含锆磷酸盐包埋材料铸钛性能的实验研究
摘要
前言
本研究采用二层集合法和成刃器制作30°刃状边缘蜡型，分别以不同配比的含锆磷酸盐包埋材料和日本产铸钛包埋材料包埋后进行铸造，通过测定各组刃状边缘铸件的铸入不足量，同时用电子探针分析钛基体内包埋材料主要元素的扩散情况，以评价含锆磷酸盐包埋材料的铸钛性能。探讨其用于铸钛的可行性，为临床上应用性能良好而成本较低的包埋材料提供实验依据。
材料与方法
一、实验材料：
1．含锆磷酸盐包埋材料：
将不同质量的ZrO_2与磷酸盐包埋材料混合配制成分别含30％、40％和50％ZrO_2三组包埋材料。以日本Titavest-CB专用铸钛包埋材料作为对照。
2．二层集合体及刃状边缘蜡型的制作：A框架置于光洁玻璃板上，四周用红蜡封实固定，框架内面四周及玻璃板涂布一薄层石蜡油，调和搅拌包埋材料注入A框。在B框架中，下层固定冷却后包埋材料板，新型嵌体蜡融化后注入B框架包埋材料板上层，制成二层集合体，用齿科线锯、成刃器制成规格为7×12×10mm刃状边缘蜡型。
3．铸造钛料：由北京亚联电子材料技术研究所提供。
二、实验器材：
1．真空搅拌机(美国)
2．茂福炉什avo公司，德国）
3．恒温熔蜡器
4．CYCLARC 11型加压一吸引铸钛机（Morita公司，日本）
5．喷砂机
6．镶嵌机
7．超声波清洗器
8．显微图像分析仪（Metaxnorph／DP10／SZH－IL LB；US／JP；
VIC／OLYMPUS）
9．EPM一l0Q电子探针微分析仪
三、实验方法：
1．安插铸道：用直径2．srnm，长度3nun的铸造蜡条，垂直安
插在蜡型刃状边缘的对侧，将6个蜡型均匀安插于圆形主铸道上。
2．包埋：蜡型表面用无水酒精处理后进行包埋，采用有圈包
埋，铸钛专用铸圈直径50rum，高45nun，内村0．7rum厚的石棉纸。
实验组包埋材料按蒸馏水水：粉一0．13的比例在真空搅拌机中调
和后进行包埋，对照组包埋材料按专用液：粉一0．13在真空搅拌
机中调和后进行包埋。
3．铸造：包埋后的铸圈在室温中放置历小时后焙烧。茂福炉
升温曲线为：室温开始，以每分钟6t的升温速度升至260℃，保持
60分钟后，再以每分钟6℃速度升至850℃，保持60分钟后，自然
冷却到 450t，保持 30分钟后，·CYCLARC 11型加压一吸引铸钛
机铸钛，熔金电流为 250A，两室差压 7k勿cm＼钛块质量叨。
4．铸件表面处理：铸造完成后，立即将铸圈放人冷水中，待完
全冷却后，用笔式喷砂机，气压4kg／cm＼持续 20秒，去除包埋材
料，而后用砂片切去铸道。
四、检测方法：
1．测定各组刃状边缘铸件的铸人不足量：铸人不足量的计算
方法：蜡型通过两标点直线上的MP（定点到蜡型边缘的距离）与
·2·
铸造后MP’，（同一定点到铸件边缘的距离）之差。图像采集、数
据分析使用显微图像分析仪。
2．铸钛基体内包埋材料主要元素扩散情况分析：将铸件沿纵
轴截断，用镶嵌机镶嵌于酚醛树脂内，铸件按金相要求进行研磨。
抛光，用 3％氢氟酸和硝酸的混和液进行轻度腐蚀，用超声波清洗
器在蒸馏水内清洗，用电子探针微分析仪分析铸钛基体内包埋材
料主要元素的X射线强度线分布及X射线强度面扫描。
3．数据处理：采用 SPSS．0 for indows软件包，单因素方差
分析处理铸人不足量。
白 果
一、钛铸件铸人不足量：
各组铸件铸人不足量测定结果为：实验组，30％组为133．79
t 15．26pm，40防组为 132．87 20．56帅，50助组为 IM．13士 18．
3lpm，对照组为 143．73 t 11．50urn。单因素方差分析结果提示：
各组铸件间无显著差异h北．05八
二、铸钛基体内包埋材料主要元素扩散情况分析：
电子探针分析结果：豆 d实验组的 Sika，Pka，Mgka，Zra的
X射线强度线分布提示：厂）。实验组试件反应层中＊扩散深度，
30协组约37 pm，40防组约28 pm，50％组约25 pm。（2）·实验组试
件均可见＊和P的扩散是同步的，但S的扩散深。门〕实验组
试件未见Mg义r的特征波长。对照组X射线强度线分布提示必
扩散约gPm步扩散深度约］LZPm。通过Alk队Sika，Pka的X射
线强度面扫描亦与X射线强度线分布结论相符。实验组中S强
度计数带宽且不致密，但对照组中则强度计数带很薄，且非常致
密。
·3·
讨 论
1．通过测定各组铸件铸造精度，可以认为：各组刃状边缘铸
件的铸造精度无显著差异，都可以达到临床上可接受的边缘上限
160pm范围内。
2．通过铸钛基体内包埋材料主要元素扩散情况分析，得出：
各组铸件表面反应层厚度均能达到临床上要求的 50 Pm。
结 论
适宜配比的含错磷酸盐包埋材料在铸模温度为450℃时，可
以铸造出铸造精度较好，反应层较薄的刃状边缘钛铸件。
Introduction
In this study, Ti castings were invested by three kinds of investments of which ZrO2content is respectively 30% ,40% and 50%. The castings have a 30 degree edge margin. Casting deficiency of the edge margin were measured ,the spreading of Al,Zr,P,Si and Mg chemical elements were analyzed with electron probe microanalyzer and scanned with X - ray image scanning machine. Thus, the property of casting were evaluated including accuracy of edge and thickness of reaction layer. These results were compared to the casting invested by Ti investment made in Japan, The purpose of this study is to investigate the feasibility of the ZrP99 investment being applied to Ti full crown. It will provide experimental evidence for clinical application of the ZrP99 investment with good capability and relation cheap.
Materials and Methods
1. Materials
1. 1 ZrP99 investment
Mix the powder of ZrO2 with ordinary phosphate investment to make the proportion of ZrO2 up to 30% ,40% and 50% , and respectively mark as group1,2,3. Use Morita Ti investment made in Japan as control.
1. 2 Making the two - layer collection and edge margin wax pattern
1.3 Pure Ti materials
Pure Ti blocks were provided by Beijing Yalian Electronic Material And Technology Corp. 2. Experimental methods
2.1 Insert sprue
24 models were divided into 4 groups in each hoops randomly.
2.2 Invest
ZrPgg investments were mixed respectively in proportion with distilled water in the vacual mixer. Four hoops were invested with each investment.
2. 3 Roast casting hoops
The invested hoop were placed in room temperature for 16 hour before being put into the furnace. The temperature was elevated from room temperature to 260^ at the rate of 6t per minute, kept 60 minutes raised to 850 at the same rate for 60 minutes and then cooled down to 450 naturally for 30 minutes .
2.4 Cast
During casting the temperature was kept at 450 . The whole process was controlled by the computer. The electronic was 250A. The disparity of two casting room pressure was 7kgf /cm2. The weight of Ti is 30 g.
2. 5 Surface handle
After casting, the hoops were put into water immediately. After cooled down completely, the investments were removed with sand -spraying machine, pressure 4kg/cm for 20 second. The sprues was cut.
3. The assay methodology
3.1 Determination of cast deficiency of edge margin
Six spots were randomly marked on the slope of edge margin and were divided into three groups (two spots per group). The line of each group should be vertical to the margin as fast as possible. Images were collected with microimage analyzer. The cast deficiency was determined by the distance between the two markers.
3.2 Element spreading .analysis
each casting were cut longitudinally, mosaiced in phenol -formaldhyde resin, polished and tripsised and mildly eroded by 3% mixture of hydrofluoric acid and nitric acid. After being cleaned in distilled water, X - ray intensity linear distribution of Zr,P ,Si and Mg of experimental group and Al^S^Mg and Zr of control group were analysed. Then the castings were scanned with the X - ray scanning machine.
Results
1. The cast deficiency is respectively 133. 79 15. 26 m for groupl, 132. 87 20. 56 m for group2, 144. 13 18. 31 m for group3 and143. 73 11. 50 m for control. There is no statistically significant difference(p >0.05 ).
2. Element spreading analysis
2.1 The spreading depth of Si is 37 m for groupl ,28 m for group2, 25 m for group3 and 12 m for control.
2.2 The spreading of Si and P is synchronic, but Si is deeper than P.
2. 3 There is no specific wavelength of Mg and Zr.
2.4 The spreading depth of Al in control group is 9 m.
2. 5 The results of scanning is consistent with of electron probe.
Discussion
1. It is demonstrated that the accuracy of all the castings margin have no significantly difference by determination of cast deficiency of edge margin The cast deficiency isles than 160 m, which is the maximal count of cli
本研究采用二层集合法和成刃器制作30°刃状边缘蜡型，分别以不同配比的含锆磷酸盐包埋材料和日本产铸钛包埋材料包埋后进行铸造，通过测定各组刃状边缘铸件的铸入不足量，同时用电子探针分析钛基体内包埋材料主要元素的扩散情况，以评价含锆磷酸盐包埋材料的铸钛性能。探讨其用于铸钛的可行性，为临床上应用性能良好而成本较低的包埋材料提供实验依据。
材料与方法
一、实验材料：
1．含锆磷酸盐包埋材料：
将不同质量的ZrO_2与磷酸盐包埋材料混合配制成分别含30％、40％和50％ZrO_2三组包埋材料。以日本Titavest-CB专用铸钛包埋材料作为对照。
2．二层集合体及刃状边缘蜡型的制作：A框架置于光洁玻璃板上，四周用红蜡封实固定，框架内面四周及玻璃板涂布一薄层石蜡油，调和搅拌包埋材料注入A框。在B框架中，下层固定冷却后包埋材料板，新型嵌体蜡融化后注入B框架包埋材料板上层，制成二层集合体，用齿科线锯、成刃器制成规格为7×12×10mm刃状边缘蜡型。
3．铸造钛料：由北京亚联电子材料技术研究所提供。
二、实验器材：
1．真空搅拌机(美国)
2．茂福炉什avo公司，德国）
3．恒温熔蜡器
4．CYCLARC 11型加压一吸引铸钛机（Morita公司，日本）
5．喷砂机
6．镶嵌机
7．超声波清洗器
8．显微图像分析仪（Metaxnorph／DP10／SZH－IL LB；US／JP；
VIC／OLYMPUS）
9．EPM一l0Q电子探针微分析仪
三、实验方法：
1．安插铸道：用直径2．srnm，长度3nun的铸造蜡条，垂直安
插在蜡型刃状边缘的对侧，将6个蜡型均匀安插于圆形主铸道上。
2．包埋：蜡型表面用无水酒精处理后进行包埋，采用有圈包
埋，铸钛专用铸圈直径50rum，高45nun，内村0．7rum厚的石棉纸。
实验组包埋材料按蒸馏水水：粉一0．13的比例在真空搅拌机中调
和后进行包埋，对照组包埋材料按专用液：粉一0．13在真空搅拌
机中调和后进行包埋。
3．铸造：包埋后的铸圈在室温中放置历小时后焙烧。茂福炉
升温曲线为：室温开始，以每分钟6t的升温速度升至260℃，保持
60分钟后，再以每分钟6℃速度升至850℃，保持60分钟后，自然
冷却到 450t，保持 30分钟后，·CYCLARC 11型加压一吸引铸钛
机铸钛，熔金电流为 250A，两室差压 7k勿cm＼钛块质量叨。
4．铸件表面处理：铸造完成后，立即将铸圈放人冷水中，待完
全冷却后，用笔式喷砂机，气压4kg／cm＼持续 20秒，去除包埋材
料，而后用砂片切去铸道。
四、检测方法：
1．测定各组刃状边缘铸件的铸人不足量：铸人不足量的计算
方法：蜡型通过两标点直线上的MP（定点到蜡型边缘的距离）与
·2·
铸造后MP’，（同一定点到铸件边缘的距离）之差。图像采集、数
据分析使用显微图像分析仪。
2．铸钛基体内包埋材料主要元素扩散情况分析：将铸件沿纵
轴截断，用镶嵌机镶嵌于酚醛树脂内，铸件按金相要求进行研磨。
抛光，用 3％氢氟酸和硝酸的混和液进行轻度腐蚀，用超声波清洗
器在蒸馏水内清洗，用电子探针微分析仪分析铸钛基体内包埋材
料主要元素的X射线强度线分布及X射线强度面扫描。
3．数据处理：采用 SPSS．0 for indows软件包，单因素方差
分析处理铸人不足量。
白 果
一、钛铸件铸人不足量：
各组铸件铸人不足量测定结果为：实验组，30％组为133．79
t 15．26pm，40防组为 132．87 20．56帅，50助组为 IM．13士 18．
3lpm，对照组为 143．73 t 11．50urn。单因素方差分析结果提示：
各组铸件间无显著差异h北．05八
二、铸钛基体内包埋材料主要元素扩散情况分析：
电子探针分析结果：豆 d实验组的 Sika，Pka，Mgka，Zra的
X射线强度线分布提示：厂）。实验组试件反应层中＊扩散深度，
30协组约37 pm，40防组约28 pm，50％组约25 pm。（2）·实验组试
件均可见＊和P的扩散是同步的，但S的扩散深。门〕实验组
试件未见Mg义r的特征波长。对照组X射线强度线分布提示必
扩散约gPm步扩散深度约］LZPm。通过Alk队Sika，Pka的X射
线强度面扫描亦与X射线强度线分布结论相符。实验组中S强
度计数带宽且不致密，但对照组中则强度计数带很薄，且非常致
密。
·3·
讨 论
1．通过测定各组铸件铸造精度，可以认为：各组刃状边缘铸
件的铸造精度无显著差异，都可以达到临床上可接受的边缘上限
160pm范围内。
2．通过铸钛基体内包埋材料主要元素扩散情况分析，得出：
各组铸件表面反应层厚度均能达到临床上要求的 50 Pm。
结 论
适宜配比的含错磷酸盐包埋材料在铸模温度为450℃时，可
以铸造出铸造精度较好，反应层较薄的刃状边缘钛铸件。
Introduction
In this study, Ti castings were invested by three kinds of investments of which ZrO2content is respectively 30% ,40% and 50%. The castings have a 30 degree edge margin. Casting deficiency of the edge margin were measured ,the spreading of Al,Zr,P,Si and Mg chemical elements were analyzed with electron probe microanalyzer and scanned with X - ray image scanning machine. Thus, the property of casting were evaluated including accuracy of edge and thickness of reaction layer. These results were compared to the casting invested by Ti investment made in Japan, The purpose of this study is to investigate the feasibility of the ZrP99 investment being applied to Ti full crown. It will provide experimental evidence for clinical application of the ZrP99 investment with good capability and relation cheap.
Materials and Methods
1. Materials
1. 1 ZrP99 investment
Mix the powder of ZrO2 with ordinary phosphate investment to make the proportion of ZrO2 up to 30% ,40% and 50% , and respectively mark as group1,2,3. Use Morita Ti investment made in Japan as control.
1. 2 Making the two - layer collection and edge margin wax pattern
1.3 Pure Ti materials
Pure Ti blocks were provided by Beijing Yalian Electronic Material And Technology Corp. 2. Experimental methods
2.1 Insert sprue
24 models were divided into 4 groups in each hoops randomly.
2.2 Invest
ZrPgg investments were mixed respectively in proportion with distilled water in the vacual mixer. Four hoops were invested with each investment.
2. 3 Roast casting hoops
The invested hoop were placed in room temperature for 16 hour before being put into the furnace. The temperature was elevated from room temperature to 260^ at the rate of 6t per minute, kept 60 minutes raised to 850 at the same rate for 60 minutes and then cooled down to 450 naturally for 30 minutes .
2.4 Cast
During casting the temperature was kept at 450 . The whole process was controlled by the computer. The electronic was 250A. The disparity of two casting room pressure was 7kgf /cm2. The weight of Ti is 30 g.
2. 5 Surface handle
After casting, the hoops were put into water immediately. After cooled down completely, the investments were removed with sand -spraying machine, pressure 4kg/cm for 20 second. The sprues was cut.
3. The assay methodology
3.1 Determination of cast deficiency of edge margin
Six spots were randomly marked on the slope of edge margin and were divided into three groups (two spots per group). The line of each group should be vertical to the margin as fast as possible. Images were collected with microimage analyzer. The cast deficiency was determined by the distance between the two markers.
3.2 Element spreading .analysis
each casting were cut longitudinally, mosaiced in phenol -formaldhyde resin, polished and tripsised and mildly eroded by 3% mixture of hydrofluoric acid and nitric acid. After being cleaned in distilled water, X - ray intensity linear distribution of Zr,P ,Si and Mg of experimental group and Al^S^Mg and Zr of control group were analysed. Then the castings were scanned with the X - ray scanning machine.
Results
1. The cast deficiency is respectively 133. 79 15. 26 m for groupl, 132. 87 20. 56 m for group2, 144. 13 18. 31 m for group3 and143. 73 11. 50 m for control. There is no statistically significant difference(p >0.05 ).
2. Element spreading analysis
2.1 The spreading depth of Si is 37 m for groupl ,28 m for group2, 25 m for group3 and 12 m for control.
2.2 The spreading of Si and P is synchronic, but Si is deeper than P.
2. 3 There is no specific wavelength of Mg and Zr.
2.4 The spreading depth of Al in control group is 9 m.
2. 5 The results of scanning is consistent with of electron probe.
Discussion
1. It is demonstrated that the accuracy of all the castings margin have no significantly difference by determination of cast deficiency of edge margin The cast deficiency isles than 160 m, which is the maximal count of cli
引文
1．井田一夫．合金技工．齿科技工，1992，20(12)：1264
2．郭天文，王宝成，程静涛．钛制义齿131件临床总结．实用口腔医学杂志，2000，16(5)：408-409．
3．长谷川二郎．铸造体适合精度向上．齿科技工，1992，20(11)：1152-1159．
4．苗维平．边缘部铸造性金属构造关研究．口病志，1997，64(4)：11-26．
5. Takahashi J, Zhang JZ, Okazaki M. Castability and surface hardness of titanium cast plates obtained from experimental phosphate- bonded silica investment molds. Dent Mater J, 1994,12 (2) ,238- 244
6．张建中，高桥纯造，冈崎正之．石英磷酸盐系包埋材料铸钛精度的研究口腔材料器械杂志，1997，6(3)：99-102．
7．骆小平，郭天文，欧阳官，等．锆英石作为铸钛用内包埋材料的初步研究．华西口腔医学杂志，1998，16(3)：216-218．
8．卢军霞，法永红，郭天文．不同包埋材料对铸钛适合性的影响．现代口腔医学杂志，2001，15(4)：289-290．
9. Wolf BH, Walter MH, Boening KW, et al. Margin quality of titanium and high- gold inlay and onlay:a clinical study. Dent Mater,1998,14(5) :370 -4.
10．星野浩之，草戈玄，宫川修．铸造冠适合性关研究．补缀志，1996(40)：796-805．
11. Barreto MT, Goldberg A J, Nitkin DA, et al. Effect of investment on casting high -fusing alloys. J Prosthet Dent , 1980,44:504 -507.
12. Chan D ,Guillory V, Blackman R, et al. The effects of spree design on the roughness and porosity of titanium castings. J Prosthet Dent, 1997 ;78(4) :400 -404.
13. Chan D, Blackman R, Kaiser A, et al. The effects of sprue design on the marginal accuracy of titanium castings. Journal of Oral Rehabilitation, 1998,25:424 -429.
14．骆小平，郭天文，欧阳官，等．铸模温度对铸钛机械性能及表面反应层结构的影响．中华口腔医学杂志，1997，32(6)：327-333．
15．宫相芹，冯悦慧，田立坤，等．不同配比的含锆磷酸盐包埋材料对铸钛件质量影响的实验研究．辽宁医学杂志，2002，16(2)：67-9．
16．陈治清主编。口腔材料学。北京：人民卫生出版社，1997，126-135
17．骆小平，郭天文，欧阳官．Gr2型纯钛铸造后的性能．第四军医大学学报，1996；7(3)：218-220．
18. Lioyd CH,Scrimgeour SN. Dental matrials review. J Dental, 1995,23:77
19. Oda Y, Kudoh Y, Kawada E, et al. Surface reaction between titanium castings and investments [J]. Bull Tokyo Dent Coll, 1996,37(3): 129 - 136.
2．郭天文，王宝成，程静涛．钛制义齿131件临床总结．实用口腔医学杂志，2000，16(5)：408-409．
3．长谷川二郎．铸造体适合精度向上．齿科技工，1992，20(11)：1152-1159．
4．苗维平．边缘部铸造性金属构造关研究．口病志，1997，64(4)：11-26．
5. Takahashi J, Zhang JZ, Okazaki M. Castability and surface hardness of titanium cast plates obtained from experimental phosphate- bonded silica investment molds. Dent Mater J, 1994,12 (2) ,238- 244
6．张建中，高桥纯造，冈崎正之．石英磷酸盐系包埋材料铸钛精度的研究口腔材料器械杂志，1997，6(3)：99-102．
7．骆小平，郭天文，欧阳官，等．锆英石作为铸钛用内包埋材料的初步研究．华西口腔医学杂志，1998，16(3)：216-218．
8．卢军霞，法永红，郭天文．不同包埋材料对铸钛适合性的影响．现代口腔医学杂志，2001，15(4)：289-290．
9. Wolf BH, Walter MH, Boening KW, et al. Margin quality of titanium and high- gold inlay and onlay:a clinical study. Dent Mater,1998,14(5) :370 -4.
10．星野浩之，草戈玄，宫川修．铸造冠适合性关研究．补缀志，1996(40)：796-805．
11. Barreto MT, Goldberg A J, Nitkin DA, et al. Effect of investment on casting high -fusing alloys. J Prosthet Dent , 1980,44:504 -507.
12. Chan D ,Guillory V, Blackman R, et al. The effects of spree design on the roughness and porosity of titanium castings. J Prosthet Dent, 1997 ;78(4) :400 -404.
13. Chan D, Blackman R, Kaiser A, et al. The effects of sprue design on the marginal accuracy of titanium castings. Journal of Oral Rehabilitation, 1998,25:424 -429.
14．骆小平，郭天文，欧阳官，等．铸模温度对铸钛机械性能及表面反应层结构的影响．中华口腔医学杂志，1997，32(6)：327-333．
15．宫相芹，冯悦慧，田立坤，等．不同配比的含锆磷酸盐包埋材料对铸钛件质量影响的实验研究．辽宁医学杂志，2002，16(2)：67-9．
16．陈治清主编。口腔材料学。北京：人民卫生出版社，1997，126-135
17．骆小平，郭天文，欧阳官．Gr2型纯钛铸造后的性能．第四军医大学学报，1996；7(3)：218-220．
18. Lioyd CH,Scrimgeour SN. Dental matrials review. J Dental, 1995,23:77
19. Oda Y, Kudoh Y, Kawada E, et al. Surface reaction between titanium castings and investments [J]. Bull Tokyo Dent Coll, 1996,37(3): 129 - 136.