight after desic- cation. 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. Reac- tion 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 Wy-

combe, Bucks, England

using cement cylinders (12 mm long x 6

mm diameter). After preparation these ce-

ment cylinders were stored in liquid

paraf-

fin contained in stoppered bottles at 370C for 30 min, 4 h or 340 h before testing. The

cylinders were crushed in an electro-mechan-

ical testing machine* at a cross head speed of 1 mm/min. Stress and plastic strain at

fracture, yield stress and the modulus of

elasticity in compression were taken or cal- culated from the stress-strain curves cor- rected for the machine constant.

Results and discussion.

Results obtained forthe "non-evaporable"

and "evaporable" water contents of the four

dental cement types at various times are

presented as histograms in Figure 2. The total water content of the quartz liquid pastes which simulate cement pastes at zero times is less, since no reaction water is pro- duced. The ratio of non-evaporable water to evaporable water, which represents the extent of hydration of cements, is given in Table 3. The quartz/liquid pastes were found to contain no non-evaporable water. In all

cases this ratio was found to increase as the

cements aged, showing that a type of hydra- tion reaction occurs. This ratio was also found to vary greatly among the different types of cement. Certain conclusions may be

Vol. 58No. 3

HYDRATION OF DENTAL CEMENTS

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 ce-

ments 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 ce-

ments containing hardly any non-evaporable water.

The effect of temperature on the hydra- tion of one type of dental cement, the glass- ionomer cement, is shown in Figure 3. In-

crease in temperature is seen to accelerate

the rate of hydration.

The ratio of non-evaporable water to eva-

porable water present in a cement is related

to various mechanical properties in Table 3. This table shows that the degree of hydra- tion of a cement correlates with compressive strength, yield strength, modulus of elasti- city and with the inverse of plastic strain at failure. These trends are exemplified by

the results obtained for the zinc polycar-

boxylate 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 observa-

tion which can be explained by the plasticiz- ing 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 de-

creases. (Fig. 4)

Conclusions.

The hydration of dental cements, defined

as the ratio of "non-evaporable" water to

"evaporable" water, is an important para-

meter which controls the mechanical proper- ties of dental cements. The most highly hydrated cements are the strongest, have

BINDING OF WATER IN ASPA CEMENT

1.0_

.0

z

10

2323°0C

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

x

0u0

0*

x

Xm

A

0

A

JDent ResMarch 1979

+

1001

X

a

a

a

050

1-0

1-5

NON -EVAPORABLE WATER:EVAPORABLE VOTER

Fig. 4. -The relationship between non-evaporable water: evaporable water and compressive strength:

A

x

Cement

Age(h)

Temperature (OC)

Zinc polycarboxylate

0.5, 4, 340

37

Zinc phosphate

0.5, 4, 340

37

Silicate

0.5, 4, 340

37

Glass-ionomer

0.5,4,28,96, 340

37

Glass-ionomer

various

23

Glass-ionomer

various

65

Vol. 58 No. 3

HYDRATION OF DENTAL CEMENTS

1071

the greatest modulus and show the least deformation at fracture. In general, zinc oxide cements are weaker and less hydrated than ion-leachable glass cements, and ce-

ments based on polycarboxylic acid are

weaker and less hydrated than those based on phosphoric acid. The weakest and least hydrated cement is, thus, the zinc polycar- boxylate cement. "Evaporable" water ap-

pears to act as a plasticizer, for the zinc

polycarboxylate cement is the most plastic

of all the cements. The strengths of dental

cements are directly related to the ratio of

"non-evaporable" water to "evaporable" water. The hydration of dental cements,

and thus their strength, increases as they

age.

Acknowledgments.

The authors thank the Government Chemist, Dr. H. Egan, for permission to con- tribute this paper. Reproduced by permis-

sion of the Controller of Her Britannic Ma- jesty's Stationery Office.

REFERENCES

1. LEA, F. M.: The Chemistry of Cement and

Concrete, 3rd ed., Edward Arnold, London,

1970.

2. WORNER, H. K. and DOCKING, A. R.: Den- tal Materials in the Tropics. Aust. Dent. J.

3:215-229, 1958.

3. WILSON, A. D.; KENT, B. E.; BATCHELOR,

R. F.; SCOTT, B. G.; and LEWIS, B. G.: Dental

Silicate Cements: XII. The Role of Water:

J. Dent. Res. 49:307-314, 1970.

4. PAFFENBARGER, G. C.; SCHOONOVER, I. C.

and SOUDER, W.: Dental Silicate Cements:

Physical and Chemical Properties and a Specifi- cation,J. Am. Dent. Assoc. 25:31-87, 1938.

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.