An Evaluation of Methods to Determine the Porosity of Calcium Phosphate Cements
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An evaluation of methods to determine the porosity of calcium phosphate cements Johanna Engstrand Unosson, Cecilia Persson, Ha˚ kan Engqvist Division of Applied Materials Science, Department of Engineering Sciences, Uppsala University, Uppsala, Sweden Received 19 November 2013; revised 20 March 2014; accepted 30 March 2014 Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/jbm.b.33173 Abstract: The porosity of a material can be determined using phase transformation was observed at higher temperatures. a diversity of methods; however, the results from these The results also showed that drying for 24 h in vacuum was methods have so far not been compared and analyzed for sufficient to achieve water-free cements. The porosity meas- calcium phosphate cements (CPCs). The aim of this study ured was found to vary between the porosity methods eval- was to compare a fast and easy method for porosity meas- uated herein, and to get a complete picture of a cement’s urements with some commonly used porosity methods for porosity more than one method is recommended. Water CPCs. The investigated method is based on the assumption evaporation, is, however, a fast and easy method to estimate that when a wet cement sample is dried, the volume of the the porosity of CPCs and could simplify porosity measure- evaporated water is equal to the volume of pores within the ments in the future. VC 2014 Wiley Periodicals, Inc. J Biomed Mater cement. Moreover, different methods of drying the cements Res Part B: Appl Biomater 00B:000–000, 2014. were evaluated for acidic CPCs. The results showed that dry- ing at room temperature (22 6 1C) is preferable, since a Key Words: porosity, calcium phosphate, ceramic How to cite this article: Engstrand Unosson J, Persson C, Engqvist H. 2014. An evaluation of methods to determine the poros- ity of calcium phosphate cements. J Biomed Mater Res Part B 2014:00B:000–000. INTRODUCTION been made for CPCs. Compared to cements used for, for Calcium phosphate cements (CPCs) have been studied since example, construction, the CPCs have different setting reac- the early 1980s,1,2 and there is still plenty of ongoing tions, final phase composition, and setting times. There are research within this area. Since these cements are very simi- therefore reasons to believe that the CPCs do not behave in lar to the mineral phase of bone they have a high biocom- the same way during porosity measurement and drying as patibility. However, their main limitation in comparison to the construction cements. It is hence important to evaluate the more traditionally used acrylic cements are their the drying procedures and compare porosity measurements mechanical properties, leading to numerous studies focusing for CPCs when utilizing different porosity methods in order on improving the mechanical resistance of CPCs. Since the to determine which methods can be used and which should mechanical properties are strongly linked to the porosity be avoided. (and the pore size distribution) of ceramic materials,3,4 it is Porosity can be measured using a diversity of methods of high interest to have reliable and fast methods to deter- and depending on the material analyzed different methods mine the porosity of such materials. are more commonly used. For CPCs, mainly three methods Depending on the starting powders used, the CPCs can are utilized: helium pycnometry,8–10 mercury intrusion have either a basic or acidic setting reaction; the basic porosimetry (MIP),3,11,12 and using the tabulated density cements having precipitated hydroxyapatite (PHA) as the value of the material11,13–15 to calculate the porosity. The end product; the acidic cements having dicalcium phosphate main drawbacks of these methods are the destructiveness, dihydrate (brushite) and/or dicalcium phosphate anhydrous the long analysis times and the need for special equipment, (monetite) as their end products. Studies on methods to especially for MIP and helium pycnometry, which may entail determine porosity5 and obtain dry materials6 have been that fewer samples are analyzed, compromising statistical performed for cements used in the field of construction and power. Mercury is additionally expensive and toxic; requir- has furthermore been thoroughly reviewed in “Water Trans- ing careful handling, hence adding complexity to the port in Brick, Stone and Concrete” by Hall and Hoff.7 These method. The presence of amorphous phases and unreacted studies showed that the determined porosity is highly starting materials could furthermore give misleading results affected by the drying procedure and porosity method used. when using the tabulated density (presupposes a 100 pure However, to the authors’ knowledge, no such evaluation has and crystalline material) for the calculations. Correspondence to: J. E. Unosson (e-mail: [email protected]) Contract grant sponsor: FP7 NMP project Biodesign and the Swedish Research Council VC 2014 WILEY PERIODICALS, INC. 1 In this study, an alternative method to measure the samples are immersed in a solvent, normally water or alco- porosity of CPCs is compared to some common methods hol and the weight change is monitored until a constant used for CPCs and other types of cements. The new, alterna- weight is achieved. The porosity is then calculated according tive method utilizes the assumption that the volume of to Eq. (2), where msat is the weight of the sample saturated evaporable water in a wet sample is equal to the volume of with solvent, md is the dry weight, qsolvent is the density of the voids within the sample, the accuracy of which has not the solvent used, and Va is the apparent volume. been discussed before for CPCs. However, the method is commonly being used for other cements such as Portland ðmsat 2mdÞ=qsolvent 5,6 UðÞ% 5 Á 100 (2) cement and concrete. This method is the reverse of the Va water resaturation method, which is also frequently used for other types of cements,5,7 and the only equipment The next method used on other materials is solvent needed is a balance and a method to measure the sample exchange, where wet samples are stored in a new solvent volume (using, e.g., a caliper, or Archimedes method in (normally an alcohol) and the weight reduction is monitored 18 water or mercury), which makes it a fast and easy method during the exchange process. When a constant weight is for porosity measurements. achieved, the porosity is calculated according to Eq. (3), The aims of this study were to evaluate a few of the where mwater is the weight of wet sample, malcohol is the existing porosity methods and to develop a method for weight after complete exchange, qwater is the density of porosity measurements of CPCs that is fast, easy and cheap; water, and qalcohol is the density of the alcohol used. that is, do not require any advanced equipment. The method ðm 2m Þ=ðq 2q Þ should also include a drying procedure that does not result UðÞ% 5 water alcohol water alcohol Á 100 (3) in a compositional change for the investigated CPCs. Va All above discussed methods have the disadvantage of THEORY not being able to reach all pores. Depending on the radius When discussing porosity, different expressions are used for of the molecule used, different pore sizes can be reached; the density; and a clarification of the terminology follows. however, some pores will always be considered as closed Throughout this article, apparent density describes the den- pores and will not be taken into account in the calculations. sity of a sample when the outer dimensions are used to The density of the actual bulk material can in theory be cal- measure its volume. Skeletal density describes the density culated using molecular weight and crystalline lattice achieved when calculating the volume of the solid material, parameters received from X-ray diffraction (XRD) measure- excluding pores. ments.16 However, XRD calculations do not take into Two of the commonly used methods (i.e., tabulated den- account any amorphous phases that can be present in the sity and helium pycnometry) calculate the porosity of the sample and might therefore overestimate the skeletal material from the division of the apparent density with the density. skeletal density according to Eq. (1), where qa is the appa- rent density, and qs is the skeletal density. The apparent density is normally measured by immersion in mercury MATERIALS AND METHODS using Archimedes principle,11 or by measuring the outer Acidic CPC sample preparation diameters of the sample.3 Equimolar amounts of monocalcium phosphate monohy- drate (Scharlau) and beta-tricalcium phosphate (b-TCP, q Sigma-Aldrich) were thoroughly mixed with 1 wt % diso- UðÞ% 5 12 a Á 100 (1) qs dium dihydrogen pyrophosphate (SPP, Sigma-Aldrich). The powders were blended with 0.5 M citric acid (aq) in a liquid For basic CPCs it is common to use the tabulated density to powder ratio (L/P) of 0.3 mL/g, this L/P was chosen of the material [i.e., 3.16 g/cm3 for hydroxyapatite (HA)] as since it produces a very liquid paste with a long setting the skeletal density in Eq. (1).11,13–15 However, for the acidic time (i.e., 35 min initial setting time with the Gillmore nee- CPCs helium pycnometry is more commonly used.8–10 dle method19), from which air easily can escape. Defects Helium pycnometry measures the skeletal volume of the from mixing will hence be minimized. Both SPP and citric samples by determining the difference in helium pressure acid were added to retard the setting reaction. between an empty chamber with a calibrated volume and The cement paste was transferred to cylindrical rubber the chamber containing a sample.16 molds (Ø 6 mm, height 12 mm), and allowed to set for 40 The last, and most advanced, method used on CPCs is MIP, min at room temperature [RT, 22C(61C)].