Composition effects on the pH of a hydraulic calcium phosphate cement

The pH of a hydraulic calcium phosphate cement (HCPC) made of monocalcium phosphate monohydrate (Ca(H2PO4)2·H2O; MCPM), -tricalcium phosphate (-(Ca3(PO4)2; -TCP) and water was measured as a function of reaction time and composition at room temperature. During setting, the cement pH varies from very acidic pH values, i.e., 2.5, to almost neutral pH values, i.e., 6. The cement pH profile significantly depends on the initial cement composition. However, all profiles are characterized by a sharp initial decrease of the pH due to the dissolution of MCPM crystals and the precipitation of dicalcium phosphate dihydrate (CaHPO4· 2H2O; DCPD) crystals. With an excess of MCPM, the final pH stays low, and its value can be predicted from the initial composition of the cement and solubility data. With an excess of -TCP, the end pH is close to 5, which is much lower than 5.9, the value predicted by calculation. Results suggest that the difference may be due to the presence of impurities in the cement. Replacing MCPM by phosphoric acid renders the cement paste very acidic for the initial 30 s, but then the pH profile follows that obtained with MCPM. Adding pyrophosphate ions into the cement paste postpones the position of the pH minimum. The delay, which is proportional to the concentration of pyrophosphate ions, is thought to be due to the inhibiting action of pyrophosphate ions on the precipitation of DCPD crystals.     

Study of a hydraulic calcium phosphate cement for dental applications

Calcium phosphate-based cements (CPCs) have attracted much interest because of their good osteoconductivity for bone reconstruction. We obtained CPCs by mixing calcium bis-dihydrogenophosphate monohydrate (MCPM) and calcium oxide with water or sodium phosphate buffers (NaP) as liquid phase. Cement samples with different calcium-to-phosphate ratios (Ca/P), liquid-to-powder ratios (L/P) and liquid phases were analyzed by X-rays diffraction (XRD), pH-metry, extensometry and calorimetry. Antibacterial activity on two bacterial strains (Streptococcus mutans, Lactobacillus acidophilus) and a polycontaminated bacterial inoculum was also studied using the agar diffusion method. The best mechanical properties (25 MPa) corresponded to Ca/P ratios between 1.67 and 2.5, a 1 M sodium phosphate buffer pH 7, as liquid phase and a L/P ratio of 0.6 ml g^-1. The final setting time increased with the Ca/P ratio. The setting expansion, around 1–2%, depended on the Ca/P and L/P ratios. The inner temperature of the cements rose to 45° during setting then decreased rapidly. The injectability was 100% up to 3.5 min and then decreased. It increased with increasing the L/P ratio but to the detriment of the compressive strength and setting time. XRD analysis indicated that the setting reaction led to a mixture of calcium hydroxide and calcium-deficient hydroxyapatite even for a Ca/P ratio of 1.67. Consequently, the pH of the surrounding fluids rose to 11.5–12 during their dissolution. Bacterial growth inhibition was only clearly observed for Ca/P2. This bioactive calcium phosphate cement can potentially be employed for pulp capping and cavity lining as classical calcium hydroxide-based cements, but it is not usable, in the present formulation, for root canal filling because of its short setting time.     

可缓释药物的明胶/磷酸钙骨水泥复合组织工程支架材料

采用向孔隙中灌注含聚乳酸聚乙醇酸共聚物（PLGA）载药微球的明胶溶液的方法制备了具有药物缓释功能的明胶/磷酸钙骨水泥复合组织工程支架。用扫描电子显微镜观察了微球和支架的形貌特征,用万能材料试验机测定了支架材料的抗压强度,用紫外-可见分光光度计分析了复合支架的释药率。结果表明,灌注明胶对多孔磷酸钙骨水泥支架起到显著的增强作用,抗压强度达2.42 MPa。复合支架携载硫酸庆大霉素, 具有良好的药物缓释功能,缓释时间可达30天以上,使支架在修复骨缺损的同时能消除炎症反应,成为一种集骨修复和治疗于一体的新型组织工程支架材料,具有良好的应用前景。      

Monitoring the early hydration mechanisms of hydraulic cement

Cement is one of the most widely used construction materials with one billion tonnes used annually. From an engineering point of view, it is essential that cement sets and hardens in a correct manner, indeed, modification of the setting and hardening characteristics of cement by the use of admixtures is becoming widespread in the construction industry. The reaction between cement clinker and water is a complicated chemical process which results in a rigid matrix capable of sustaining load. The increase in strength of the cement matrix is the consequence of hydration and crystal formation within the paste. Understanding the mechanisms of hydration and how they can be modified could result in new cement blends and admixtures tailor-made to suit any particular set of design criteria. In this paper it is shown that the temporal change in electrical response can be used to monitor the progress of hydration, and give an insight into mechanisms of hydration. Data are presented for several cement paste consistencies over the frequency range 20 Hz to 300 kHz.     

Development of an octocalcium phosphate cement

From previous studies it is known that alpha-tertiary calcium phosphate and dicalcium phosphate form a cement upon mixing with water. In this study this cement was optimized in terms of the milling of the constituents, their molar ratio, the amount of hydroxyapatite added and the water/powder ratio. The optimum Ca/P molar ratio of the cement mixture was 1.36±0.03. X-ray diffraction showed the reaction product to be octocalcium phosphate. Addition of precipitated hydroxypatite of over 3% diminished the final strength of the cement significantly. However, admixtures of only 2% of precipitated hydroxyapatite (a) kept the final compressive strength at 30±5 MPa after soaking in Ringers solution at 37°C, (b) diminished the initial setting time from 27.5 to 10 min and the final setting time from 65 to 40 min, (c) diminished the time in which the final strength was reached from 36 to less than 14 h. The tensile strength of this cement is 19±1% of its compressive strength. The optimum water/powder ratio as found in this study was 0.30 g/g.     

Formation of macropores in calcium phosphate cement implants

A calcium phosphate cement (CPC) was shown to harden at ambient temperatures and form hydroxyapatite as the only end-product. Animal study results showed that CPC resorbed slowly and was replaced by new bone. For some clinical applications, it would be desirable to have macropores built into the CPC implant to obtain a more rapid resorption and concomitant osseointegration of the implant. The present study investigated the feasibility of a new method for producing macropores in CPC. Sucrose granules, NaHCO₃, and Na₂HPO₄ were sieved to obtain particle sizes in the range of 125 m to 250 m. The following mixtures of CPC powder (an equimolar mixture of tetracalcium phosphate, Ca₄(PO_{4 2}O, and dicalcium phosphate anhydrous, CaHPO₄) and one of the above additive granules were prepared: control–no additive; mixture A–0.25 mass fraction of sucrose; mixture B–0.25 mass fraction of NaHCO₃; mixture C–0.25 mass fraction of Na₂HPO₄, and mixture D–0.33 mass fraction of Na₂HPO₄. Cement samples were prepared by mixing 0.3 g of the above mixtures with 0.075 ml of the cement liquid (1 mol/l Na₂HPO₄). After hardening, the specimens were placed in water for 20 h at about 60 °C to completely dissolve the additive crystals. Well-formed macropores in the shapes of the entrapped crystals were observed by scanning electron microscope (SEM). The macroporosities (mean±standard deviation; n = 6) expressed as volume fraction in % were 0, 18.9 ± 1.7, 26.9 ± 1.6, 38.3 ± 4.4 and 50.3 ± 2.7 for the control, A, B, C and D, respectively. The diametral tensile strengths (mean±standard deviation; n = 3) expressed in MPa were 10.1 ± 0.7, 3.7 ± 0.3, 2.4 ± 0.2, 1.5 ± 0.5 and 0.4 ± 0.1, respectively, for the five groups. The results showed that macropores can readily be formed in CPC implants with the use of water-soluble crystals. The mechanical strength of CPC decreased with increasing macroporosity. © 2001 Kluwer Academic Publishers     

铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响

研究了铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响及其在复合磷酸盐磷酸镁水泥中的稳定性。实验结果表明,复合磷酸盐磷酸镁水泥抗压强度随着铅离子掺量的增加而降低,其中硝酸铅掺量达到10%时,复合磷酸盐磷酸镁水泥的各个龄期的抗压强度发生明显下降。铅离子对复合磷酸盐磷酸镁水泥凝结时间没有明显影响。在复合磷酸盐磷酸镁水泥水化过程中,铅离子对水泥体系的pH值影响不大,但能够造成水泥水化放热峰出现的时间延迟,水化放热的总量减少并影响主要水化产物的结晶程度。在复合磷酸盐磷酸镁水泥水化反应后期,当硝酸铅掺量达到10%以上时,在水化产物中出现了较为明显的Pb2P2O7的衍射峰。复合磷酸盐磷酸镁水泥固化铅离子的浸出毒性试验结果(43μg/L)远低于国家标准要求(5mg/L)。     

Calorimetric study of magnesium potassium phosphate cement

The thermal behavior of magnesium potassium phosphate cement (MKPC) during the early reaction period has been monitored by isothermal conduction calorimetry at 298 K. It is found that the typical heat evolution curve of the MKPC hydration has one endothermic valley and two distinct exothermic peaks. It is believed that the endothermic valley corresponds to the dissolution of potassium dihydrogen phosphate and the exothermic peaks are related to the dissolution of magnesia and the formation of magnesium potassium phosphate hexahydrate, respectively. The influences of the water to powder ratio, the magnesium to phosphate molar ratio and the setting retarder content on the reaction can be reflected in a change of shape and intensity of the peaks on the heat flow curve. The variation trend is consistent with the change of the setting time of MKPC pastes.     

Injectability evaluation of tricalcium phosphate bone cement

Calcium phosphate cements are biomaterials made from a mixture of calcium phosphate powder in aqueous solutions that forms a paste that reacts at the body temperature and hardens as a result of precipitation reactions. These cements are commonly used in dentistry and orthopedic bone filling surgeries, which require extremely invasive procedures. The challenge consists in formulating an injectable paste by additives incorporation. In this work, three different additives (carboxymethylcellulose, agar polymer and sodium alginate) were incorporated to tricalcium phosphate, in concentrations of 0.4, 0.8, 1.6, 3.2 and 6.4 wt.%. Injectability was evaluated through a new method developed for this purpose. Results showed that it was possible to obtain injectable compositions of α-tricalcium phosphate cement. It was verified that the injectability depends on the rheological behavior of the pastes and injection time. In this study, pastes with viscosity suitable for good homogenization and injection were obtained.     

Scanning electron microscopy imaging of hydraulic cement microstructure

Use of the scanning electron microscope (SEM) with X-ray microanalysis allows study of clinker and cements; permitting measuring bulk phase abundance and surface areas of the phases, as well as bulk chemistry of constituent phases can be carried out. Direct imaging of hydraulic cements by SEM yields a more complete picture of both bulk and surface phase compositions. Mass percentages obtained by SEM imaging are in good agreement with percentages based upon QXRD and may differ significantly from those estimated by the Bogue calculations. The finer-grained phases (gypsum, tricalcium aluminate, and ferrite) show much higher surface areas per unit mass than the coarser-grained phases such as alite and belite. Such data are being applied to develop better relationships between the cement material properties and performance properties and to provide starting images for a cement hydration simulation model being developed at NIST.     

On the development of an apatitic calcium phosphate bone cement

Development of an apatitic calcium phosphate bone cement is reported. 100 μ Particles of tetracalcium phosphate (TTCP) and dicalcium phosphate dihydrate (DCPD) were mixed in equimolar ratio to form the cement powder. The wetting medium used was distilled water with Na₂HPO₄ as accelerator to manipulate the setting time. The cement powder, on wetting with the medium, formed a workable putty. The setting times of the putty were measured using a Vicat type apparatus and the compressive strength was determined with a Universal Testing Machine. The nature of the precipitated cement was analyzed through X-ray diffraction (XRD), fourier transform infrared spectrometry (FTIR) and energy dispersive electron microprobe (EDAX). The results showed the phase to be apatitic with a calcium-to-phosphorous ratio close to that of hydroxyapatite. The microstructure analysis using scanning electron microscopy (SEM) showed hydroxyapatite nano-crystallite growth over particulate matrix surface. The structure has an apparent porosity of ∼ 52%. There were no appreciable dimensional or thermal changes during setting. The cement passed the in vitro toxicological screening (cytotoxicity and haemolysis) tests. Optimization of the cement was done by manipulating the accelerator concentration so that the setting time, hardening time and the compressive strength had clinically relevant values.     

In vitro aging of a calcium phosphate cement

Cement samples made of -tricalcium phoshate (-TCP), phosphoric acid (PA) and water mixtures were incubated in several aqueous solutions to determine their stability over time. The effects of the cement composition and the incubating temperature were investigated in more detail. The cement samples contained mostly dicalcium phosphate dihydrate (DCPD) and remnants of -TCP crystals. Depending on the initial cement composition, a certain amount of dicalcium phosphate (DCP) crystals were formed. The larger the initial PA concentration, the larger the DCP amount. After setting, the cement composition was stable for at least 16 days up to 60 °C. Above that temperature, the DCPD crystals decomposed into DCP crystals. The latter reaction provoked a decrease of the pH of the incubation solution, phenomenon expected for a cement sample containing an excess of PA. As the cement samples contained an excess of -TCP, it was postulated that -TCP crystals became so covered by DCP or DCPD crystals during setting that the setting reaction was stopped prematurely. The latter phenomenon gave a good explanation for the low pH values measured in the incubation solutions. ©©2000 Kluwer Academic Publishers     

Structural stability of calcium phosphate cement during aging in water

A calcium phosphate cement (CPC) has been prepared by mixing dicalcium phosphate anhydrate (DCPA, CaHPO₄) and calcium hydroxide (Ca(OH)₂) with a sodium phosphate (Na₂HPO₄) solution. After setting and hardening, the cement is aged in water. High resolution structural and microstructure analyses are carried out to evaluate the stability of the CPC in water over a period of 150 days. The lattice parameters of the apatite crystal remain the same throughout the aging process. The size of apatite crystallites is not changed either; nevertheless, the shape of the particles changes from equiaxed to rod-like.     

In vivo behaviour of three calcium phosphate cements and a magnesium phosphate cement

Three types of calcium phosphate cements and one magnesium phosphate cement were implanted subcutaneously in rats under exclusion of direct cellular contact. Retrieval times were either 1, 2, 4 or 8 weeks. Before and after retrieval the compressive strength, the diametral tensile strength, the quantitative chemical composition, the qualitative phase composition, the FTIR spectrum and the microstructure were determined. The three calcium phosphate cements maintained their strength during implantation. The phase DCPD was completely transformed into a Na- and CO₃-containing apatite, the phases DCP and CDHA only partially. It could not be ruled out that OCP is also transformed into a bone-mineral-like apatite to a certain extent. That this latter process occurs much faster during the turn-over of living bone, is probably due to the very small crystal size of the OCP particles in bone.     

Effect of crystal seeding on the hydration of calcium phosphate cement

In this paper, the effect of crystal seeding on the hydration of calcium phosphate cement (CPC) has been carefully investigated. The setting time of the CPC slurry not containing any crystal seeds was 150 min, while the setting time for the specimen containing 5 wt% low crystallinity hydroxyapatite used as a crystal seed was 7 min. This improvement in the setting time was due to HAP serving as a substrate for heterogeneous nucleation which accelerated nucleation. In addition, the compressive strength of the specimen containing the crystal seeding was deduced and we report values different from those previously reported in the literature. The calorimetric curve indicated that crystal seeding could reduce the induction period. A.c. impedance spectroscopy revealed that at the beginning of hydration, the rate of reaction increased and also that the mean diameter and porosity decreased as the seed content increased. At the end of the hydration reaction the situation was changed with the mean diameter and porosity in the sample without any seeds being a minimum, which indicated that the compressive strength was a maximum. This result could be explained by the dissolution and reprecipitation of small hydration products produced by the high rate of reaction produced by the introduction of the crystal seeds.     

In-situ observation on the transformation of calcium phosphate cement into hydroxyapatite

In the present study, the in-situ transformation of calcium phosphate cement into hydroxyapatite (HAp) within the first hour is monitored with a synchrotron X-ray beam. A disodium hydrogen phosphate solution is used as cement liquid to activate the reaction between dicalcium phosphate anhydrous (DCPA) and calcium hydroxide (Ca(OH)₂). The XRD analysis indicates that the amounts of DCPA and Ca(OH)₂ first decrease within the first min of the reaction. Then, the intensity of DCPA's XRD peaks starts to increase instead in the period of 5 to 20 min. After 20 min, the DCPA particles are consumed slowly to form fine HAp particles. Large pores are evident upon the completion of reaction.     

Comparison of titanium soaked in 5 M NaOH or 5 M KOH solutions

Commercially pure titanium plates/coupons and pure titanium powders were soaked for 24 h in 5 M NaOH and 5 M KOH solutions, under identical conditions, over the temperature range of 37° to 90 °C. Wettability of the surfaces of alkali-treated cpTi coupons was studied by using contact angle goniometry. cpTi coupons soaked in 5 M NaOH or 5 M KOH solutions were found to have hydrophilic surfaces. Hydrous alkali titanate nanofibers and nanotubes were identified with SEM/EDXS and grazing incidence XRD. Surface areas of Ti powders increased > 50–220 times, depending on the treatment, when soaked in the above solutions. A solution was developed to coat amorphous calcium phosphate, instead of hydroxyapatite, on Ti coupon surfaces. In vitro cell culture tests were performed with osteoblast-like cells on the alkali-treated samples.     

磷酸钙骨水泥化学活性及机械性能研究

在研究磷酸四钙制备方法的基础上,讨论其化学活性,发现该物质在高温时热稳定性不好,易于向能量更低的羟基磷灰石转化;在室温下又容易吸附空气中的水分子,发生缓慢水解.因此最好真空保存.