酸碱调节对硫酸钙骨水泥理化性能影响的体外研究

doi:10.3877/cma.j.issn.2096-0263.2024.03.001

中华老年骨科与康复电子杂志 ›› 2024, Vol. 10 ›› Issue (03) : 125 -131. doi: 10.3877/cma.j.issn.2096-0263.2024.03.001

生物材料

酸碱调节对硫酸钙骨水泥理化性能影响的体外研究

伦登兴¹, 徐丽娜², 李思影¹, 李世龙¹, 张伟航¹, 胡永成³^,^†(

)

^1. 261041　潍坊市人民医院（山东第二医科大学第一附属医院）骨肿瘤科
^2. 261041　潍坊市人民医院（山东第二医科大学第一附属医院）呼吸与危重症医学科
^3. 300211　天津市天津医院骨与软组织肿瘤科

收稿日期:2023-10-25 出版日期:2024-06-05
通信作者: 胡永成
基金资助:
2023年度山东省医务职工科技创新计划联合立项项目(SDYWZGKCJHLH2023061); 2023年度潍坊医学院附属医院科技发展项目(2023FYM013)

In vitro study on the effect of acid-base regulation on the physicochemical properties of calcium sulfate bone cement

Dengxing Lun¹, Lina Xu², Siying Li¹, Shilong Li¹, Weihang Zhang¹, Yongcheng Hu³^,^†()

^1. Department of Bone Oncology, Weifang People's Hospital (the First Affiliated Hospital of Shandong Second Medical University), Weifang 261041, China
^2. Department of Respiratory and Critical Care Medicine, Weifang People's Hospital (the First Affiliated Hospital of Shandong Second Medical University), Weifang 261041, China
^3. Department of Bone and Soft Tissue Oncology, Tianjin hospital, Tianjin 300211, China

Received:2023-10-25 Published:2024-06-05
Corresponding author: Yongcheng Hu

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引用本文：

伦登兴, 徐丽娜, 李思影, 李世龙, 张伟航, 胡永成. 酸碱调节对硫酸钙骨水泥理化性能影响的体外研究[J]. 中华老年骨科与康复电子杂志, 2024, 10(03): 125-131.

Dengxing Lun, Lina Xu, Siying Li, Shilong Li, Weihang Zhang, Yongcheng Hu. In vitro study on the effect of acid-base regulation on the physicochemical properties of calcium sulfate bone cement[J]. Chinese Journal of Geriatric Orthopaedics and Rehabilitation(Electronic Edition), 2024, 10(03): 125-131.

目的

探讨碱性碳酸钙对硫酸钙骨水泥的理化性能的影响，为制备适合酸碱度的、可注射性硫酸钙骨水泥提供理论依据。

方法

按CaCO₃在硫酸钙复合物的质量比，分为0%、5%、10%、20%、30%组共5组。充分混合不同含量与外科级硫酸钙制备骨水泥的粉剂。将浓度为3%的甲基纤维素溶液作为骨水泥的液剂。按液固比0.4∶1，混合上述骨水泥的粉剂和液剂，搅拌均匀，形成浆体。根据不同的模具，测量并记录CaCO₃/硫酸钙复合物的初凝时间、终凝时间、抗压强度、体外降解率及pH值变化。

结果

单纯硫酸钙的初凝时间和终凝时间分别为（4.96±0.20）、（5.83±0.12）min。随着CaCO₃的含量的增加，初凝时间和终凝时间呈先增长后降低的趋势（F=25.428、P<0.001；F=30.780、P<0.001）。当含量为10%时初凝时间和终凝时间最长[（13.17±1.87）min和（14.22±2.00）min]。单纯硫酸钙的抗压强度为（23.33±6.35）MPa。随CaCO₃的含量的增加，抗压强度先增强后降低，当含量为20%，抗压强度最大（27.33±5.86）MPa；但CaCO₃对硫酸钙抗压强度的影响无统计学差异（F=1.272，P=0.344）。单纯硫酸钙在降解过程均呈酸性环境（pH=5.32），不同含量碳酸钙均能提高pH值；且当含量10%时，体外降解过程中酸碱度趋于平衡（pH=6.67）。

结论

碳酸钙能改变硫酸钙骨水泥的理化性能，当含量为10%时，能够提供最佳的凝固时间，给术者操作提供足够的时间；且不影响硫酸钙凝固后的抗压强度；此外，当含量为10%时，体内降解过程中的酸碱度也有利于促进新骨的形成。但含量大于10%，其降解时间较短，仍需添加其他的改性剂。

关键词: 碳酸钙, 硫酸钙, 骨水泥成形术, 抗压强度, 凝固时间

Objective

To investigate the effect of basic calcium carbonate on the physical and chemical properties of medical grade calcium sulfate, and to provide a theoretical basis for the preparation of injectable calcium sulfate bone cement with suitable for pH.

Methods

According to the mass ratio of CaCO₃ in calcium sulfate complex, they were divided into 5 groups: 0%, 5%, 10%, 20% and 30%. The powder of bone cement was prepared by fully mixing different contents and surgical grade calcium sulfate. Methylcellulose solution with a concentration of 3% was used as the liquid agent of bone cement. According to the liquid-solid ratio of 0.4∶1, the powder and liquid of the bone cement are mixed and stirred evenly to form a slurry. According to different molds, the initial setting time, final setting time, compressive strength, in vitro degradation rate and pH value of CaCO₃/ calcium sulfate composite were measured and recorded.

Results

The initial setting time and final setting time of calcium sulfate were (4.96±0.20) min and (5.83±0.12) min, respectively. With the increase of CaCO₃ content, the initial setting time and final setting time increased first and then decreased (F=25.428, P<0.001; F=30.780, P<0.001). When the content was 10%, the initial setting time and final setting time were the longest (13.17±1.87 and 14.22±2.00). The compressive strength of pure calcium sulfate is (23.33±6.35) MPa. With the increase of CaCO₃ content, the compressive strength first increases and then decreases. When the content is 20%, the maximum compressive strength is (27.33±5.86) MPa; However, there was no significant difference in the effect of CaCO₃ on the compressive strength of calcium sulfate (F=1.272, P=0.344). The degradation process of pure calcium sulfate was in acidic environment (pH=5.32), and different content of calcium carbonate could increase the pH value; When the content was 10%, the pH tended to balance (pH=6.67).

Conclusion

Calcium carbonate can change the physical and chemical properties of calcium sulfate bone cement. When the concentration is 10%, it can provide the best setting time and enough time for the operator; And does not affect the compressive strength of calcium sulfate after solidification; In addition, when the concentration is 10%, the pH in the process of degradation in vivo is also conducive to promote the formation of new bone. However, when the concentration is more than 10%, the degradation time is short, and other modifiers still need to be added.

Key words: Calcium carbonate, Calcium sulfate, Cementoplasty, Compressive strength, Setting time

图1 碳酸钙-初凝时间和终凝时间曲线图：随着CaCO3含量的增加，初凝时间和终凝时间呈先增加后减少的趋势

表1 不同含量的CaCO₃对硫酸钙的固化时间的影响（

±s）

含量	初凝时间（min）	终凝时间（min）	抗压强度（MPa）
0% CaCO₃	4.96±0.20	5.83±0.12	23.33±6.35
5% CaCO₃	12.29±0.36	14.11±0.38	23.33±4.16
10% CaCO₃	13.17±1.87	14.22±2.00	26.67±3.79
20% CaCO₃	11.04±1.41	11.99±1.35	27.33±5.86
30% CaCO₃	7.99±1.04	9.28±0.41	19.67±2.31

表1 不同含量的CaCO₃对硫酸钙的固化时间的影响（

±s）

含量	初凝时间（min）	终凝时间（min）	抗压强度（MPa）
0% CaCO₃	4.96±0.20	5.83±0.12	23.33±6.35
5% CaCO₃	12.29±0.36	14.11±0.38	23.33±4.16
10% CaCO₃	13.17±1.87	14.22±2.00	26.67±3.79
20% CaCO₃	11.04±1.41	11.99±1.35	27.33±5.86
30% CaCO₃	7.99±1.04	9.28±0.41	19.67±2.31

表2 不同含量的CaCO₃对硫酸钙的固化时间的结果统计学

显著性	0VS1	0VS2	0VS3	0VS4	1VS2	1VS3	1VS4	2VS3	2VS4	3VS4
初凝时间	<0.0001	<0.0001	<0.0001	0.010	0.430	0.270	0.004	0.079	0.001	0.020
终凝时间	<0.0001	<0.0001	<0.0001	0.003	0.916	0.071	0.001	0.060	0.001	0.028
抗压强度	1.000	0.408	0.324	0.364	0.362	0.279	0.319	0.852	0.077	0.057

表2 不同含量的CaCO₃对硫酸钙的固化时间的结果统计学

显著性	0VS1	0VS2	0VS3	0VS4	1VS2	1VS3	1VS4	2VS3	2VS4	3VS4
初凝时间	<0.0001	<0.0001	<0.0001	0.010	0.430	0.270	0.004	0.079	0.001	0.020
终凝时间	<0.0001	<0.0001	<0.0001	0.003	0.916	0.071	0.001	0.060	0.001	0.028
抗压强度	1.000	0.408	0.324	0.364	0.362	0.279	0.319	0.852	0.077	0.057

图2 碳酸钙含量-抗压强度曲线图：随CaCO₃含量的增加，抗压强度先增高后降低，浓度为20%时抗压强度达到最高值，30%时最低

图3~6 硫酸钙降解过程中pH变化。图3　0~31天；图4　第5天；图5　第15天；图6　第31天

表3 硫酸钙降解过程中pH值变化（

±s）

时间点	0%CaCO₃	5% CaCO₃	10% CaCO₃	20% CaCO₃	30% CaCO₃
pH0	7.4	7.4	7.4	7.4	7.4
pH1	6.290±0.116	6.290±0.014	6.277±0.004	6.367±0.026	6.410±0.050
pH2	5.787±0.012	5.987±0.049	6.043±0.048	6.073±0.025	6.135±0.005
pH₃	5.660±0.008	5.953±0.040	6.003±0.031	6.043±0.040	6.100±0.040
pH₄	5.650±0.014	6.007±0.054	6.110±0.071	6.147±0.045	6.170±0.020
pH₅	5.583±0.017	6.057±0.005	6.130±0.036	6.153±0.027	6.195±0.035
pH₆	5.433±0.012	6.007±0.020	6.080±0.045	6.157±0.068	6.150±0.030
pH₇	5.403±0.034	5.927±0.031	6.023±0.054	6.163±0.076	6.155±0.025
pH₉	5.330±0.024	5.830±0.014	5.953±0.021	6.323±0.240	6.215±0.035
pH₁₁	5.327±0.026	5.837±0.009	5.947±0.005	6.513±0.315	6.455±0.025
pH13	5.417±0.012	5.883±0.025	6.023±0.033	6.690±0.365	6.690±0.040
pH15	5.340±0.016	5.840±0.042	6.023±0.033	6.497±0.265	6.860±0.020
pH₁₇	5.310±0.022	5.780±0.022	6.000±0.036	6.727±0.272	6.855±0.015
pH₁₉	5.327±0.017	5.807±0.021	6.103±0.031	6.833±0.205	6.940±0.009
pH₂₁	5.303±0.009	5.787±0.021	6.137±0.037	6.910±0.158	6.965±0.005
pH₂₃	5.303±0.012	5.773±0.025	6.240±0.094	6.860±0.768	6.985±0.015
pH₂₅	5.417±0.012	5.867±0.029	6.43±0.120	7.320±0.323	7.080±0.010
pH₂₇	5.307±0.019	5.777±0.031	6.513±0.130	7.327±0.360	7.025±0.005
pH₂₉	5.277±0.017	5.753±0.029	6.483±0.082	7.326±0.299	7.050±0.020
pH₃₁	5.317±0.012	5.787±0.025	6.610±0.119	7.333±0.184	7.110±0.030
平均	5.462±0.242	5.892±0.131	6.165±0.198	6.672±0.452	6.608±0.386

表3 硫酸钙降解过程中pH值变化（

±s）

时间点	0%CaCO₃	5% CaCO₃	10% CaCO₃	20% CaCO₃	30% CaCO₃
pH0	7.4	7.4	7.4	7.4	7.4
pH1	6.290±0.116	6.290±0.014	6.277±0.004	6.367±0.026	6.410±0.050
pH2	5.787±0.012	5.987±0.049	6.043±0.048	6.073±0.025	6.135±0.005
pH₃	5.660±0.008	5.953±0.040	6.003±0.031	6.043±0.040	6.100±0.040
pH₄	5.650±0.014	6.007±0.054	6.110±0.071	6.147±0.045	6.170±0.020
pH₅	5.583±0.017	6.057±0.005	6.130±0.036	6.153±0.027	6.195±0.035
pH₆	5.433±0.012	6.007±0.020	6.080±0.045	6.157±0.068	6.150±0.030
pH₇	5.403±0.034	5.927±0.031	6.023±0.054	6.163±0.076	6.155±0.025
pH₉	5.330±0.024	5.830±0.014	5.953±0.021	6.323±0.240	6.215±0.035
pH₁₁	5.327±0.026	5.837±0.009	5.947±0.005	6.513±0.315	6.455±0.025
pH13	5.417±0.012	5.883±0.025	6.023±0.033	6.690±0.365	6.690±0.040
pH15	5.340±0.016	5.840±0.042	6.023±0.033	6.497±0.265	6.860±0.020
pH₁₇	5.310±0.022	5.780±0.022	6.000±0.036	6.727±0.272	6.855±0.015
pH₁₉	5.327±0.017	5.807±0.021	6.103±0.031	6.833±0.205	6.940±0.009
pH₂₁	5.303±0.009	5.787±0.021	6.137±0.037	6.910±0.158	6.965±0.005
pH₂₃	5.303±0.012	5.773±0.025	6.240±0.094	6.860±0.768	6.985±0.015
pH₂₅	5.417±0.012	5.867±0.029	6.43±0.120	7.320±0.323	7.080±0.010
pH₂₇	5.307±0.019	5.777±0.031	6.513±0.130	7.327±0.360	7.025±0.005
pH₂₉	5.277±0.017	5.753±0.029	6.483±0.082	7.326±0.299	7.050±0.020
pH₃₁	5.317±0.012	5.787±0.025	6.610±0.119	7.333±0.184	7.110±0.030
平均	5.462±0.242	5.892±0.131	6.165±0.198	6.672±0.452	6.608±0.386

图7 硫酸钙复合材料的降解率

表4 硫酸钙复合材料的降解率（%，

±s）

降解率	0%CaCO₃	5% CaCO₃	10% CaCO₃	20% CaCO₃	30% CaCO₃
m₀	0	0	0	0	0
m₅	11.35±0.05	12.19±0.26	11.24±0.07	11.57±0.18	12.32±0.37
m₁₀	25.13±1.70	25.03±0.07	23.64±0.62	25.58±0.03	26.48±0.17
m₁₅	36.64±2.00	37.59±0.13	35.43±0.56	38.51±0.21	40.69±0.15
m₂₀	47.80±1.93	47.80±1.93	47.80±1.93	51.06±0.20	54.11±0.31
m₂₅	59.01±1.79	62.11±0.07	58.07±0.71	63.37±0.16	67.45±0.16
m30	69.62±1.78	73.44±0.16	69.44±0.79	75.27±0.28	79.43±0.21
m35	80.86±1.36	85.45±0.05	80.80±0.96	87.22±0.44	92.11±0.14
m40	90.87±1.45	88.15±0.20	92.68±1.30	97.38±0.58	99.23±0.54

表4 硫酸钙复合材料的降解率（%，

±s）

降解率	0%CaCO₃	5% CaCO₃	10% CaCO₃	20% CaCO₃	30% CaCO₃
m₀	0	0	0	0	0
m₅	11.35±0.05	12.19±0.26	11.24±0.07	11.57±0.18	12.32±0.37
m₁₀	25.13±1.70	25.03±0.07	23.64±0.62	25.58±0.03	26.48±0.17
m₁₅	36.64±2.00	37.59±0.13	35.43±0.56	38.51±0.21	40.69±0.15
m₂₀	47.80±1.93	47.80±1.93	47.80±1.93	51.06±0.20	54.11±0.31
m₂₅	59.01±1.79	62.11±0.07	58.07±0.71	63.37±0.16	67.45±0.16
m30	69.62±1.78	73.44±0.16	69.44±0.79	75.27±0.28	79.43±0.21
m35	80.86±1.36	85.45±0.05	80.80±0.96	87.22±0.44	92.11±0.14
m40	90.87±1.45	88.15±0.20	92.68±1.30	97.38±0.58	99.23±0.54

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In vitro study on the effect of acid-base regulation on the physicochemical properties of calcium sulfate bone cement

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In vitro study on the effect of acid-base regulation on the physicochemical properties of calcium sulfate bone cement