CN103422089A - Nd-YAG laser cladding method for preparing thickness adjustable biological ceramic composite coating adopting bone-like structure - Google Patents

Nd-YAG laser cladding method for preparing thickness adjustable biological ceramic composite coating adopting bone-like structure Download PDF

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CN103422089A
CN103422089A CN2013103101315A CN201310310131A CN103422089A CN 103422089 A CN103422089 A CN 103422089A CN 2013103101315 A CN2013103101315 A CN 2013103101315A CN 201310310131 A CN201310310131 A CN 201310310131A CN 103422089 A CN103422089 A CN 103422089A
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laser cladding
coating
bioceramic
yag laser
composite coating
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王迎春
耿铁
屈少敏
王赞
张映霞
唐静静
赵斌
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Henan University of Technology
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Abstract

本发明公开了一种Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,包括下述步骤:1、将稀土、与CaCO3按比例混合制备成复合粉末;2、将第一步所得复合粉末堆覆在钛合金基体表面形成预制涂层;3、Nd-YAG激光熔覆复合粉末,即可得到高结合力生物陶瓷复合涂层。本发明由于在原材料中添加了稀土成分,提高了HAP相结构的稳定性;所得涂层与金属基体结合强度高,为化学冶金结合,可解决生物陶瓷涂层在人体中容易脱落的问题;同时原材料价格便宜,购买方便,易于贮存;制备工艺简单,易于实施,具有良好的市场应用前景及商业价值。

The invention discloses a method for Nd-YAG laser cladding a bone-like structure bioceramic composite coating with adjustable thickness, which comprises the following steps: 1. Rare earth, Mix with CaCO 3 in proportion to prepare a composite powder; 2. Stack the composite powder obtained in the first step on the surface of the titanium alloy substrate to form a prefabricated coating; 3. Nd-YAG laser cladding the composite powder to obtain a high-binding biological Ceramic composite coating. The invention improves the stability of the HAP phase structure due to the addition of rare earth components in the raw materials; the obtained coating has high bonding strength with the metal substrate, which is a chemical metallurgical combination, which can solve the problem that the bioceramic coating is easy to fall off in the human body; at the same time The raw material is cheap, convenient to purchase and store; the preparation process is simple and easy to implement, and has good market application prospect and commercial value.

Description

Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法Method of Nd-YAG laser cladding thickness-adjustable bone-like structure bioceramic composite coating

技术领域 technical field

本发明涉及生物陶瓷材料领域,尤其是涉及一种Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法。 The invention relates to the field of bioceramic materials, in particular to a method for Nd-YAG laser cladding a bone-like structure bioceramic composite coating with adjustable thickness.

背景技术 Background technique

70年代以来问世的羟基磷灰石(Ca10(PO4)6(OH)2, HAP)医用生物陶瓷是目前前国内外正在蓬勃发展的生物材料。由HAP微晶陶瓷制备的植入材料能与人体自然骨很好的结合,是已发现的生物相容性最好的生物陶瓷材料。磷酸钙基的生物陶瓷在目前临床应用中应用最为广泛,其主要产品为HAP、磷酸三钙(Ca3(PO4)2, TCP)、焦磷酸钙(β-Ca2P2O7, β-TTCP)等。磷酸三钙、焦磷酸钙具有良好的骨诱导能力,是一种理想的可降解生物陶瓷材料,其成骨性能等生理功能非常接近HAP。由HAP与可降解生物陶瓷组成的复合材料的综合生理性能将优于单一的HAP生物陶瓷。目前临床应用时,是将该生物陶瓷材料利用等离子喷涂的方法将其喷涂在金属基体上形成涂层。临床使用发现,等离子喷涂法制备的生物陶瓷涂层的主要缺点为:1、涂层的组织与结晶度不均匀,这将减小涂层的生物相容性与稳定性;2、涂层与基体的粘结强度较差,使得涂层在临床应用中出现剥落。 Hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 , HAP) medical bioceramic, which came out in the 1970s, is currently a vigorously developing biomaterial at home and abroad. The implant material made of HAP microcrystalline ceramics can be well combined with the natural bone of the human body, and is the best biocompatible bioceramic material that has been found. Calcium phosphate-based bioceramics are currently the most widely used in clinical applications, and their main products are HAP, tricalcium phosphate (Ca 3 (PO 4 ) 2 , TCP), calcium pyrophosphate (β-Ca 2 P 2 O 7 , β -TTCP) etc. Tricalcium phosphate and calcium pyrophosphate have good osteoinductive ability and are ideal biodegradable bioceramic materials. Their physiological functions such as osteogenic performance are very close to HAP. The comprehensive physiological properties of composite materials composed of HAP and degradable bioceramics will be better than single HAP bioceramics. At present, in clinical application, the bioceramic material is sprayed on a metal substrate by a plasma spraying method to form a coating. Clinical use found that the main disadvantages of bioceramic coatings prepared by plasma spraying are: 1. The structure and crystallinity of the coating are not uniform, which will reduce the biocompatibility and stability of the coating; The poor bond strength of the substrate makes the coating peel off in clinical application.

针对羟基磷灰石生物陶瓷涂层及等离子喷涂工艺仍然存在的上述问题,用激光熔覆工艺制备含HAP的钙磷基生物活性陶瓷涂层近年得到了发展。传统的激光熔覆制备工艺中使用CO2激光器,以添加稀土的                                                

Figure 2013103101315100002DEST_PATH_IMAGE001
与CaCO3的混合粉末为原材料能在熔覆层中得到包含HAP成分的生物陶瓷复合涂层。值得注意的是由于CO2激光由于自身的波长吸收特性,CO2激光熔覆不添加稀土成分的
Figure 101136DEST_PATH_IMAGE001
与CaCO3 成分时无法得到生物陶瓷涂层。Nd : YAG固体激光器的波长为1.064μm,与CO2气体激光器(波长为10.64μm)相比,它输出的波长较短。但是对于金属材料而言,激光波长越短,吸收系数越大(图中a与b处),但是对陶瓷与玻璃材料而言(图中A与B处),情况正好相反,如图1所示,所以 ⑴ 当CO2激光熔覆与CaCO3混合粉末制备生物陶瓷涂层时,混合粉末对CO2激光的吸收率将远远高于金属基体,原材料
Figure 929732DEST_PATH_IMAGE001
发生烧蚀或分解,降低涂层中HAP的生成含量,同时制备出的HAP成分容易发生分解,所得HAP的含量降低;与之相反,Nd-YAG激光熔覆混合粉末时,金属基体对Nd-YAG激光的吸收率将远远高于混合粉末。⑵ 能量传递方式:Nd-YAG激光熔覆过程中,混合粉末合成生物陶瓷的能量来自吸收Nd-YAG激光束能量而熔化的金属基体,这为激光熔覆过程中HAP的存在提供了加工与热力学条件。 In view of the above problems still existing in hydroxyapatite bioceramic coating and plasma spraying process, the preparation of HAP-containing calcium phosphorus-based bioactive ceramic coating by laser cladding process has been developed in recent years. The traditional laser cladding preparation process uses a CO2 laser to add rare earth
Figure 2013103101315100002DEST_PATH_IMAGE001
The mixed powder with CaCO3 as raw material can get bioceramic composite coating containing HAP component in the cladding layer. It is worth noting that CO 2 laser cladding does not add rare earth components due to its own wavelength absorption characteristics.
Figure 101136DEST_PATH_IMAGE001
Bioceramic coatings could not be obtained with CaCO3 composition. The Nd : YAG solid-state laser has a wavelength of 1.064μm, and it outputs a shorter wavelength compared to a CO 2 gas laser (wavelength of 10.64μm). But for metal materials, the shorter the laser wavelength, the larger the absorption coefficient (a and b in the figure), but for ceramics and glass materials (a and b in the figure), the situation is just the opposite, as shown in Figure 1 , so (1) when CO 2 laser cladding When mixing powder with CaCO 3 to prepare bioceramic coating, the absorption rate of the mixed powder to CO 2 laser will be much higher than that of metal matrix, raw material
Figure 929732DEST_PATH_IMAGE001
Ablation or decomposition occurs, reducing the content of HAP in the coating, and the prepared HAP components are prone to decomposition, and the content of HAP is reduced; in contrast, when Nd-YAG laser cladding mixed powder, the metal matrix has a negative effect on Nd- The absorption rate of YAG laser will be much higher than that of mixed powder. (2) Energy transfer mode: During the Nd-YAG laser cladding process, the energy of mixing powders to synthesize bioceramics comes from the metal matrix that absorbs the energy of the Nd-YAG laser beam and melts, which provides processing and thermodynamics for the existence of HAP in the laser cladding process. condition.

经文献检索发现,中国专利申请号:200510030117.5,名称:激光熔覆原位合成制备生物陶瓷复合涂层的方法,该专利涉及Nd-YAG激光熔覆生物陶瓷复合涂层的制备工艺,其涉及的复合生物陶瓷涂层材料主要由HAP 与β-Ca2P2O7组成,但是该专利涉及的复合生物陶瓷涂层由于原材料中没有添加稀土成分, 进而该专利涉及的复合生物陶瓷涂层原材料中不存在稀土成分。激光熔覆过程中原材料中稀土的添加, 能催化HAP 等钙磷基生物陶瓷相的形成并可抑制其分解, 提高HAP 相结构的稳定性。此外稀土在激光涂覆生物陶瓷涂层中, 少量分布于晶内, 大部分分布在局部晶粒间。稀土的掺杂, 促进晶粒细化, 具有自然骨组织晶粒的不规则性和纤维组织等特征。Nd-YAG激光熔覆过程中,激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%,并且合成羟基磷灰石的工艺参数范围扩大。 After literature search, it was found that Chinese patent application number: 200510030117.5, name: laser cladding in-situ synthesis method for preparing bioceramic composite coating, this patent involves the preparation process of Nd-YAG laser cladding bioceramic composite coating, which involves The composite bioceramic coating material is mainly composed of HAP and β-Ca 2 P 2 O 7 , but the composite bioceramic coating involved in this patent does not add rare earth components to the raw materials, and the raw materials of the composite bioceramic coating involved in this patent Rare earth components are absent. The addition of rare earths in raw materials during laser cladding can catalyze the formation of calcium-phosphorus-based bioceramic phases such as HAP and inhibit their decomposition, improving the stability of the HAP phase structure. In addition, in the laser-coated bioceramic coating, a small amount of rare earth is distributed in the grain, and most of it is distributed in the local intergranular. The doping of rare earth promotes grain refinement, which has the characteristics of irregularity and fibrous structure of natural bone tissue grains. In the Nd-YAG laser cladding process, when the laser process parameters are the same as the raw material composition, the grain size of the bioceramic coating with rare earth addition is 5-10 times lower than that of the bioceramic coating without rare earth addition, and the tissue has bone-like tissue Irregularity and fibrous structure and other characteristics, the bonding strength is increased by 30%-50%, the content of hydroxyapatite in the phase composition is increased by 10-30%, and the range of process parameters for synthesizing hydroxyapatite is expanded.

发明内容 Contents of the invention

本发明的目的在于针对现有CO2激光熔覆制备生物陶瓷涂层的不足,提供一种以添加了稀土成分的

Figure 109040DEST_PATH_IMAGE002
与CaCO3的混合粉末为原材料制作涂层厚度可调的具有类骨组织结构的复合生物陶瓷涂层的Nd-YAG激光熔覆制备方法。 The purpose of the present invention is to address the deficiency of existing CO2 laser cladding to prepare bioceramic coatings, to provide a kind of bioceramic coating with added rare earth components
Figure 109040DEST_PATH_IMAGE002
Nd-YAG laser cladding preparation method of composite bioceramic coating with bone-like tissue structure with adjustable coating thickness by mixing powder with CaCO 3 as raw material.

为实现上述目的,本发明可采取下述技术方案: To achieve the above object, the present invention can take the following technical solutions:

本发明所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,包括下述步骤: The method for the bone-like structure bioceramic composite coating with adjustable thickness of Nd-YAG laser cladding of the present invention comprises the following steps:

第一步,将稀土、

Figure 321847DEST_PATH_IMAGE002
与CaCO3按比例混合制备成复合粉末; In the first step, the rare earth,
Figure 321847DEST_PATH_IMAGE002
Mix with CaCO3 in proportion to prepare composite powder;

第二步,将第一步所得复合粉末堆覆在钛合金基体表面形成预制涂层; In the second step, the composite powder obtained in the first step is stacked on the surface of the titanium alloy substrate to form a prefabricated coating;

第三步,Nd-YAG激光熔覆复合粉末,即可得到高结合力生物陶瓷复合涂层。 In the third step, Nd-YAG laser cladding composite powder can obtain high binding force bioceramic composite coating.

所述第二步中堆覆在钛合金基体表面的复合涂层厚度≤2mm。 The thickness of the composite coating deposited on the surface of the titanium alloy substrate in the second step is ≤2mm.

所述钛合金基体为Ti6Al4V、Ti-5Al-2.5Fe、Ti-6Al-7Nb、Ti-13Nb-13Zr或Ti-12Nb-6Zr-2Fe。 The titanium alloy matrix is Ti6Al4V, Ti-5Al-2.5Fe, Ti-6Al-7Nb, Ti-13Nb-13Zr or Ti-12Nb-6Zr-2Fe.

所述复合粉末的制备方法为:将稀土、

Figure 965318DEST_PATH_IMAGE002
与CaCO3按稀土 1-2%、
Figure 238167DEST_PATH_IMAGE002
 70-74%、CaCO3  24-29%的重量百分比称取后,放入容器中混合均匀、静置脱水,然后再次混合、静置强化脱水,入混料机中混合均匀,即可得到平均粒径50-100μm,含水量5.8~6.8%的混合粉末。所述激光熔覆时的工艺参数条件为:保护气体为氩气,光斑直径3mm,输出功率800~1200W,扫描速率1~3mm/s。 The preparation method of the composite powder is: the rare earth,
Figure 965318DEST_PATH_IMAGE002
With CaCO 3 by rare earth 1-2%,
Figure 238167DEST_PATH_IMAGE002
70-74%, CaCO 3 24-29% by weight, weighed, put into the container and mix evenly, stand for dehydration, then mix again, stand for enhanced dehydration, put into the mixer and mix evenly, you can get the average Mixed powder with a particle size of 50-100μm and a water content of 5.8-6.8%. The process parameter conditions during the laser cladding are as follows: the protective gas is argon, the spot diameter is 3mm, the output power is 800-1200W, and the scan rate is 1-3mm/s.

所述激光熔覆时激光的波长为1.06μm。 The laser wavelength during the laser cladding is 1.06 μm.

所述生物陶瓷复合涂层的厚度≤2mm,其物相组成中,HAP的体积分数占30~70%,其余为TCP、β-Ca2P2O7和钛酸钙的混合物;复合涂层与钛合金基体的结合强度为30-45Mpa。 The thickness of the bioceramic composite coating is ≤2mm, and in its phase composition, the volume fraction of HAP accounts for 30-70%, and the rest is a mixture of TCP, β-Ca 2 P 2 O 7 and calcium titanate; the composite coating The bonding strength with the titanium alloy substrate is 30-45Mpa.

本发明的优点体现在以下几个方面: The advantages of the present invention are reflected in the following aspects:

第一,由于Nd-YAG激光(波长1.06μm)对生物陶瓷混合粉末具有透过性的特点,故与钛合金基体表面进行激光熔覆过程中,混合粉末能够获得制备HAP生物陶瓷的独特的反应热力学与反应动力学,故在钛合金基体表面能够制备性能优良的复合生物陶瓷涂层; First, because the Nd-YAG laser (wavelength 1.06 μm) has the characteristics of permeability to the bioceramic mixed powder, the mixed powder can obtain a unique reaction for preparing HAP bioceramic during the laser cladding process with the surface of the titanium alloy substrate. Thermodynamics and reaction kinetics, so a composite bioceramic coating with excellent performance can be prepared on the surface of the titanium alloy substrate;

第二,在原材料中添加了稀土(包括Y2O3、Ce2O3、La2O3等)成分,提高了HAP 相结构的稳定性。稀土成分可促进晶粒细化, 具有自然骨组织晶粒的不规则性和纤维组织等特征;熔覆制备的复合生物陶瓷涂层中主要成分为性质稳定的羟基磷灰石、磷酸三钙、可降解的焦磷酸钙与钛酸钙,生物相容性优异;相同Nd-YAG激光工艺参数与原材料成分相同情况下,原材料中添加稀土制备的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,物相组成中羟基磷灰石的含量提高10-30%。 Second, rare earth (including Y 2 O 3 , Ce 2 O 3 , La 2 O 3 , etc.) components are added to the raw materials to improve the stability of the HAP phase structure. Rare earth components can promote grain refinement, and have the characteristics of irregular grains and fibrous tissue of natural bone tissue; the main components of the composite bioceramic coating prepared by cladding are stable hydroxyapatite, tricalcium phosphate, Degradable calcium pyrophosphate and calcium titanate have excellent biocompatibility; under the same Nd-YAG laser process parameters and the same raw material composition, the bioceramic coating prepared by adding rare earth to the raw material is better than the bioceramic coating without adding rare earth The grain size is reduced by 5-10 times, the organization has the characteristics of irregular bone tissue and fibrous tissue, and the content of hydroxyapatite in the phase composition is increased by 10-30%.

第三,涂层与金属基体结合强度高,为化学冶金结合,可解决生物陶瓷涂层在人体中容易脱落的问题;相同Nd-YAG激光工艺参数与原材料成分相同情况下,原材料中添加稀土制备的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的结合强度提高30%-50%,并且合成羟基磷灰石的工艺参数范围扩大。 Third, the bonding strength between the coating and the metal substrate is high, which is a chemical metallurgical combination, which can solve the problem that the bioceramic coating is easy to fall off in the human body; under the same Nd-YAG laser process parameters and the same raw material composition, the raw material is prepared by adding rare earth The bonding strength of the bioceramic coating is 30%-50% higher than that of the bioceramic coating without adding rare earths, and the range of process parameters for synthesizing hydroxyapatite is expanded.

第四,原材料价格便宜,购买方便,易于贮存;制备工艺简单,易于实施,具有良好的市场应用前景及商业价值。 Fourth, the raw materials are cheap, easy to purchase, and easy to store; the preparation process is simple, easy to implement, and has good market application prospects and commercial value.

附图说明 Description of drawings

    图1是材料对不同波长的激光的吸收率示意图。 Figure 1 is a schematic diagram of the absorption rate of materials for different wavelengths of laser light.

具体实施方式 Detailed ways

下面结合实施例对本发明做进一步的阐述。 Below in conjunction with embodiment the present invention is further elaborated.

实施例1: Example 1:

第一步,将Y2O3

Figure 967089DEST_PATH_IMAGE002
与CaCO3按1:72:27之比例(重量百分比)称取,放入容器中混合均匀、静置脱水,然后再次混合、静置强化脱水,入混料机中混合均匀,得到平均粒径50-100μm,含水量6.2%的混合粉末; In the first step, Y 2 O 3 ,
Figure 967089DEST_PATH_IMAGE002
Weigh it with CaCO 3 at a ratio of 1:72:27 (weight percentage), put it in a container and mix it evenly, let it stand for dehydration, then mix it again, let it stand for enhanced dehydration, put it into a mixer and mix it evenly to get the average particle size 50-100μm, mixed powder with a water content of 6.2%;

第二步,将第一步所得混合粉末堆覆在Ti6Al4V合金基体表面(采用其他的钛合金基体效果相同),厚度0.5mm; In the second step, the mixed powder obtained in the first step is stacked on the surface of the Ti6Al4V alloy substrate (using other titanium alloy substrates has the same effect), with a thickness of 0.5mm;

第三步,采用iLS-YC-30A YAG型激光器,在保护气体为氩气,光斑直径3mm,输出功率900W,扫描速率2mm/s的工艺参数下,用Nd-YAG高能激光束对混合粉末与金属基体进行激光熔覆工艺处理,形成钛合金表面Nd-YAG激光熔覆生物陶瓷复合涂层。经测试,获得的涂层晶粒细化, 具有自然骨组织晶粒的不规则性和纤维组织等特征。涂层厚度0.5mm,与金属基体之间为化学冶金结合,结合强度为35Mpa,涂层的物相组成为37%HAP(体积百分比),其余物相为TCP、β-Ca2P2O7、钛酸钙的混合物。(相同Nd-YAG激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%。并且合成羟基磷灰石的工艺参数范围扩大。) The third step is to use the iLS-YC-30A YAG laser, under the process parameters of argon as the shielding gas, 3mm spot diameter, 900W output power, and 2mm/s scan rate, use Nd-YAG high-energy laser beam to mix the powder and The metal substrate is processed by laser cladding process to form Nd-YAG laser cladding bioceramic composite coating on the surface of titanium alloy. After testing, the grains of the obtained coating are refined, and have the characteristics of irregularities and fibrous tissue of natural bone tissue grains. The thickness of the coating is 0.5mm, and it is a chemical metallurgical bond with the metal substrate. The bonding strength is 35Mpa. The phase composition of the coating is 37% HAP (volume percentage), and the remaining phases are TCP, β-Ca 2 P 2 O 7 , A mixture of calcium titanate. (Under the same Nd-YAG laser process parameters and the same raw material composition, the grain size of the bioceramic coating with rare earth addition is 5-10 times lower than that of the bioceramic coating without rare earth addition, and the tissue has the irregularity of bone-like tissue And fibrous structure and other characteristics, the bonding strength is increased by 30%-50%, and the content of hydroxyapatite in the phase composition is increased by 10-30%. And the range of process parameters for synthesizing hydroxyapatite is expanded.)

实施例2: Example 2:

第一步,同实施例1。 The first step, with embodiment 1.

第二步,将第一步所得混合粉末堆覆在Ti6Al4V合金基体表面(采用其他的钛合金基体效果相同),厚度1.0mm; In the second step, the mixed powder obtained in the first step is stacked on the surface of the Ti6Al4V alloy substrate (using other titanium alloy substrates has the same effect), with a thickness of 1.0mm;

第三步,采用iLS-YC-30A YAG型激光器,在保护气体为氩气,光斑直径3mm,输出功率1000W,扫描速率2mm/s的工艺参数下,用Nd-YAG高能激光束对混合粉末与金属基体进行激光熔覆工艺处理,形成钛合金表面Nd-YAG激光熔覆生物陶瓷复合涂层。经测试,获得的涂层晶粒均匀,结晶性能好,具有自然骨组织晶粒的不规则性和纤维组织等特征。涂层厚度1.0mm,与金属基体之间为化学冶金结合,结合强度为37Mpa,涂层的物相组成为43%HAP(体积百分比),其余物相为TCP、β-Ca2P2O7、钛酸钙的混合物。 The third step is to use the iLS-YC-30A YAG laser, under the process parameters of argon as the shielding gas, 3mm spot diameter, 1000W output power, and 2mm/s scan rate, use Nd-YAG high-energy laser beam to mix powder and The metal substrate is processed by laser cladding process to form Nd-YAG laser cladding bioceramic composite coating on the surface of titanium alloy. After testing, the obtained coating has uniform crystal grains, good crystallization performance, and has the characteristics of irregular grains and fibrous tissue of natural bone tissue. The thickness of the coating is 1.0mm, and it is a chemical metallurgical bond with the metal substrate. The bonding strength is 37Mpa. The phase composition of the coating is 43% HAP (volume percentage), and the remaining phases are TCP, β-Ca 2 P 2 O 7 , A mixture of calcium titanate.

    相同Nd-YAG激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%。并且合成羟基磷灰石的工艺参数范围扩大。 Under the same Nd-YAG laser process parameters and the same raw material composition, the grain size of bioceramic coatings with rare earth additions is 5-10 times lower than that of bioceramic coatings without rare earth additions, and the tissue has bone-like irregularities and Features such as fibrous tissue, the bonding strength is increased by 30%-50%, and the content of hydroxyapatite in the phase composition is increased by 10-30%. And the range of process parameters for synthesizing hydroxyapatite is expanded.

实施例3: Example 3:

第一步,将Ce2O3

Figure 983587DEST_PATH_IMAGE002
与CaCO3按2:74:24之比例(重量百分比)称取,放入容器中混合均匀、静置脱水,然后再次混合、静置强化脱水,入混料机中混合均匀,得到平均粒径50-100μm,含水量6.2%的混合粉末; In the first step, Ce 2 O 3 ,
Figure 983587DEST_PATH_IMAGE002
Weigh it with CaCO 3 according to the ratio of 2:74:24 (percentage by weight), put it in a container and mix it evenly, let it stand for dehydration, then mix it again, let it stand for enhanced dehydration, put it into a mixer and mix it evenly to get the average particle size 50-100μm, mixed powder with a water content of 6.2%;

第二步,将第一步所得混合粉末堆覆在Ti6Al4V合金基体表面(采用其他的钛合金基体效果相同),厚度1.5mm; In the second step, the mixed powder obtained in the first step is stacked on the surface of the Ti6Al4V alloy substrate (using other titanium alloy substrates has the same effect), with a thickness of 1.5mm;

第三步,采用iLS-YC-30A YAG型激光器,在保护气体为氩气,光斑直径3mm,输出功率1000W,扫描速率1mm/s的工艺参数下,用Nd-YAG高能激光束对混合粉末与金属基体进行激光熔覆工艺处理,形成钛合金表面Nd-YAG激光熔覆生物陶瓷复合涂层。经测试,获得的涂层晶粒细, 具有自然骨组织晶粒的不规则性和纤维组织等特征。涂层厚度1.5mm,与金属基体之间为化学冶金结合,结合强度为43Mpa,涂层的物相组成为47%HAP(体积百分比),其余物相为TCP、β-Ca2P2O7、钛酸钙的混合物。 The third step is to use the iLS-YC-30A YAG laser, under the process parameters of argon gas as the shielding gas, 3mm spot diameter, 1000W output power, and 1mm/s scan rate, use Nd-YAG high-energy laser beam to mix powder and The metal substrate is processed by laser cladding process to form Nd-YAG laser cladding bioceramic composite coating on the surface of titanium alloy. After testing, the obtained coating has fine grains and has the characteristics of irregular and fibrous tissue grains of natural bone tissue. The thickness of the coating is 1.5mm, and it is a chemical metallurgical bond with the metal substrate. The bonding strength is 43Mpa. The phase composition of the coating is 47% HAP (volume percentage), and the remaining phases are TCP, β-Ca 2 P 2 O 7 , A mixture of calcium titanate.

相同Nd-YAG激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%。并且合成羟基磷灰石的工艺参数范围扩大。 Under the same Nd-YAG laser process parameters and the same raw material composition, the grain size of bioceramic coatings with rare earth additions is 5-10 times lower than that of bioceramic coatings without rare earth additions, and the tissue has bone-like irregularities and Features such as fibrous tissue, the bonding strength is increased by 30%-50%, and the content of hydroxyapatite in the phase composition is increased by 10-30%. And the range of process parameters for synthesizing hydroxyapatite is expanded.

实施例4: Example 4:

第一步,同实施例3; The first step, with embodiment 3;

第二步,将第一步所得混合粉末堆覆在Ti6Al4V合金基体表面(采用其他的钛合金基体效果相同),厚度2.0mm; In the second step, the mixed powder obtained in the first step is stacked on the surface of the Ti6Al4V alloy substrate (using other titanium alloy substrates has the same effect), with a thickness of 2.0mm;

第三步,采用iLS-YC-30A YAG型激光器,在保护气体为氩气,光斑直径3mm,输出功率1200W,扫描速率1mm/s的工艺参数下,用Nd-YAG高能激光束对混合粉末与金属基体进行激光熔覆工艺处理,形成钛合金表面Nd-YAG激光熔覆生物陶瓷复合涂层。经测试,获得的涂层晶粒细, 具有自然骨组织晶粒的不规则性和纤维组织等特征。涂层厚度2.0mm,与金属基体之间为化学冶金结合,结合强度为45Mpa,涂层的物相组成为67%HAP(体积百分比),其余物相为TCP、β-Ca2P2O7、钛酸钙的混合物。 The third step is to use the iLS-YC-30A YAG laser, under the process parameters of argon as the shielding gas, 3mm spot diameter, 1200W output power, and 1mm/s scan rate, use Nd-YAG high-energy laser beam to mix powder and The metal substrate is processed by laser cladding process to form Nd-YAG laser cladding bioceramic composite coating on the surface of titanium alloy. After testing, the obtained coating has fine grains and has the characteristics of irregular and fibrous tissue grains of natural bone tissue. The thickness of the coating is 2.0mm, and it is a chemical metallurgical bond with the metal substrate. The bonding strength is 45Mpa. The phase composition of the coating is 67%HAP (volume percentage), and the remaining phases are TCP, β-Ca 2 P 2 O 7 , A mixture of calcium titanate.

相同Nd-YAG激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%。并且合成羟基磷灰石的工艺参数范围扩大。 Under the same Nd-YAG laser process parameters and the same raw material composition, the grain size of bioceramic coatings with rare earth additions is 5-10 times lower than that of bioceramic coatings without rare earth additions, and the tissue has bone-like irregularities and Features such as fibrous tissue, the bonding strength is increased by 30%-50%, and the content of hydroxyapatite in the phase composition is increased by 10-30%. And the range of process parameters for synthesizing hydroxyapatite is expanded.

实施例5: Example 5:

第一步,将La2O3

Figure 422177DEST_PATH_IMAGE002
与CaCO31:70:29之比例(重量百分比)称取,放入容器中混合均匀、静置脱水,然后再次混合、静置强化脱水,入混料机中混合均匀,得到平均粒径50-100μm,含水量6.2%的混合粉末; In the first step, La 2 O 3 ,
Figure 422177DEST_PATH_IMAGE002
Weigh it with CaCO 3 at a ratio of 1:70:29 (weight percentage), put it in a container and mix it evenly, let it stand for dehydration, then mix it again, let it stand for enhanced dehydration, put it into a mixer and mix it evenly to get the average particle size 50-100μm, mixed powder with a water content of 6.2%;

第二步,将第一步所得混合粉末堆覆在Ti6Al4V合金基体表面(采用其他的钛合金基体效果相同),厚度2.0mm; In the second step, the mixed powder obtained in the first step is stacked on the surface of the Ti6Al4V alloy substrate (using other titanium alloy substrates has the same effect), with a thickness of 2.0mm;

第三步,采用iLS-YC-30A YAG型激光器,在保护气体为氩气,光斑直径3mm,输出功率1200W,扫描速率2mm/s的工艺参数下,用Nd-YAG高能激光束对混合粉末与金属基体进行激光熔覆工艺处理,形成钛合金表面Nd-YAG激光熔覆生物陶瓷复合涂层。经测试,获得的涂层晶粒细, 具有自然骨组织晶粒的不规则性和纤维组织等特征。涂层厚度2.0mm,与金属基体之间为化学冶金结合,结合强度为42Mpa,涂层的物相组成为61%HAP(体积百分比),其余物相为TCP、β-Ca2P2O7、钛酸钙的混合物。 The third step is to use the iLS-YC-30A YAG laser, under the process parameters of argon as the shielding gas, 3mm spot diameter, 1200W output power, and 2mm/s scan rate, use the Nd-YAG high-energy laser beam to mix the powder and The metal substrate is processed by laser cladding process to form Nd-YAG laser cladding bioceramic composite coating on the surface of titanium alloy. After testing, the obtained coating has fine grains and has the characteristics of irregular and fibrous tissue grains of natural bone tissue. The thickness of the coating is 2.0mm, and it is a chemical metallurgical bond with the metal substrate. The bonding strength is 42Mpa. The phase composition of the coating is 61% HAP (volume percentage), and the remaining phases are TCP, β-Ca 2 P 2 O 7 , A mixture of calcium titanate.

相同Nd-YAG激光工艺参数与原材料成分相同情况下,添加稀土的生物陶瓷涂层比未添加稀土的生物陶瓷涂层的晶粒度降低5-10倍,组织具有类骨组织的不规则性和纤维组织等特征,结合强度提高30%-50%,物相组成中羟基磷灰石的含量提高10-30%。并且合成羟基磷灰石的工艺参数范围扩大。 Under the same Nd-YAG laser process parameters and the same raw material composition, the grain size of bioceramic coatings with rare earth additions is 5-10 times lower than that of bioceramic coatings without rare earth additions, and the tissue has bone-like irregularities and Features such as fibrous tissue, the bonding strength is increased by 30%-50%, and the content of hydroxyapatite in the phase composition is increased by 10-30%. And the range of process parameters for synthesizing hydroxyapatite is expanded.

Claims (7)

1.一种Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:包括下述步骤: 1. a method for the bone-like structure bioceramic composite coating with adjustable thickness of Nd-YAG laser cladding, it is characterized in that: comprise the steps: 第一步,将稀土、                                                
Figure 2013103101315100001DEST_PATH_IMAGE001
与CaCO3按比例混合制备成复合粉末;
In the first step, the rare earth,
Figure 2013103101315100001DEST_PATH_IMAGE001
Mix with CaCO3 in proportion to prepare composite powder;
第二步,将第一步所得复合粉末堆覆在钛合金基体表面形成预制涂层; In the second step, the composite powder obtained in the first step is stacked on the surface of the titanium alloy substrate to form a prefabricated coating; 第三步,Nd-YAG激光熔覆复合粉末,即可得到高结合力生物陶瓷复合涂层。 In the third step, Nd-YAG laser cladding composite powder can obtain high binding force bioceramic composite coating.
2.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述第二步中堆覆在钛合金基体表面的复合涂层厚度≤2mm。 2. the method for the bone-like structure bioceramic composite coating of adjustable thickness of Nd-YAG laser cladding according to claim 1, it is characterized in that: in the described second step, the composite coating stacked on the surface of titanium alloy substrate Layer thickness ≤ 2mm. 3.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述钛合金基体为Ti6Al4V、Ti-5Al-2.5Fe、Ti-6Al-7Nb、Ti-13Nb-13Zr或Ti-12Nb-6Zr-2Fe。 3. the method for the bone-like structure bioceramic composite coating of adjustable thickness of Nd-YAG laser cladding according to claim 1, it is characterized in that: described titanium alloy matrix is Ti6Al4V, Ti-5Al-2.5Fe, Ti -6Al-7Nb, Ti-13Nb-13Zr or Ti-12Nb-6Zr-2Fe. 4.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述复合粉末的制备方法为:将稀土、
Figure 556128DEST_PATH_IMAGE001
与CaCO3按稀土 1-2%、
Figure 444450DEST_PATH_IMAGE001
 70-74%、CaCO3  24-29%的重量百分比称取后,放入容器中混合均匀、静置脱水,然后再次混合、静置强化脱水,入混料机中混合均匀,即可得到平均粒径50-100μm,含水量5.8~6.8%的混合粉末。
4. the method for the bone-like structure bioceramic composite coating of adjustable thickness of Nd-YAG laser cladding according to claim 1, it is characterized in that: the preparation method of described composite powder is: mix rare earth,
Figure 556128DEST_PATH_IMAGE001
With CaCO 3 by rare earth 1-2%,
Figure 444450DEST_PATH_IMAGE001
70-74%, CaCO 3 24-29% by weight, weighed, put into the container and mix evenly, stand for dehydration, then mix again, stand for enhanced dehydration, put into the mixer and mix evenly, you can get the average Mixed powder with a particle size of 50-100μm and a water content of 5.8-6.8%.
5.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述激光熔覆时的工艺参数条件为:保护气体为氩气,光斑直径3mm,输出功率800~1200W,扫描速率1~3mm/s。 5. The method for Nd-YAG laser cladding thickness-adjustable bioceramic composite coating with bone-like structure according to claim 1, characterized in that: the process parameter conditions during the laser cladding are: the shielding gas is argon Gas, spot diameter 3mm, output power 800-1200W, scan rate 1-3mm/s. 6.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述激光熔覆时激光的波长为1.06μm。 6 . The method for Nd-YAG laser cladding a thickness-adjustable bone-like structure bioceramic composite coating according to claim 1 , characterized in that: the laser wavelength during laser cladding is 1.06 μm. 7.根据权利要求1所述的Nd-YAG激光熔覆厚度可调的类骨结构生物陶瓷复合涂层的方法,其特征在于:所述生物陶瓷复合涂层的厚度≤2mm,其物相组成中,HAP体积分数占30~70%,其余为TCP、β-Ca2P2O7和钛酸钙的混合物;复合涂层与钛合金基体的结合强度为30-45Mpa。 7. The method for Nd-YAG laser cladding thickness-adjustable bone-like structure bioceramic composite coating according to claim 1, characterized in that: the thickness of the bioceramic composite coating is ≤ 2mm, and its phase composition Among them, the volume fraction of HAP accounts for 30-70%, and the rest is a mixture of TCP, β-Ca 2 P 2 O 7 and calcium titanate; the bonding strength between the composite coating and the titanium alloy substrate is 30-45Mpa.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1778989A (en) * 2005-09-29 2006-05-31 上海交通大学 Method for preparing bioceramic composite coating by laser cladding in situ synthesis
CN102031518A (en) * 2010-12-30 2011-04-27 同济大学 method for preparing material with biological ceramic composite coating laser-clad on surface of titanium alloy
CN102851664A (en) * 2012-08-03 2013-01-02 华中科技大学 Method for preparing hydroxy apatite biological ceramic coating containing fluorine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1778989A (en) * 2005-09-29 2006-05-31 上海交通大学 Method for preparing bioceramic composite coating by laser cladding in situ synthesis
CN102031518A (en) * 2010-12-30 2011-04-27 同济大学 method for preparing material with biological ceramic composite coating laser-clad on surface of titanium alloy
CN102851664A (en) * 2012-08-03 2013-01-02 华中科技大学 Method for preparing hydroxy apatite biological ceramic coating containing fluorine

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Application publication date: 20131204