α—磷酸三钙—磷酸四钙生物骨水泥的研究

对α-磷酸三钙（α-TCP）-磷酸四钙（TTCP）体系的胶凝特性进行了研究。探讨了α-TCP/TTCP复合骨水泥的水化硬化过程、水化产物、水化反应动力学、反应转化率、硬化体微观结构等变化规律及强度变化的根本原因。     

α-磷酸三钙-磷酸四钙生物骨水泥的研究

对α-磷酸三钙 (α TCP) 磷酸四钙 (TTCP)体系的胶凝特性进行了研究。探讨了α TCP TTCP复合骨水泥的水化硬化过程、水化产物、水化反应动力学、反应转化率、硬化体微观结构等变化规律及强度变化的根本原因。     

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)。     

淀粉基水化温升抑制剂对水泥-粉煤灰复合胶凝材料水化的影响

本实验主要研究了淀粉基水化温升抑制剂( TRI)对水泥-25%粉煤灰、水泥-50%粉煤灰复合胶凝材料凝结时间、抗压强度、水化放热历程的影响,并与纯水泥进行比较.通过对比TRI在水泥和粉煤灰上的吸附性能和水化产物的变化,对其影响机理进行了分析.结果表明:随TRI掺量增加,凝结时间都延长,早期强度都降低,复合体系后期(60 d)强度存在损失,但不影响纯水泥后期强度,水化放热速率峰值都大幅度降低,缓解了集中放热.水泥对TRI的吸附能力更强,导致复合体系中单位水泥吸附的TRI更多,使得降峰效果更好,同时也导致凝结时间延长更多,增大早期强度损失. TRI不影响纯水泥最终水化程度,但会延缓粉煤灰的火山灰反应,因此降低了复合体系60 d强度.     

新型钇-羟基磷灰石骨水泥的制备及性能研究

利用高温固相法合成了掺钇的磷酸四钙,将其与无水磷酸氢钙以物质的量比1∶1混合制备了钇-羟基磷灰石骨水泥(Y-HAC)。结果表明:少量钇的掺入不会改变骨水泥的水化产物,骨水泥能正常水化,水化产物为弱结晶羟基磷灰石。与纯羟基磷灰石骨水泥(HAC)相比,Y-HAC的湿态抗压强度提高了120%,干态抗压强度提高了85%。同时,钇的掺入还提高了材料的孔隙率。Y-HAC的微观结构呈现紧密结合的片状羟基磷灰石结晶体。体外释放实验表明,钇的释放量极低,说明钇-羟基磷灰石骨水泥具有较好的稳定性。Y-HAC是一种很有前途的骨组织修复材料,并可用于载药材料和骨组织工程支架材料。     

Na2SO4·10H2O对磷酸钾镁水泥水化硬化的影响

磷酸钾镁水泥凝结硬化过快及水化放热集中的问题严重制约着其大规模工程应用,相变材料的吸热储能功能为解决这一问题提供新途径。研究了无机水合盐Na_2SO_4·10H_2O(NS)对磷酸钾镁水泥(MKPC)水化温升、工作性能和抗压强度的影响,并结合XRD、FT-IR、SEM等分析手段及其水化放热速率曲线探究了NS对MKPC性能的影响机制。结果表明:NS的溶解和相变过程吸收大量热,同时释放出结晶水,降低了MKPC体系中Mg~(2+)、PO_4~(3-)和H~+的溶出速率及浓度,MKPC系统内部水化反应速率降低,凝结时间延长,流动度增大,水化放热和水化温升变得更加平缓,在水化早期,MKPC的硬化体强度随NS掺量增加略有降低。在一定的NS掺量(≤4%)内,MKPC水化产物的结晶度提高,后期强度稳定增长,掺有2%NS的MKPC的28d强度将高于基准组。     

粉煤灰掺量对磷酸钾镁水泥水化动力学的影响

使用等温微量热仪测定了粉煤灰掺量分别为0、5%、10%、15%、20%和25%的磷酸钾镁水泥((Magnesium potassium phosphate cement,MKPC)在20℃的水化放热速率和放热量。根据Knudsen和Kondo水化动力学公式计算了MKPC水化最终放热量Q_∞、各阶段的水化阻力N和反应速率常数K,研究了粉煤灰掺量对MKPC水化历程的影响机理。结果表明:对于不同粉煤灰掺量的MKPC最终放热量和动力学参数的计算,Knudsen和Kondo水化动力学公式都具有优异的适用性,拟合相关度很高。磷酸钾镁水泥的水化过程可分为6个阶段,水化反应始于第二阶段,水化进行至第四阶段时MKPC由结晶成核直接进入到扩散阶段。随着粉煤灰掺量从0提高到15%,MKPC体系中反应组分MgO和KH_2PO_4的含量减少,水化放热量降低,粉煤灰主要以物理填充作用参与MKPC水化,对磷酸镁水泥水化过程影响较小。当粉煤灰掺量为15%~25%、硼砂相对含量减少时,粉煤灰的火山灰效应显著,水化放热量增大,MKPC各水化阶段的N和K值的变化较大。     

磷酸镁水泥水化热的影响因素研究

采用八通道微量热仪研究了不同m(M)/m(P)(氧化镁和磷酸二氢钾质量比)比值、水胶比(W/B)、硼砂掺量、粉煤灰掺量和磷酸盐种类对磷酸镁水泥水化热的影响规律。实验结果表明,磷酸镁水泥的水化存在吸热和放热两个过程,包含一个吸热谷和两个放热峰,吸热谷产生于磷酸盐的溶解,放热峰与氧化镁溶于酸性溶液及产物的形成有关;提高m(M)/m(P)比值、水胶比、硼砂掺量和粉煤灰掺量都会降低磷酸镁水泥水化的放热速率和放热量;以磷酸二氢铵、磷酸二氢钠、磷酸二氢钾为磷酸盐所制备的磷酸镁水泥的水化放热峰峰值和放热量分别达到了0.430714,0.145677,0.194626 W和1198.949,452.798,902.872J,表明了磷酸盐种类对磷酸镁水泥水化热和放热速率有显著的影响,这与三者的溶解度和pH值有关。     

硫铝酸盐复合水泥体系水化特征研究

通过正交试验研究了硫铝酸盐复合水泥中不同掺量的普通硅酸盐水泥、石膏、硅灰及粉煤灰对其强度、自收缩以及水化热的影响。结果表明:普通硅酸盐水泥及石膏的掺入显著改变了硫铝酸盐复合水泥水化进程,硅灰及粉煤灰是影响后期强度的主要因素;自收缩试验结果表明普通硅酸盐水泥和石膏是影响硫铝酸盐复合水泥水化早期自收缩的主要因素;水化热测试结果表明粉煤灰和普通硅酸盐水泥在水化前6 h起到显著作用,粉煤灰降低了水化放热,而普通硅酸盐水泥增加水化放热;硅灰及石膏对6~24 h水化放热影响显著。结合XRD及SEM测试结果,表明普通硅酸盐水泥和石膏的存在加速了硫铝酸盐复合水泥水化早期钙矾石生成,随着石膏浓度的下降,发生转晶(AFm),随着后期硫铝酸盐水泥中β-C₂S的水化以及硅灰、粉煤灰的火山灰反应产生C-S-H凝胶,使得体系致密化。     

膨润土对磷酸镁水泥性能的影响

采用膨润土等量取代磷酸镁水泥的方法,研究了膨润土对磷酸镁水泥流动度、凝结时间、强度、水化热和早期收缩的影响,并对水化产物进行了分析与讨论。结果表明,膨润土降低了磷酸镁水泥的流动度、凝结时间和强度,为保证施工的可操作性,其掺量应控制在10%以内;膨润土有效降低了磷酸镁水泥的放热速率和放热量,减少了其早期收缩;掺有膨润土的磷酸镁水泥的水化产物中存在膨润土的主要成分蒙脱石和石英;膨润土影响了磷酸镁水泥的水化过程、水化产物的数量及其结晶程度。     

Improvement of Mechanical Properties of Self Setting Calcium Phosphate Bone Cements Mixed With Different Metal Oxides

Calcium phosphate cements (CPC), based on multicomponent powder mixtures of calcium orthophosphates with medium particle sizes in the region of 1 ‐ 20 μm, set isothermally in an aqueous environment to form hydroxyapatite (HA). HA cement reactants include tetracalcium phosphate (TTCP), tricalcium phosphate (TCP), dicalcium phosphate anhydrate (DCPA), dicalcium phosphate dihydrate (DCPD), monocalcium phosphate (MCPA) or octacalcium phosphate (OCP). The aim of this study was to improve the mechanical performance of TTCP / DCPA cement by adding several metal oxides to tetracalcium phosphate during the fabrication process. Cements based on tetracalcium phosphate mixed with silica or titanium oxide showed significant increases in compressive strength, approximately 80 ‐ 100 MPa, whilst no change in the mechanical behavior of CPC was observed if zirconia was added. X‐ray diffraction measurement confirmed the setting reaction of doped cements was similar to that of pure CPC. Low crystalline HA was found to be the main constituant of set cement; additional phases, such as calcium titanate or calcium zirconate, were not involved in the reaction. A mechanical reinforcement effect was thought to result from changes in the thermodynamic or kinetic solubilities of doped tetracalcium phosphates, this would lead to slower HA crystal formation and a more cross‐linked cement structure.     

Addition of sodium hyaluronate and the effect on performance of the injectable calcium phosphate cement

An injectable calcium phosphate cement (CPC) with porous structure and excellent anti-washout ability was developed in the study. Citric acid and sodium bicarbonate were added into the CPC powder consisting of tetracalcium phosphate (TTCP) and dicalcium phosphate dihydrate (DCPD) to form macro-pores, then different concentrations of sodium hyaluronate (NaHA) solution, as liquid phase, was added into the cement to investigate its effect on CPC’s performance. The prepared CPCs were tested on workability (injectable time and setting time), mechanical strength, as well as anti-washout ability. The experimental results showed that addition of NaHA not only enhanced the anti-washout ability of the CPC dramatically but also improve its other properties. When NaHA concentration was 0.6 wt%, the injectable time elongated to 15.7 ± 0.6 min, the initial and final setting times were respectively shorten to 18.3 ± 1.2 and 58.7 ± 2.1 min, and the compressive strength were increased to 18.78 ± 1.83 MPa. On the other hand, Addition of NaHA showed little effect on porous structure of the CPC and enhanced its bioactivity obviously, which was confirmed by the apatite formation on its surface after immersion in simulated body fluid (SBF). In conclusion, as an in situ shaped injectable biomaterials, the CPC with appropriate addition of NaHA would notably improve its performance and might be used in minimal invasive surgery for bone repair or reconstruction.     

A Natural Bone Cement—A Laboratory Novelty Led to the Development of Revolutionary New Biomaterials

Research on calcium phosphate chemistry at NIST led to the discovery of the worlds first self-hardening calcium phosphate cements (CPC) in 1987. Laboratory, animal, and clinical studies were conducted to develop CPC into clinically useful biomaterials. The combination of self-hardening capability and high biocompatibility makes CPC a unique material for repairing bone defects. Near perfect adaptation of the cement to the tissue surfaces in a defect, and a gradual resorption followed by new bone formation are some of the other distinctive advantages of this biomaterial. In 1996 a CPC, consisting of tetracalcium phosphate and dicalcium phosphate anhydrous, was approved by the Food and Drug Administration (FDA) for repairing cranial defects in humans, thus becoming the first material of its kind available for clinical use. This paper will review the course of the development, the physical and chemical properties, and clinical applications of CPC.     

Effect of molecular weight and concentration of poly(acrylic acid) on the formation of a polymeric calcium phosphate cement

Previous investigations have noted that the tetracalcium phosphate (TTCP)/dicalcium phosphate anhydrous (DCPA) apatite forming calcium phosphate cement (CPC) possesses many favorable properties from a biomaterials standpoint. Despite these positive properties various shortcomings have limited clinical usage of these materials and fostered investigations into the effect of numerous additives. The present study concerns the effect of poly(acrylic acid) (PAA) addition and the influence of factors such as molecular weight and concentration of the additive on the properties of the set cement. One-way ANOVA was conducted using all results obtained, to firstly derive the influence of concentration within each molecular weight group, and secondly to derive the influence of molecular weight within each concentration group. All investigated mechanical properties were influenced by both molecular weight and concentration of the additive. Higher molecular weights tended to result in cements with shorter setting times and higher compressive, diametral and biaxial flexural strengths than their lower molecular weight counterparts. The effect of concentration on the properties of the set cement however was somewhat more complex, a negative correlation was observed between the initial setting time and PAA concentration. In regards to the final setting time, any correlation with concentration was difficult to derive as a consequence of the highly brittle nature of cements made with low concentrations. In regard to mechanical properties, intermediate concentrations tended to give higher strengths than both their higher and lower counterparts, however the exact pattern was largely specific to the mechanical strength test employed. We conclude that molecular weight and concentration of PAA influence the setting behavior and final mechanical properties of the TTCP/DCPA cement, and that selection of an appropriate PAA solution can lead to the production of cements with properties superior to those formed in the absence of the polymer.     

磷酸钙骨水泥的水化反应机理研究

本文对新型的人工骨材料磷酸钙骨水泥的水化反应机理进行了研究，结果表明，ＣＰＣ水化反应的热力学基础在于各种磷酸钙盐溶解差异，当ＰＨ〉４．２时，羟基磷灰石ＨＡＰ的溶解度最小，其它磷酸钙盐在水中可通过溶沉淀出ＨＡＰ；ＣＰＣ采用两种酸碱性不同的磷酸钙盐，可以利用酸碱副产物的中和反庆使体系ＰＨ值稳定，使水化反庆保持一的推动力，由磷酸四钙ＴＥＣＰ和无水磷酸氢钙ＤＣＰＡ组成的ＣＰＣ，其水化反应的动力学前期由ＤＣ     

Mechanical and rheological properties and injectability of calcium phosphate cement containing poly (lactic-co-glycolic acid) microspheres

To enhance tissue ingrowth and promote rapid resorption, efforts were made to build macropores into calcium phosphate cement (CPC); however, this led to a decrease in its mechanical properties. In this study, poly (lactic-co-glycolic acid) (PLGA) microspheres were incorporated into CPC to impart macroporosity and maintain early strength. The influences of the content of PLGA microspheres on the mechanical strength, rheological properties, injectability, setting time, and microstructure of CPC were also systematically investigated. At the PLGA to CPC mass ratios of 20/80 and 30/70, the compressive strength of the composites was similar to that of CPC without PLGA microspheres. The rheological results indicated that PLGA microspheres/CPC pastes showed plastic and shear-thinning behaviors. The addition of PLGA microspheres to CPC resulted in the increase of viscosity and yield stress of the pastes. Simultaneously, the injectability of the pastes decreased with the addition of PLGA microspheres. When the PLGA to CPC ratio was 20/80, the injectability of the paste was still higher than 95%. The calcium phosphate cement containing 20 wt.% PLGA microspheres exhibited excellent injectability and satisfactory setting time without strength degradation. Obviously, such an in situ macropores-generable CPC should have potential prospects for the wider applications in orthopedics, oral, and maxillofacial surgery.     

Properties and mechanisms of fast-setting calcium phosphate cements

The setting time of a calcium phosphate cement consisting of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA) was reduced from 30 to 5 min by use of a cement liquid that contained a phosphate concentration of 0.25 mol/l or higher. The diametral tensile strength and conversion of the cement ingredients to hydroxyapatite (OHAp) during the first 3 h were also significantly increased by the phosphate. However, the phosphate produced no significant effects on the properties of the 24-h cement samples. Results from additional experiments in a slurry system verified that the high phosphate concentration in the solution accelerated the formation of OHAp in the TTCP + DCPA system, and this reaction could explain the fast-setting properties of the cements.Certain commercial materials and equipment are identified in this paper to specify the experimental procedure. In no instance does such identification imply recommendation or endorsement by the American Dental Association or National Institute of Standards and Technology or that the materials or equipment identified is necessarily the best available for the purpose.     

丝素纤维强化磷酸钙骨水泥的性能

采用在磷酸钙骨水泥(CPC)中掺入丝素纤维(SFF)来强化CPC。用X射线衍射(XRD)、红外光谱(FT-IR)研究材料的结构,用ISO水泥标准维卡仪测定CPC的凝固时间,用扫描电镜(SEM)观察材料的表面形态,在Instron上测定样品的力学性能。结果表明,CPC中的磷酸三钙和磷酸氢钙在固化过程中基本上转化为羟基磷灰石,SFF的加入加快了磷酸氢钙的转化。CPC的凝固时间随着掺入SFF含量的增加而缩短;弯曲强度和弯曲断裂功均随着SFF含量的增加而增加,尤其弯曲断裂功增加显著,但当SFF含量大于1.5%,两者均随着SFF含量的增加而所下降,但均比纯CPC的高;在CPC中加入1.5%的SFF,压缩强度和压缩断裂功均明显比纯CPC的高。     

不同碳纳米管/羟基磷灰石复合粉末的添加对磷酸钙骨水泥性能和结构的影响

采用物理共混法(PB)、化学共沉积法(CC)和仿生浸泡法(BI)合成了多壁碳纳米管/羟基磷灰石复合粉(MWNTs/HA), 并将其作为磷酸钙骨水泥(CPC)的固相粉末之一, 分别制备了相应的CPC样品。由于MWNTs对液相中水分子的吸附、毛细管作用以及表面存在较多的亲水基团, 使得含有MWNTs的CPC样品的亲水性得以提高, 且初凝时间和终凝时间都有所缩短, 但仍满足临床应用的要求。由于CPC中的MWNTs/HA复合粉末的合成方式不同, 使之对CPC的抗压性能、CPC中HA的结晶性、微观形貌影响均较大, 但并不影响CPC的晶相组成。其中PB法所合成的MWNTs/HA复合粉末能促进CPC中纳米级HA晶体的转化和生长, 使针状HA含量的表现为最高, 且抗压力学性能为最好, 其抗压强度和弹性模量分别较空白CPC提高了48.23%和41.87%。     

自固化硅羟基磷灰石骨水泥的制备及性能研究

采用磷酸四钙和磷酸氢钙为羟基磷灰石水泥(HAC)粉末,5wt%硅酸钠水溶液为固化液, 制备了硅羟基磷灰石水泥(s-HAC). 结果显示: s-HAC的凝结时间和抗压强度性能明显优于以水为固化液的HAC. XRD和IR结果分析表明: s-HAC的最终水化产物为硅羟基磷灰石. s-HAC在Tris-HCl缓冲溶液中不仅能够释放出Ca、P离子,而且还能释放出Si离子, s-HAC的体外降解性优于HAC. 细胞培养实验显示: MG₆₃细胞不仅能够在s-HAC和HAC表面粘附并保持正常的细胞形态; 而且MG₆₃细胞在s-HAC上的光密度(OD)值和碱性磷酸酶(ALP)活性明显高于HAC, 这说明s-HAC能促进成骨细胞增殖和分化.