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A characterization of polymethylmethacrylate bone cement
SS Haas, GM Brauer and G Dickson J Bone Joint Surg Am. 1975;57:380-391.

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artificial The dentures material has in this also country been for at least used degree of the amounts a negligible of in our studies (see Handling on the nepnoducibil- neurosurgeons to form replacements for skull defects. per cent. on commercially cementl The and 2150 Section.94 per The cent. opaque Washington. Bone WASHINGTON.20#{149} Accordingly. it sets in vivo. 1 2 gram). England. New Jersey 49 GrayStates by Cer- per 83. polymethylmethacrylate cement. MAt.7 cement. DICKSON. and 20037. but it vast majority of thirty medicine years. G.C.D. which is increased by rapid mixing. in that application. peroxide (calculated as benzoyl peroxide) 1 . with 1: Surgical lIng Howmedica. The results of the chemical analyses of the powder for the nadiolucent cement are as follows: polymethylmethacrylate 95. The porosity. Bureau Simplex . distributed in the United Rutherford. the dough time.29 grams (S. 0. Medical D. 12 Characteristics). tam Simplex Bone Cement Road. The average amounts of liquid and powder in five vials and packages. hanWing characteristics. may reach 10 per cent. Cement D.19. Materials on the package label. of StanP Radi- Washington.12. S. . Medical 07070. by North Hill Plastics. commercial adequately identification materials and instruments are identified specify the experimental procedure. and physical properties. For these analyses.3 per cent our styrene For barium copolymer nadiopaque sulphate ne- . A chemical determine sible presence similar to the analysis of ingredients and was performed to the major constituents to investigate the posof properties written as it is polymenized orthopaedic litera- in of additives commonly found in formulations bone cement. ported on the basic characterization ofthe material 1I. to some degree. we undertook a study of the chemical and physical properties as well as handling qualities of the bone cement. Analytical Studies of powder was evaluated and As the set gradually shrinkvided The mination constancy of weight liquid bags as prodeterof pow- by the manufacturer by weight age of up to 5 per cent was observed. of Polymethylmethacrylate M.. and hydroquinone 0. fractions THE JOURNAL 10 per The cent ether analysis) proportionate Bureau identified of Standards.08 gram) and 39.C. M. handling time. and temperature to be most affected by environmental kneading of the dough the residual monomer the strength increases. . is necessarily nor the does best it imply available that for the this material purpose. BRAUER. or instrument duction methanol of the other extractable extractable powder AND JOINT and were SURGERY of radiolucent OF BONE 380 . and manufacturer’ 16. The manufacturer’s label states that forty grams of powder and twenty milliliters ( 18.. Division. In no imply recommendation or endorsement in this report to instance does such by the National showed components.D. ultraviolet point. HAAS. polymethylmethacrylate bone ceencountered be attributed in the handling to the only of the contents of randomly selected materials.28 per cent.62 These analyses were utilized. mass. on request. were 19. period University. The practicing spectrophotometry nuclear magnetic techniques composition melting resonance refractive and gas is chromatography The chemical as follows: toluidine 2. The unique feature of the employment of polymethylmethacrylate as a bone cement is that. dependent on consistent of different recently has ment been used extensively in onthopaedic has been the primary constituent of the surgery. den and vials of liquid. manufactured N16.t. but are available from the authors infrared index.9 grams) of liquid are provided in the pnemeasured containers and are to be mixed in their entirety. respectively. and available to the obtained on the was polymethylmethacrylate orthopaedic as provided cement serial numbers Avenue. Much tune about methacrylate joint and chemical the oven-all bone cement.A Characterization BY S. This fact has imposed entirely different constraints on its handling and has also invited a re-examination of its physical vivo. selected at random from two different batches. PH. and time.D.D. stated methylmethacrylate pen cent. (as in the Pennsylvania National Surgical NW.5 per cent. studies were performed bone surgeon. Obviously the reproducibility of the performance of the material is.28 and replacement In contrast. of a vial and a plastic of (membrane filtration-sterilized) powder (gamma radiation-sterilized). AND G. . Ltd.0076 are in agreement with the composition over * a fourteen-month George Washington D. 20234 P Bone Cement residual monomer s composition was cent and methylmethacrylate for the radiolucent analyses manufacturer’s 0.4 for the liquid dimethyl-pper cent. 0. determined 97. London Inc.C. 24. content A volume rise tem- packages indicated The prepackaged sterile liquid bag of sterile that different batches were material routinely consists represented. t Dental dards. by in amounts The would ity of and appear the ratios of variation to have performance of the component effect the material powder found and liquid. ABSTRACT: Polymethylmethacrylate cement is characterized in terms of chemical composition.3 per cent. polystyrene 2. mate qualities variability Only The mechanical properties of the cement approxithose of polymethylmethacrylate denture base Some of the variability cement could batches.*. were perature material decreases setting found and ages.82 grams (S. The details of the methods has been in the recent clinical efficacy of polymethylparticularly as an adjunct to total much less has been re- analysis of ingredients and of the cured material are beyond the scope of this communication.

of the cured product under in the presence of reducing clinical agents.000.4 per cent after 215 days.28 large per within the limits of analytical error. powder benzoyl most and OF POLYMETHYLMETHACRYLATE BONE CEMENT 381 properties of the at least prodpar- the ether extractbe affect uct. respectively. 242. weight as obtained distributions from for room-temperatureperoxide in the product peroxide in water. 57-A. 203. and it may decrease the amount of degradation of polymeric material caused by exposure to ionizing radiation during sterilization. The compositions during the mandoes not reach inand and is entrapped cured material peroxide storage in at room in monomer weight is an important in determining were quite similar. Although polystyrene is employed in some acrylic resins to limit water sorption.3 imen cylinders then declines polymerization. yielding high Thus. ufacture of the powden some monomer itiating sites during the polymerization of the powder the powder particles. Apparently. of the specthe amount hours hours.) Polystyrene is only a minor component of the powder the first few after twenty further storage. conditions. VOL.49. and it will mechanical leach fraction of radiopaque It was anticipated that in the powder. However. (Benzoyl peroxide is known to undergo explosive decomposition when exposed to DMPT. improve value. It should be noted that other by-products system may interfere in the colof the cured product. pen cent is present after in air for thirty to sixty quite rapidly during to 2. After four without stirring. the physical Furthermore. viscosity-average molecular weight was determined (American Society for Testing and Materials Method D-2857-70 for dilutesolution viscosity of polymers 4). require peroxide was 2. or with monomer content is calculated the monomer concentrations barium sulphate agree Data from six-month-old tion of the on the basis of cements is probably amount not (0. even after storage for many months. Its residual monomer content was 1 I per cent. The analyses of monomer content of cured samples stored for various lengths of time from thirty minutes to seven months indicate that about 3. zation It is likely of the liquid that the matrix which forms on polymenimolecutohas ceportion of the mix has a higher contains if present NO.78.000. peroxide also would polymethylmethacry- out of the cement because tially and be absorbed in the tissue medium. 3. and the infrared spectrum. peroxide gel permeation polymethylmethacrylate The magnitude of the residual was small. Following in a vacuum the performance of a polymer. the measured values should be initiator-accelerator tect variations among different and thus afford a rapid check mercial products. respectively. powder. and weight-average (Mw) molecular weights and the ratio 195. the monomer concentration decreases slowly and reaches a value of 2. the present results agree well with those cured reported by Smith and Bains .4 per cent.3 per cent ofcopolymen containing methylmethacstynene in the powder.000. which con- ceivably could be present in the enviroflment surrounding an implant. for radiolucent and cement. and one-half content was at 37 dein a vacdried (2. of common.21 pen cent. rylate Since there is. the monomer A sample months stored and .60 able present and 2. but if of resin without content. However. polymers then weight The and cured . The residual monomer concentrations in specimens containing barium sulphate were ened material somewhat than for lower products per unit of weight of hardfree of the filler. 1) are typical of freeradical initiated vinyl polymers The number-average (Mn).000. Therefore.7 pen cent storage minutes. according to the manufac83. and 4. tuner. The melting of a purified ether ex- 107 degrees tract of the powder. was still present in the hardened water for three weeks and temperature. D = Mw/Mn for the powder 198.CHARACTERIZATION 2. It may possibly reduce the temperature rise on polymerization. 0. were found to match those of benzoyl peroxide. were 44. for this purpose.8 per cent of styrene. The slightly lower molecular weight of the powder compared with the cured resin was somewhat unexpected. specimens indicated that the variacontent content. polymeric is unlikely Since this peroxide is either benzoyl peroxide.33 and radiopaque of the some unneacted mass. Generally. the residual initial monomer ratio in the mix from effect a has a small powder-to-liquid on Molecular of 2/ 1 to a ratio of 3/ 1 had little factor cent) of residual monomer.3 per cent). some decomposition of peroxide at the surface of the cement may occur.000.69 per cent. this copolymenic constituent to 1 . monomer. both of which are insoluble that any appreciable amount of the or it will ograms (Fig. APRIL unreacted in large 1975 residual concentrations. centigrade is leached out. and 4. monomer. weight weight-average can be used to de- drying the measured residual peroxide amounted to 0. molecular material with increasing constant become practically considered as the maximum concentration of peroxide in the final product. if the sample is stored in water (at 37 degrees centignade) months reduced grees monomer in water. Gel permeation chromatograms were and number-average Determinations also used molecular of molecular to determine weight. viscosity-average (Mv). after On late formulations which benzoyl point ( 105 to an initiator is the most centigrade) for polymerization. as expected. Additional confirmation was obtained from the explosive reaction resulting from addition of dimethyl-p-toluidine (DMPT) to the purified extract. figures for cured material were 5 1 . After curing. molecularthe powder chromatand onimetric determination values for peroxide.000. The presence of styrene in the powder is advantageous in improving working (mixing) properties. for three in water then contains 2. This will adversely lar weight than the powder particles which it cements gether. The analogous leach out However. batches of the same material on the quality control of cornthe mechanical properties of molecular at some high of weight.62 per cent. respectively. the amount enough The present in the bone cement uum for one and one-half months lost even more monomer. The hardened material. Commercial polymethylmethacrylate generally a higher molecular weight than was found for the bone .

could between dough i0 1 and setting time was designated as handling time. setting time.000 15 Handling Characteristics by mixing routine the powder and of clinical usage. On the other hand. mass (by trial polymethylmethacrylate is usually polymerized at eletemperatures which make it possible to increase the of polymerization. Effect 2 z grams/twenty intermittently throughout the study to verify the Unless otherwise noted. styrogel. varying speeds. mixing temtime. powder-to-liquid batch ment. THE JOURNAL OF BONE AND JOINT SURGERY . as defined in this study. for Properties).25 per cent solution of the polymer. such as the time of attainment temperature midway been so designated. DICKSON surgically dough sured to form CD gloved finger was arbitrarily designated as the time. four (1) or variables placement one might in the molds. milliliters mix we used ten grams of rather than forty and We did employ the full amounts. have into with Thus. Handling time. peak and kneading on dough powder-to-liquid ratio. Setting time and peak temperature were meaby placing the dough mass in Teflon cylindrical molds a specimen to ensure fifteen millimeters Copper-constantan in length in the and fifteen of millimeters in diameter. AND G. Molecular weight distribution of commercial bone-cement powder and cured product from gel permeation chromatographic measurements of a 0. M. denture base (which are similar to bone cement) are reported to viscosity-average molecular weights ranging from to 600. the manufacturer’s final setting position. includes both the period when the material is readily workable and the subsequent period when it is hardening rapidly and should be held without movement dough ture. Usually two specimens were made from each mix and temperatures were recorded simultaneously on a dual-channel strip recorder. and temperature. (Other points time-temperature curve. number. that the industrial grades (see section on Mechanical rapid diffusion of the monomer dough times weight. A timer was started when all of the liquid had been added to the powder. time. stationary phase. is necessary. forty We maintained 2/ 1 as recommended manufacturer indicated. The time at which the cement mass no longer adhered to a of barium-sulphate content. in the handling the the desired time. a sterile wooden powder-to-liquid except The cetongue ratio where of C. a powder nonIndusmolecular ing kneading without were of the mass before barium sulphate.) C. S.) 100 MOLECULAR FIG. HAAS. encounter with clinically or the powder comparatively to obtain appropriate lower Initially.000 polymethylmethacrylate. otherwise powder twenty. atmospheric volume the mixand the components. but in most cases and five milliliters of liquid in the interests of economy. z BaSO4 KNEADING liquid Before Specimens according were prepared to the prescribed ferred uid this was done the powder was weighed and transto a stainless-steel or ceramic mixing bowl.382 S. mixing speed of sixty strokes per minute at 25 degrees tigrade and 20 to 40 per cent relative humidity.) 1 8-gauge ment was blade. Mobile phase. BRAUER. perature. The elapsed time from start of the mix to attainment of peak temperature was on the of a have time C. (2) studied: kneading 80 15 10 presence or absence of barium non-kneading of the dough sulphate. thermocouples (preshaped 5 accurate positioning center the mass) were placed in the dough masses and held in position with glass plates. WEIGHT M x between ambient The difference and peak. crosslinked vated degree resins have 150. handling time.) arbitrarily 5 designated the setting time. G. tetrahydrofuran. We determined tempera- and peak the total ratio. of initial time. validity of using smaller the test specimens were from ten grams of powder and five milliliters of liquid. The liqwas withdrawn from the vial with a glass syringe and spinal needle and added then mixed by hand with the standard by the to the powder. conditions. prepared at a cenFIG. it is not surprising better physical properties However.

of effect to 24 Finally.4* 1 1 7* Powder-to-liquid rather * 3/I 52* p<O. regard variable this setting to temperature temperature Mixing handling and and and time. with intermediate determinations per cent. but the peak temperature remained constant. and 39 degrees 19 to 76 per cent. Cement con- set somewhat more slowly and had a slightly time and dough time. setting time. Increasing the temperature of the mixing from trol in order to attain the most predictable results in handling the cement. Trials was done in the incubator in the incubator were run at centigrade. but in concert. 32. varying and four determinations of setting handling peak temperature ent combinations were made for each of conditions. 2). One trial was run in a nitrogen atmosphere the effect were kept opened bag times about 4. Kneading reduced the setting and handling times taming longer VOL. in either vessel a desiccator over water. countered in surgery. incubator was dough for purpose. as shown in Table II. for which a decrease of approximately one mmute (from nine to eight) was observed when the humidity was raised from 20 to 74 per cent. Larger removal The peak temperature variation was not significant.3 kneaded ratio 2/1 9 . Humidity ranged at to and days did not affect the aforementioned mixes made using powder stored 21 . An humidity observation slight decreases in dough time. to 7 or heated powder was In a few instances the to 37 degrees centigrade. preconditioned both in and plastic cent) humidity bag. through except that the mixing the cuffed ports.) 0.005. (mixing bowls (4) powder-toof dough time and differtime. if several of the variables introduced all happen to drive the reaction in one direction. Our purpose and environmental mainly to define or a closed ranges. and tem- temperature The each No as cement average marked without 1.. There was no significant effect on the peak temperature of polymerization.3 Barium Mixing sulphate temperature present + 19* than Mix 24 degrees 32 degrees centigrade rather + - 1. and peak temperatures are not directly applicable to the clinical of mixing and do not exactly situation specimen duplicate because the standard conditions the laboratory preparation used in the conditions en- to 32 degrees centigrade shortened the dough time. for two However. 2). had handling and peak temperatures mixes made from degrees centigrade higher than observe of oxygen separate deprivation. and handling temperature was essentially the compo- 24 degrees cooled als. magnitudes in Table effects effects by are shown the for atmo- variable Two determinations time. setting time. setting time were decreased as the environmental time. but had the same peak 3.CHARACTERIZATION OF POLYMETHYLMETHACRYLATE BONE CEMENT 383 TABLE EFFE CTS OF VARIABLES I ON SETTING BEHAVIOR Differences Mixing Conditions Dough (Seconds) Time in Average Handling Time (Seconds) + 15* Values Setting Time (Seconds) +34* Peak Temperature (Degrees cent. setting time. The experimentally determined dough time. more detailed data were obtained with apparatus providing a well controlled humidity. and handling time (Fig. the centigrade. as well as the peak temperature. The greatest effect was on setting time . were barium. was preconatmosphere.5 in water for six weeks 1 5 minutes less and . from 45 liquid 25.94* + 2. of the sixteen spheric humidity stant temperature from (24 20 per cent to 75 per cent at a condegrees centigrade). after ditioned differences were observed from the bag. of adding some three observations drops on the directly bowl in studying the effects of various technical factors on the mixing technique was those variables which the surgeon can con- to six water the powder prior to mixing. setting time. As the study progressed. Dough time. The effects of varying atmospheric temperatures are shown in Figure 3. some differences in setting and raised barium handling 57-A. Preconditionin a dry or humid atmovanin an unsetting about pow- atmosphere infant control of the with with used time. (3) environmental centigrade bath). were usually Trials for determirun with molds at molds were In some tnout of the 5 per der stored for the same period in an unopened bag in a desiccator at less than 5 per cent relative humidity. ously. NO. but they do apply in general. APRIL 1975 . time. (humidity to produce were of distilled made less than extremes increased. when the powder. hand perature placed liquid prior to placement in mold). and handling time. Varying the powder-to-liquid ratio from 2/1 to 3/1 reduced the dough time. than Difference statistically significant. in a dry or in a humid and peak temperatures were carried out as described previ- was added directly to the powder ing the powder in the sealed bag sphere ables. handling time. in the experimental The powder environment for at least thirty minutes nation of peak temperature before mixing. marked changes can occur. No significant effect was noted when nents were mixed in a nitrogen atmosphere. and handling time with increased humidity. and when water (Table II). the peak temperature slightly. The effects of the factors controllable by the surgeon are individually rather small. but there were After the basic trends of the temperature effects at 24 and 32 degrees centigrade were identified (Fig. of these elicited of 24 or 32 degrees in constant-temperature ratio of 2/1 or 3/1 .

were made from rise which occurs during the polymerizacement has been referred to by a number of To investigate the feasibility of controlrise. COMBINATION ON SETTI NG BEHAVIOR Peak Dough Time (Seconds) Effects of relative humidity (mixed RH RH at 142 519 661 77 Handling Time Setting Time Temperature (Seconds) (Seconds) (Degrees cent. HAAS. manufacturer’s All batch specimens number. Effect Initial After 32 degrees kneaded.384 behavior perimental reviewing ences.17. specimens were polymerized in degrees molds port). G. and 9 degrees in peak temperature. BRAUER. mixing bowl. reaction because Effects of mixing temperature (temperature of cement. of age of material trial five months 170 322 325 492 486 75 77 161 THE JOURNAL OF BONE AND JOINT SURGERY . The results are shown in Table II. 3 appears that inherent differences between sponsible for some variations in behavior The possibility of unfavorable tissue of the temperature tion of the bone authors 14. handling time. at 7 degrees (Other centigrade effects of polymerization later in this in re- are discussed Teflon Under molds previously these conditions. Material from several cause over different we batches obtained was cement used throughout the as the study. I I I I I I I I 20 25 30 0 35 40 could not Thus. 182 seconds in setting time. centigrade. and peak temperature. Radiopaque. these On differ- variables TEMPERATURE EFFECT 90 PEAK TEMPERATURE 70 0 C) w a: a: j we were able to find only two possible explanations: of the ingredients on storage or batch variations. components from the same batch used in both segof the study were aged at least eight weeks (stock was stored To determine a representative in the prepackaged kits at room temperthe effect of aging under these conditrial was performed on the same Q. centigrade. Thus. 12 w I- c U) w I- TTING batch of material after an interval of approximately five months from the initial evaluation. The data indicate that no significant differences were produced by aging for five months. These to any of the experimental differences conditions. other points are averages of four to fourteen determinations. tiofls. AN D AGING ( RH). centigrade. AND G.23 ling temperature batches are reof the cement. it FIG.) Powder desiccated 45 per cent RH) Mixed Mixed at 20 per cent at 74 per cent 147 120 I 14 106 410 369 298 302 556 489 412 408 82 82 85 87 Powder stored over water (mixed at 48 per cent RH) Water Effects of added to mix of variables combinations Radiolucent. 1 19 seconds handling centigrade be related time. need bearose as in sequentially z w I- the fourteen-month period of the investigation. as compared polymerized cooled to 7 degrees centigrade. and atmosphere) on dough time. M.16. The more detailed segment of the study was initiated eight weeks after the initial survey was completed. setting time. Brack- ets on points material with show the standard same deviations. DICKSON with were to explain any of the exobserved. aging which the could data and not be associated under investigation attempting S. peak temperatures were reduced with 93 degrees in molds centigrade previously heated to To ascertain 52 degrees lar specimens for simito 38 Volume changes Changes in volume under atmospheric TABLE EFFECT OF RELATIVE HUMIDITY II S OF VARIABLES. those ments material ature). 3/1 2/I 88 222 224 404 312 626 72 76 24 degrees not kneaded. S. Points for dough time are averages oftwo to seven determinations. Analysis of data on ten batches showed differences great as sixty-three seconds in dough time.

Changes in the water level in the pipette during the polymerization of the cement were recorded. Charnley However. Specimens 1 . mixing the final equal the cement-bone Regardless and less speed. which was poured into the volume dilatometer before the dough time. To ascertam changes in volume under increased pressure. Through water which a stopper. shrinkage was observed in all specimens. and 5 were measured in a water-filled volume dilatometer. the marked differences between initial portions of curve 1 and curves 4 and 5 are not dependent on BaSO4 content. and only shrinkage could be expected to produce or cement-prosthesis of the mass of the or absence in one instance from the maximum crevices or voids at interface. volume shrinkages mately 7. and. by evaporation this large was not used and is not reasons. Porosities ranging from 1 to 10 per cent of the volume of the cement were observed in the specimens prepared ity may by release TIME Typical curves IN MINUTES FIG.1 ‘. respectively. by vaporization of the monomer. 57-A. 4 as described be produced of absorbed to show by changes in volume. The methylmethacrylate on changing is approximately 2 1 per cent. This who reported he was working also although is in contrast net expansion with a somewhat to the findings of of the cement.0 _1 z w z = 0 normal mix of cement without barium sulphate proximately 36 per cent monomer. in Table III were calculated curves (Fig. employed the as a result resin and and enlargement pressure. porosmixing. Although specimen I contained BaSO4 while specimens 4 and 5 did not. 4). Volume and the effect of barium change was expressed as time before rapid shrinkage as the initial at approximately twenty-five mmof volume change There is perhaps measured in this cement would or prosthetic procom- utes after start becomes very some clinical way.CHARACTERIZATION OF POLYMETHYLMETHACRYLATE BONE CEMENT 385 the are period before rapid polymerization pressure volume variable.l ent expansion in some instances and shrinkage in others. and the initial mass were sulphate was also studied. The values given for shrinkage in Table III do not represent the entire amount of diminished volume which occurs on polymerization. with a constant pressure of 1 . approximately volume to) the mi- ple. place. however. Displacement of the plunger during polymerization was recorded by means of a dial gauge.7 I . and with phate 38 per cent monomer. polymerization This 22. The effects of varying the mixing speed. The general pattern of volume change of the polymerizing mass is shown in Figure 4. and there a slight in the porosity will of monomer that subject of and monomer 5 10 20 remains to shrinkage. specimens 2 and 3 were measured in a stainless-steel mold. was larger clinically age given versus volume volume The mass of these larger than the amount usually placed in a flask completely was agitated with a magnetic filled with distilled stirrer. 4. in the speci- w -J 0 > 1.6 per cent and 8 per cent. specimens of the cement in the dough stage were of the heat of reaction. and corrected for volume change of the water as a result of heat released by the curing mass. sample. by peak or plateau and the volume The values for shrinkfrom volume change arbitrarily selecting the bulb of a thermometer and the open end of a calibrated pipette were placed below the water level. pressure) probably formation showed due to apparent thermal expansion expansion of bubbles before of samples. APRIL 1975 tial observed 1. unpolymerized Probably 30 men is the major cause for deviations from the calculated shrinkage. changes with appar- of VOLUME - CHANGE CURVE I 2 3 4 5 BQSO4 + + - specimens PRESSURE 0.7 MPa (250 psi) imposed by an Instron testing machine through a plunger to the sam- or both. All specimens were dough air during the temperature of polymerization is high enough. the sample size. significance to shrinkage early expansion of the interstices of the bone per cent change from initial volume of the sample. evaluated. No expansion was observed during this period in specimens under the higher pressure. polymerization from monomer Since the initial shrinkage of to polymer volume of a contains apbarium sulof approxiwill take observed likely to of the device be some amount cement. Both types of curves were obtained with both barium-containing and barium-free specimens. different maprepara- which. 3. Our larger samples (polymerized at atmospheric contraction. Bulk volume by the experimental occur 2 3 shrinkage is seated shrinkage procedure two clinically be started). volume since flow any into of mixing (when the rate low) as the final volume. NO. terial volume. During the subsequent period of rapid polymerization. the in total joint replacements. duce ponents. mixed in the normal manner and placed in the test apparatus after time with the exception of specimen 5. before before the clinically may (or for at least occur can experimentally First. some the prosthetic volume-change ‘5 - ‘5 ‘5 measurements loss 4 I is not Second.7 at atmospheric MPO 0. a methylmethacrylate . a portion of the dough mass was placed in a cylindrical stainless-steel mold thirty-two millimeters in diameter and ten millimeters high. was presence than (or of barium. During the initial VOL.l 0. if incorporation of air during for change in volume of cement during polymerization.

The values for porosity (Table III) were calculated from the differences between the experimentally determined densities and the densities for specimens containing no porosity.8) 4.5) 4.0 3.6) Numbers in parentheses are standard deviations.01) 1. tion.386 S.3 8. but perhaps a slight reduction at the ratio 3/1.2 5.7) 28 2 5.5) mold BaSO4 BaSO4 15 13 - 1.127 1. Variations in powder-to-liquid ratio had little effect on porosity.5) 7. No.19 (0. between porosity definite increases.6) Polymerized in compression mold Vigorousmixing Normal mixing Minimum mixing 1 I I 8 10 - - 1. BRAUER.2 (0.7 (0.1) - 1.13 (0. exact correlation indication Also. there less shrinkage required to wet all of the powder.8) 8. S.23 1 . of mixing filler was not (Table Ill) more rapid However.02) 6.134 1.3) (0.3 1. comparison a vertical light from the fifteen was made calculated of porous mold.1 (1.6) Polymerized in constantpressure mold BaSO4 present BaSO4 absent Rate of mixing Polymerized Vigorous Normal Minimum I I 5.20 (0.8 in water mixing mixing mixing 2 6 4 2.6 0.17 (0.4 (1. HAAS. set faster and The difference or of presence was observed to float during in net shrinkage as a function or absence of radiopaque appears to be a tendency and more porosity with curing.09 (0.6)* 3. and no mixing beyond that there is an indication of less porosity in those containing barium sulphate. for water under atmospheric pressure. Density determinations were made using values for volume derived from water displacement for irregularly shaped specimens and from calculations on the basis of dimensional measurements of the uniformly molded specimens.2 (0. It would appear from these findings that application of pressure during curing of the cement in the clinical situation is desirable in attempting to eliminate voids. with the lowest value of about 1 per cent for specimens processed under continuous load in the steel die.0 (1.7) - 3.6 (0.4) Powder-to-liquid 3/I ratio (gimi) - 2/I 3/2 Molding pressure Polymerized in water Polymerized in compression mold Polymerized in constantpressure mold * 4.7 (1. of Specimens AND POROSITY OF BONE CEMENT Variable Shrinkage (Per cent) Density (g/cm) Porosity (Per cent) Ba504 content in water Polymerized BaSo4 present Ba504 Polymerized absent in compression present absent 8 4 2.4 (1.7) - - 7.7) 4.02) 1. toward mixing.6) 1.7 (0.01) 1.22 (0. specimens Although and shrinkage.150 1.3 (0. processed in there is no there is a Porosity Porosity (void and content) Density was Changes verified visually by direct observation with a light microscope using source and observation of sawed specimens by fifteen-millimeter to quantify these quantitatively and from cylindrical observations.2(0.01) 9. DICKSON TABLE EFFECTS OF PREPARATION VARIABLES ON SHRINKAGE. AND III DENSITY. speed large.7) 9 6 - 2. M.2 (0. prosthesis.5) 9. JOURNAL OF One BONE would AND JOINT expect SURGERY a . There was an increase in porosity as the pressure on the cement was decreased.8 (0.01) 4.19 (0.5 (0.2 (0.5 (0. Higher values were obtained for specimens made in compression molds and the highest values (up to 10 per cent in some instances). G.8 (0.01) 1.3) 6. 18 1.8 9. G. by Porosity preparing sixty was evaluated as a function of mixing speed samples at mixing rates of 1 80 strokes per strokes per minute. No effort Porosity was of the densities of lower bulk shrinkage as the porosity for the specimens polymerized in water non-porous (standard) specimens. in addition to the benefits of producing flow of the cement into interstices for better seating of the THE minute.3 2.4 (1.

CHARACTERIZATION OF POLYMETHYLMETHACRYLATE BONE CEMENT 387 compared with specimens more dense dense one. of an indentation of a given tests. an average of individual curves for three specimens. the specimens did not show similar physical properties until approximately twelve hours after preparation. using the indicated aging temperature. 25. The system in clinical practice is open that is. Association thirty-eight thick. by indentation lated to completeness of polymerization. to harden in and 37 degrees the molds centigrade. Even though stored at the same temperature (37 degrees) after one hour. 5 cooling the cement during the rapid mens allowed to harden in the molds approached VOL. is a reflection of several properties. Those who advocate cooling of the metal components or cooling the cement with water during polymerization. curves derived from speci- polymerized in molds at 7 degrees centigrade and at 37 degrees centigrade and on similar specimens in molds provided at 37 degrees centigrade and stored relative information on the effect polymerization. the abutment of the prosthetic the calcar femoris may prevent transmission pressure simultaneously which is also to the cement with coincident mass. and higher mens stored temperatures Indentation shortened and recovery the time. arthroplasty. The similarity of final physical properties was also observed when we determined the tensile strengths of specimens molded No in molds during curing would seem to be slight - for several reasons. 15 3) to molded specimens in diameter and two millimeters allowed at 7.7- a I 160 millimeter Specification millimeters mens were equilibrated done ward. cement (less voids) to be stronger than a less slowly during the first few hours formed would appear to be an undehowever. curve specimens. grade. it is not known of shrinkage contributes to possibility of significantly obby application of pressure Shrinkage during curing sirable property. tions. In the case of the femoral component in total hipreplacement lar against applied occurs material. This indicates that a lower degree of polymerization is obtained for the specimens at 25 degrees centigrade. polymerization the hardening of flow. Specipreviously Tests were days afterdeterminacentiall specimicromewhich at intervals from fifteen minutes to thirty In the intervals from initial to subsequent specimens Regardless showed with were stored at 25 and 37 degrees of storage or mold temperature. Specimens the shrinkage polymerized 25 degrees lower recovery in molds at 25 degrees had. the cement can flow into interstices in the bone as pressure is applied. Curve 1 is 2 for mold two and the final indentation 1975 and 3. at 7 degrees recovery Specicentigrade values very at of Average curves for indentation polymerized 37 degrees DAYS FIG. mens ters steel ball (American Dental No. whether this small amount loosening of prostheses. reached in about four to five days (Fig. It has twenty-four value was which stored were it allows repeated evaluation as opposed to destructive in mechanical as indicated specimen as been shown speciare reacdepth 27 at 37 degrees differences of a polymer. properties of different tests. after setting. to reduce the exothermic reaction. 5). values than specimens centigrade and stored at higher indentation and polymerized either at 7 or 37 degrees material and the practical Mechanical end-point Properties and stored at 37 degrees centigrade. are that it ages. Differences were noted for both indentation and recovery curves in the speed of attainment of a steady state. and curve 3 for four specimens. to set in the mold centigrade reached of the final recovery Although specimens at 7 degrees the same and final were re- The tility. and recovery of bone cement. 57-A. should be aware of this. that mens and behavior elasticity. after two hours. an initial indentation of 100 to 200 of recovery off to a constant (25 a percentage leveled to 65 per cent) value gradually of 70 to 80 per 5* cent. For self-curing rylic dental filling resins. In practice. the actual with Finally. The advantages including strength. APRIL . of a material during and after indentation ductest tigrade. NO. At a mold and storage temperature of 37 degrees centhe indentation hours. or both. colof of the of the at 7 and 37 degrees significant difference centigrade was six days found. The viating the effects of shrinkage at 37 degrees centigrade. a close correlation between of indentation and residual monomer has been noted well Indentation Hardness and recovery were tester by applying measured with loads through a Rocka 12. obtained allowed and recovery did not change after and 90 per cent in four hours. Lower mold or storage temperature lengthened the time to reach a steady state.

6 Cement (1. breaking ofrupture. MPa N 91 .3) (1. Rather. 5. MPa * (60) To convert MPa to psi multiply by 145. it was found average ences that barium-sulphate-containing values in all parameters cements had lower The greatest differstrength.5) 41.225. The results indicate that the matrix which forms on polymerization of the liquid portion of the mix has properties very similar to those of the powder particles. the inden- artificial compressive powder-to-liquid recommended to 3/1 or re- tation versus imum.9) 47. the additives. This would be lation of the extremity lowing placement of For purposes of covery criteria On comparison of the bone cements commercial within acrylic the same range of the results of mechanical properties with those quoted in the literature for resins. 122) of rupture (American was calculated curves Dental from was derived strength. it would appear to be important system to minimize during the early the stresses on the joint replacement period. Smaller tested. indication monomer of the values relationship against indentation by plotting values our for residual content was obtained Specification Modulus breaking the slope The load. G. modulus transverse MPa* 28. there is a progressive increase in various parameters of mechanical performance. Among of the cement. strength or post-insertion lower values for other properties (Table IV).6)1 Radiolucent 32. covery value as specimens which were allowed to set at 37 degrees. may be responsible for the reduced strength compared porosity and especially important during maniputo obtain reduction of the joint folthe prosthetic components. the indentation and reof the bone acrylic with other similar materials. and modulus ofelasticity (Young’s modulus) are shown in Table IV. To convert N to lb force multiply by 0. M. Our determinations mechanical show that properties on temperature. Water Sorption and Solubility deNo. Transsixty-five by Association the transverse calculated from from com- recovery between indentation hours. Our evaluation of specimens prepared and were in tensile strength. No significant difference in compressive modulus ratio was seen when the of 2/1 was increased characteristics established for cement teeth: approach that is. be expected that other monomer content. transverse modulus of rupture.9 (1. indicating of indentation depth on monomer content. respectively. compressive specimens of the same age set at room straight-line curve was obtained.5-millimeter) at 37 degrees centigrade for seven THE JOURNAL of the cement in water days. obtained cent). Specimens stored per cent of the final of the final recovery at room temperature value in four same verse ten manner as those for the compression deflection was measured on specimens by 2. These differences were 10 per cent. it can will vary with the for tensile strength. residual monomer may be important.9 51.2) Commercial Acrylic Resins2’ 55-76 Tensile Compressive Transverse Modulus Young’s From strength. sterilization procedures.388 5. BRAUER. and in the range of in the other polymerization cement does not immediately reach a state of equilibrium with reference to its physical properties. AND G.7 (2.6) 76-131 - 83-1 17 loading data. testing.9 strength.5 millimeters No. DICKSON TABLE MECHANICAL PROPERTIES IV OF BONE CEMENT Radiopaque Cement (1. were Dental Association Specification in weight resulting from by the increase immersing dried discs (fifty by 0. 1 (3. of ninety-six The for recovery micrometers maximum values are and recovery and somewhat 50 of 79 per cent per less cent than (88 cement mmthose per 1 10 micrometers commercial strength duced to 3/2. To whatever extent these findings have a bearing on potential causes of loosening of the components.1) (3.9 56. of values Modulus the of elasticity stress-strain monomer-content pressive and transverse obtained loading data.1 (3. A the dependence Similarly. In comparing mechanical properties of cements contaming barium sulphate versus those tested. modulus of rupture. transverse strength. they value in four attained 78 An and attained only 80 per cent hours.1) 93. polymethylmethacrylate of the cured Compressive was evaluated by loading specimens prepared in cylindrical steel molds twelve millimeters high and six millimeters in diameter in an Instron testing machine. but to have Several factors of the cement these. differences were found stored at 37 degrees centigrade (body temperature) gives an parameters approximation of the behavior of this cement in its clinical application. HAAS. which did not. and by the net loss OF BONE AND JOINT SURGERY . Tensile strength was assessed on diametrically loaded specimens prepared in the Water sorption termined (American 12 2) and solubility. MPa load. the bone cement was found to be for compressive strength. comparison. MPa loading 2070 (90) 2200 2200 2300 (80) (50) 2690-3280 2690-3280 From compressive data. t Standard deviations are shown in parentheses.

5 0. Other modes of failure in which the cement may be suspect are more common: for example. Under our laboratory conditions. Water solubility indicates the propensity for leaching aqueous fects out of additives environment. not been to reduce the presof gradually The data obtained in our study provide some guidance opin without advantage a high has the disinsertion as to the handling techniques timum properties in the cement. VI AND S0LuBILITY 2250(60) 2390 (60) 3/2 * (2. with the rate of rise on polymerization heat is released when the possible ent cement polymerization ways are limited. to reduce so that the peak the temperature will be is to reduce and the bone the temperatures of the cement. so that temperature of requiring of the cement. coolof polymerization risk of subseduring is to by ina it is mixed. also will slow the rate setting time and due to movement way to reduce ratio a higher of the peak or by prosthesis temperature incorporating the setting period.03 0. 3.7)t (MPa) 2320 (40) 8 8 used for this comparison are shown TABLE WATER S0RIrn0N 91. The increased powder-to-liquid ratio the cement reduces the setting time to Powder-to-Liquid Ratio No. APRIL 1975 . The application of undue prosthetic device during the early part of the possibly contribute to loosening of the device. Water sorption in this by the substance This property. are extremely values methylmethacrylate resins and are within the specification limits for denture base materials 2 (a maximum of 0. to the cement. terial to reach the dough temperature at which which tend In general. during service and biological investigated in an efby us. present study. The of a higher in cases of cement tem- Cement t Standard deviations powder-to-liquid of pathological may be required ratio may be beneficial fractures in which large to fill defects. Changes in relative humidity and small variations in powder-to-liquid ratio have only minor effects on handling behavior. sorption. The feasibility of using certain higher homologues of methylmethacrylate which yield products with good mechanical properties also merits further exploration. the prosthesis.CHARACTERIZATION OF POLYMETHYLMETHACRYLATE BONE CEMENT 389 to harden for several force period Thus.04 max. max.4 0.5 and 0.1) BaSO4. when placed if excessive. The setting characteristics of the cement are such that. but of the cement instability and reduced mechanical viously undesirable in the present water better sion. the material continues immersion. of Compressive Strength Modulus Elasticity of Specimens (g/ml) 3/1 2/1 8 (MPa) 94. The clinically amounts from heat reduction in peak perature the already ADASpec.7(2.04 represents it was 0. reaction however. in an aqueous envileads to dimensional improved. technique lead to irregularities tics of the cement rather than cal and chemical properties. forcing materials.4 milmilli- ligram gram gram per cm per cm 2 2 and for radiopaque The solubilities study cement were 0. damage to adjacent Incorporation of rein- 12 (mg/cm2) Sorption Solubility (mg/cm2) (mg/cm2) 0. For radiolucent the sorption 0. duced as the amount of kneading is increased. such investigation of the modes of clinical use of the cement for fixation of a Failures which can be attributed directly as fracture of the cement. information of water ronment. although limited provides some of the cement should on the shortcomings be milli- per cm 2. to a characterizaas to which more will the net uptake tion of the material. A fixed the monomer polymerizes.7 0. A small amount of be beneficial and cement this study in leading to due to expanare typical of best come from failure following prosthesis to bone. some make thesis extent insertion and of results in a more and viscous positioning mix.03 after this initial set. use which of the may pros- more difficult to accomplish. seating The however. 57-A. peak One the heat being a longer way can setting temperature is to reduce be dissipated This period after reached. respectively.5 contained in parentheses. in addition to reducing the peak temperature. although the major part of the setting occurs in about ten initiated at a lower ing of the cement and lead quent to a longer loosening temperature. The time required for the mastage is greatly affected by the and the setting time is re- A second possible before way insertion. advisable The properties information to minimize such forces. might also improve the mechanical properties of the cement. VOL. Practically.04 0.5) 93. A third possible decrease the the volume creasing of monomer to be polymerized TABLE EFFECT OF POWDER-TO-LIQUID MODULUS OF V ON COMPRESSIVE OF CEMENT* powder-to-liquid RATIO ELASTICITY STRENGTH AND large amount of a reinforcing filler in the cement. caused by leaching or components The mechanical have Discussion difficult to prove. which are obuse. hours on a may it is in weight the when the same cement specimens were again measured dried after minutes. Radiopaque Cement Radiolucent Cement Requirements may afford weakened some protection bone. may of the components obtained in strength. NO.04 milligram per cm 2 for solubility). to produce the variations in the handling characteristo variations in its final physi- of the cement and the attendant disadvantage that polymenization may not be as nearly complete as at a higher temperature. increasing the powder-to-liquid ratio from 2/1 to 3/1 reduced the peak temperature by more than 10 degrees centigrade without reduction ofstrength. loosening of the prosthesis with or without infection may be to some extent the result of deterioration of the bone at the cement interfaces as a consequence of the high temperature quantity Therefore.1 (0.7 milligram per cm 2 for sorption and 0.

The amounts of material provided in the premeasured after mixing. The reproducibility of handling characteristics can be greatly aSfected by lack of strict adherence to a standardized mixing procedure. 201. p. . and Co. and Devices. p. neutral molecules. modulus of ticity. and transverse bending strengths. this is re- monomer of the total mass is residual in an aqueous environment. experimental LD-50 values for acrylic and methacrylic esters show that the higher homologues of the series tend to be less toxic bly 18 terial used. setting time. S. Ed. and indentation and recovery. effect however. of the Porosity cement ranged mass. Use of a reinforcing filler to reduce the necessary monomer content one method of shrinkage. Although some effects were individually minor. although this was not investigated in detail. properties Also. composite strength more nearly matching that materials with approximately and two to five bone times modulus Cold-curing the compressive of elasticity the set cement. AND 1972. ALBERT. the improvements in physical properties suggested as desirable in a bone cement of elasticity. 2. mately ture polymerization or by peroxide of approxi- permitted to polymerize grees centigrade. Ltd. with the exception of the presence of peroxide (approximately 2 per cent) in the powder. and Summary components revealed no covery cent studies. BRAUER. greater These than what differences of ma- would be required to determine whether this would reduction of the amount of monomer in surrounding Use of a higher advantageous. HAAS. Ed. mechanical performance of polymethylmethacrylate cement approximates that of polymethylmethacrylate of methylmethacrylate cement are used as dental such materials have required handling bone cement the improved clinical service restorative materials 8 Whether or not or could readily be modified to have the and tissue-response characteristics of determined. Methuen Guide Guide to Dental to Dental Materials Materials ASSOCIATION: Ed. 6. 1968. by further Residual cement to surrounding temperature was greatly In our investigation. and temperarise were found to be most affected by environmental and thus contained unreacted monomer of time than did specimens polymerized A reinforced resin system initially. American Dental Chicago. weakness in the collection of the of data. 4. of the might cement also from Any permit tissue. Chicago. handling time. a complementary marked departures The cement up to 5 per cent cent of the volume during combination of these could produce from expected performance.4 per cent either diffusion out of the cement. However. Dough time. would whether provide or not better ture base resin and repair materials. as determined by studies of tensile. A potential for subsequent loosening of the components may lie in the finding that the cement attains strength rather gradually. and Devices. to the period of greatest Hartman 20 per cent was be important. M. Aging at room temperature strable were. since molecular weight the rate at which monomer it dissolves fuses into the tissues is likely to be slower. contain less monomer temperature and kneading of the dough mass. of its final We found recovery that the material value in the first attained fifteen 80 per minutes Conclusions of The analyses of the liquid and powder commercial medical methylmethacrylate significant variation from the information given on the manufacturer’s package insert. when specimens were duced to 1 . There results in the evaluation were error. penetrate membranes readily 1 Furthermore. pressive. JOINT SURGERY JOURNAL OF BONE . G. AMERICAN ADRIEN: DENTAL DENTAL Selective AssocIATIoN: Toxicity and Related Topics. was found to exhibit volume contraction of on setting. In general. 210. Association. Water sorption and solubility characteristics were also similar to those of denture base resins. Among have been higher bone. as assessed by indentation its final and re- has not been mechanical is not known. twice modulus of the mix of cement providing a cement would appear to be with lower volume that is a of the creased of pressure by rapid mixing speed and reduced by application properties polymerization. 258. but experimental 37 degrees centigrade. AMERICAN 3. reduced S. London. were somewhat ferior in cement containing barium sulphate. Note: The authors thank Philltp Leo and Albert for assistance References I . than three of not more 0. on of the components for up to five months in their sealed packages had no demonthe some performance inconsistent of the cement. if shrinkage does have an effect it might be expected to contribute to loosening at the bone-cement interface. in reduction of the the cement sets. 6. Variations in humidity. . the remaining reached in about eighteen hours. Mechanical from Porosity 1 to 10 per was inof cornelasinthe bone den- Shrinkage not great of the bone cement during setting is probaenough to have a major effect on its service- ability. might be and difGenerally. 3 per cent is also present after curing. Thereafter. and mixing speed within ranges likely to be encountered in an operating room had little effect. p. AND G. DICKSON the cement system more is generally characteristics temperature polymerization from peak considered to be one of the more which slows to the tissues undesirable for reducing peak the rate of to pass packages of liquid and powder Some unreacted (residual) polymerization of the cement.390 The escape of monomer of the cement. mately After 3 per cent four months were quite constant. monomer remains after the After one hour. approximonomer. This may that large forces are often generated in the prosthetic components immediately after which corresponds cement. but slowly period in molds previously cooled to 7 dethese specimens also polymerized for a longer in molds at would also evidence result in tissues. provided they have no more water-attracting groups and a molecular weight of handling characteristics which could be attributed to experimental may be caused by inherent variation in the batches than 1 50. 1972. American Dental THE Association. powder-to-liquid ratio.

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