Metal composite material and femoral condyle prosthesis and preparation method and application thereof

Abstract

The present invention relates to a metal composite material comprising: a base layer, an intermediate layer, and a surface oxide layer sequentially laminated on at least one side of the base layer; the base layer is titanium-based or titanium alloy-based; the intermediate layer is zirconium-based or zirconium alloy-based; and the surface oxide layer contains zirconium oxide. This metal composite material exhibits excellent wear resistance and can be used as a femoral condyle prosthesis, reducing aseptic loosening and lowering the revision rate of joint prostheses. Furthermore, a femoral condyle prosthesis, a method for preparing the metal composite material or the femoral condyle prosthesis, and the use of the metal composite material in the preparation of artificial joint prostheses are also provided.

Description

Technical Field

[0001] The present invention relates to the technical field of medical implant materials and artificial joint prostheses, and in particular to a metal composite material, a femoral condyle prosthesis, a preparation method of the metal composite material or the femoral condyle prosthesis, and applications of the metal composite material. Background Art

[0002] Total knee replacement has become the most effective and successful surgery for treating end-stage knee arthritis. Ten-year clinical follow-up data show that the survival rate of knee prostheses after surgery has reached over 90% (Rand JA, Ilstrup DM. Survivorship analysis of total knee arthroplasty. Cumulative rates of survival of 9200 total knee arthroplasties. J Bone Joint Surg Am 1991; 73A: 39-409), and the patient's knee joint function can be significantly improved. However, after a period of implantation, knee prostheses (such as ultra-high molecular weight polyethylene tibial liners) will cause aseptic loosening due to wear, resulting in the need for revision of the knee prosthesis. In order to reduce wear, the following various methods have been tried: for example, improving the design of the knee prosthesis, improving the accuracy of the implantation position of the various components of the knee prosthesis, and replacing the material of the knee prosthesis.

[0003] In terms of knee prosthesis materials, tibial liners are generally made of ultra-high molecular weight polyethylene, while femoral condyle materials are mainly ceramics, cobalt-chromium-molybdenum alloys, and zirconium-niobium alloys. However, ceramic materials are prone to brittle fracture. Cobalt-chromium-molybdenum femoral condyles have low toughness and poor fatigue life. They can also experience aseptic loosening, leading to postoperative revisions. Furthermore, they release cobalt (Co), chromium (Cr), and nickel (Ni) metal ions, causing metal ion allergic reactions in patients. Zirconium-niobium alloys use rare metals, resulting in high raw material costs, making them difficult for ordinary patients to benefit.

[0004] Based on this, there is an urgent need to develop a knee joint prosthesis material that can effectively reduce wear. Summary of the Invention

[0005] Based on this, the purpose of the present invention includes providing a metal composite material with good wear resistance, which can be used as a femoral condyle prosthesis, reduce aseptic loosening, and reduce the revision rate of joint prostheses. In addition, a femoral condyle prosthesis is provided, and a method for preparing the metal composite material or the femoral condyle prosthesis is also provided. The application of the aforementioned metal composite material in the preparation of artificial joint prostheses is also provided.

[0006] In a first aspect of the present invention, there is provided a metal composite material comprising: a base layer, and an intermediate layer and a surface oxide layer sequentially stacked on at least one side of the base layer;

[0007] in,

[0008] The material of the base layer is titanium-based or titanium alloy-based;

[0009] The material of the intermediate layer is zirconium-based or zirconium alloy-based;

[0010] The surface oxide layer contains zirconium oxide.

[0011] In some embodiments, one or more of the following features are present:

[0012] (a1) The thickness of the substrate layer is 30 mm to 100 mm;

[0013] (a2) the thickness of the intermediate layer is 0.5 mm to 5 mm;

[0014] (a3) the average grain size of the intermediate layer is ≤10 μm;

[0015] (a4) The connection between the base layer and the intermediate layer is metallurgical bonding;

[0016] (a5) the thickness of the surface oxide layer is 3 μm to 25 μm; and

[0017] (a6) The surface roughness of the surface oxide layer is ≤0.1 μm.

[0018] In some embodiments, one or more of the following features are present:

[0019] (b1) the average grain size of the intermediate layer is ≤ 5 μm;

[0020] (b2) the thickness of the surface oxide layer is 5 μm to 10 μm; and

[0021] (b3) The surface roughness of the surface oxide layer is ≤0.05 μm.

[0022] In some embodiments, one or more of the following features are present:

[0023] (c1) The substrate layer is made of industrial pure titanium, (α+β) two-phase titanium alloy or β-type titanium alloy;

[0024] (c2) The material of the intermediate layer is industrial pure zirconium, (α+β) two-phase zirconium alloy or β-type zirconium alloy;

[0025] (c3) the main component of the surface oxide layer is zirconium oxide; and

[0026] (c4) The surface oxide layer is formed by in-situ oxidation of the surface of the intermediate layer away from the base layer.

[0027] In a second aspect of the present invention, a femoral condyle prosthesis is provided, comprising the metal composite material according to the first aspect of the present invention.

[0028] In a third aspect of the present invention, a method for preparing a metal composite material or a femoral condyle prosthesis is provided, comprising the following steps:

[0029] Explosively compounding a base layer blank and an intermediate layer blank to obtain a titanium-zirconium composite blank; wherein the base layer blank is made of titanium or titanium alloy, and the intermediate layer blank is made of zirconium or zirconium alloy;

[0030] Hot rolling and annealing the titanium-zirconium composite blank to obtain a titanium-zirconium composite blank having a base titanium layer and an intermediate zirconium layer; and

[0031] The forging process is performed, and then one side of the intermediate zirconium layer is in-situ oxidized to form a surface oxide layer.

[0032] In some embodiments, the forging process and then in-situ oxidation on one side of the intermediate zirconium layer to form a surface oxide layer comprises the following steps:

[0033] removing the oxide layer on the surface of one side of the middle zirconium layer of the titanium-zirconium composite blank, performing cold deformation, and refining the grains on the surface of one side of the middle zirconium layer to obtain a composite blank to be forged;

[0034] Forging and annealing the composite blank to be forged to obtain a titanium-zirconium composite forging having a base titanium layer and an intermediate zirconium layer; and

[0035] The surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is processed to be less than or equal to 0.2 μm, and then heated under the condition of contact with oxygen to form a surface oxide layer by in-situ oxidation.

[0036] In some embodiments, one or more of the following features are present:

[0037] (d1) the thickness of the base layer blank is 30 mm to 100 mm;

[0038] (d2) the thickness of the intermediate layer blank is 0.5 mm to 5 mm;

[0039] (d3) the microstructure of the intermediate layer blank is an equiaxed structure;

[0040] (d4) the average grain size of the intermediate layer blank is ≤ 10 μm; and

[0041] (d5) The thickness of the surface oxide layer formed by in-situ oxidation is 3 μm to 25 μm.

[0042] In some embodiments, explosively compounding the base layer blank and the intermediate layer blank comprises:

[0043] The intermediate layer blank is placed above the base layer blank with a gap of 0.05mm to 10mm, explosives are placed on the surface of the intermediate layer blank away from the base layer blank, and the explosives are detonated to compositely connect the base layer blank and the intermediate layer blank.

[0044] In some embodiments, in the step of hot rolling the titanium-zirconium composite blank,

[0045] The rolling temperature is 500° C. to 900° C., and / or the heating time is 0.8 to 1.0 min / mm, and / or the deformation is controlled to be 30% to 90%.

[0046] In some embodiments, the base layer blank is made of pure titanium, the rolling temperature is 600±10°C, the heating time is 0.8-0.82 min / mm, and the deformation is controlled to be 50%±2%; or,

[0047] The base layer blank is made of titanium alloy, the rolling temperature is 850±10° C., the heating time is 0.98-1.0 min / mm, and the deformation is controlled to be 50%±2%.

[0048] In some embodiments, the cold deformation method is selected from any one of rolling cold deformation, ball rolling cold deformation and shot peening cold deformation;

[0049] The conditions for performing the cold deformation are selected from any one of the following:

[0050] The rolling cold deformation method is adopted, wherein each time the pressing is performed by 0.01mm to 0.05mm;

[0051] The ball cold deformation method is adopted, wherein the ball diameter is 0.8mm to 3mm;

[0052] The shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8mm-3mm, the pressure is 0.8MPa-5.0MPa, and the processing time is 0.4min-5min.

[0053] In some embodiments, the cold deformation is performed under any one of the following conditions:

[0054] The rolling cold deformation method is adopted, wherein each pressing is 0.02±0.001mm;

[0055] The ball cold deformation method is adopted, wherein the ball diameter is 1±0.05mm;

[0056] The shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8-0.82 mm, the pressure is 2±0.1 MPa, and the processing time is 0.5±0.02 min.

[0057] In some embodiments, after the cold deformation, the grain size of the surface of one side of the intermediate zirconium layer is refined to ≤10 μm, preferably ≤5 μm.

[0058] In some embodiments, in the step of forging the composite blank to be forged,

[0059] The forging temperature is 450°C to 760°C, and / or the heating time is 30 minutes to 300 minutes, and / or the mold preheating temperature is ≥190°C.

[0060] In some embodiments, the base layer blank is made of pure titanium, the forging temperature is 600±10°C, the heating time is 30±5min, and the mold preheating temperature is 200±10°C; or,

[0061] The material of the base layer blank is titanium alloy, the forging temperature is 750±10°C, the heating time is 60±5min, and the mold preheating temperature is 250±10°C.

[0062] In some embodiments, in the step of heating under oxygen exposure,

[0063] The volume ratio of oxygen in the contact gas is 10% to 100%; and / or,

[0064] The heating temperature is 490°C to 760°C; and / or,

[0065] The heating time is 0.5h~5h.

[0066] In some embodiments, the surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is processed to ≤0.2 μm, and then heated under oxygen contact conditions to form a surface oxide layer by in-situ oxidation.

[0067] The surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is processed to ≤0.1 μm, the heating temperature is 650±10° C., and the heating time is 3 h±0.1 h.

[0068] In a fourth aspect of the present invention, there is provided use of the metal composite material described in the first aspect of the present invention, or the metal composite material prepared by the preparation method described in the third aspect of the present invention, in the preparation of artificial joint prostheses.

[0069] In some embodiments, the artificial joint prosthesis comprises a knee joint prosthesis;

[0070] Preferably, the knee joint prosthesis comprises a femoral condyle prosthesis.

[0071] The metal composite material provided in the present invention has a base layer, an intermediate layer and a surface oxide layer stacked in sequence (an intermediate layer and a surface oxide layer are provided on at least one side of the base layer), wherein the base layer and the intermediate layer are completely metallurgically bonded and are firmly welded together, and the interface bonding strength is high, and then the surface of the intermediate layer away from the base layer is firmly bonded to the surface oxide layer formed in situ. Further, the metal composite material provided by the present invention is a titanium-zirconium metal composite material, the base layer adopts a titanium material (such as titanium-based, titanium alloy-based), which has higher strength and hardness and high mechanical safety, and the intermediate layer adopts a zirconium material (zirconium-based, zirconium alloy-based). On the one hand, it can be firmly combined with the base layer, and on the other hand, it can provide a surface that can be self-oxidized to form a dense surface oxide layer containing zirconium oxide, with high surface hardness and good wear resistance. Moreover, the raw material cost of the metal composite material is low, which can significantly reduce the product price, thereby benefiting ordinary patients.

[0072] When this metal composite material is used as a femoral condyle prosthesis, it can effectively reduce wear, reduce aseptic loosening, and lower the revision rate of joint prostheses; moreover, the release of metal ions is small or non-existent, and the risk of allergies caused by metal ions is low; and the cost is low, which can benefit ordinary patients.

[0073] In the preparation method of the metal composite material and femoral condyle prosthesis provided in the present invention, the base layer and the intermediate layer can be composited by explosive composite, rolling composite and diffusion bonding composite methods to form a strong and firm interface bonding force; further, based on the metal surface provided by the intermediate layer, a cold deformation method (such as rolling, ball or shot peening, etc.) is adopted in combination with annealing treatment to fully utilize the dynamic and static recrystallization principles to refine the grain size of the titanium zirconium composite blank surface (the surface on one side of the intermediate zirconium layer), thereby providing a good smooth surface foundation for in-situ oxidation to form a dense oxide layer, and the aforementioned metal composite material and femoral condyle prosthesis can be prepared. Among them, the metal composite material can be used to prepare artificial joint prostheses including but not limited to femoral condyles. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more completely understand the present application and its beneficial effects, a brief introduction to the drawings required for the description of the embodiments will be given below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work. It should also be noted that the drawings are all drawn in a simplified form and are only used to conveniently and clearly assist in explaining the present invention. The various dimensions of each component shown in the drawings are arbitrarily shown and may be accurate or not drawn to scale. For example, in order to make the illustrations clearer, the dimensions of the components are appropriately exaggerated in some places in the drawings. Unless otherwise specified, the components in the figures are not drawn to scale. The present invention does not limit every dimension of each component.

[0075] In the following description, the same reference numerals denote the same parts.

[0076] Figure 1 This is a schematic diagram of the cross-sectional structure of a metal composite material or a femoral condyle prosthesis according to an embodiment of the present invention; an intermediate layer and a surface oxide layer are provided on one side of the base layer;

[0077] Figure 2 Schematic diagram of the cross-sectional structure of a metal composite material or a femoral condyle prosthesis according to an embodiment of the present invention; an intermediate layer and a surface oxide layer are provided on both sides of the base layer;

[0078] Figure 3 Schematic diagram of explosive bonding of a base layer and an intermediate layer in one embodiment of the present invention;

[0079] Figure 4 FIG. 4 is a microstructure diagram of a Zr-2.5Nb (wt%) intermediate layer blank in one embodiment of the present invention.

[0080] Explanation of the reference numerals: 11, base layer blank; 12, intermediate layer blank; 14, explosive layer; 21, base layer; 22, intermediate layer; 23, surface oxidation layer. DETAILED DESCRIPTION

[0081] The present invention will be further described in detail below in conjunction with the accompanying drawings, embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present invention and are not used to limit the scope of the invention. The purpose of providing these embodiments and examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive. It should also be understood that the present invention can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the present invention, and the equivalent forms obtained also fall within the protection scope of the present invention. In addition, in the description below, a large amount of specific details are given in order to provide a more complete understanding of the present invention. It should be understood that the present invention can be implemented without one or more of these details.

[0082] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing embodiments and examples and are not intended to limit the present invention.

[0083] the term

[0084] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0085] The terms "and / or", "or / and", and "and / or" used herein include any one of two or more related listed items, and also include any and all combinations of the related listed items, wherein the arbitrary and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical and" and also undoubtedly includes technical solutions connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution of all being connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solution of all being connected by "logical AND").

[0086] In the present invention, "plurality", "multiple", "multiple times", etc., unless otherwise specified, refer to a number greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0087] Herein, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc. shall be based on the ability to implement the technical solution of the present invention, solve the technical problem of the present invention, and achieve the expected technical effect of the present invention.

[0088] Herein, the terms "preferred," "better," "more preferred," and "suitable" are merely used to describe preferred implementations or examples and should not be construed as limiting the scope of protection of the present invention. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0089] In the present invention, “further”, “further”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of the present invention.

[0090] In the present invention, the terms "optionally," "optional," and "optional" mean optional or dispensable, i.e., they refer to either option being selected from two parallel options: "with" or "without." If a technical solution contains multiple "optional" clauses, each "optional" clause is independent unless otherwise specified and there are no conflicts or constraints.

[0091] In the present invention, the terms "first," "second," "third," and "fourth," etc., in "the first aspect," "the second aspect," "the third aspect," and "the fourth aspect," etc., are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the technical features indicated. Furthermore, "first," "second," "third," and "fourth," etc., serve only as non-exhaustive enumeration and description and should be understood not to constitute a closed-ended limitation on quantity.

[0092] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0093] In the present invention, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is deemed to be continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, including the two endpoint integers of the numerical range and each integer between the two endpoints is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for broad inclusion of numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0094] The temperature parameters in the present invention, unless otherwise specified, may be either constant temperature or fluctuating within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the precision range of the instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0095] In the present invention, the term "room temperature" generally refers to 4°C to 35°C, preferably 20°C ± 5°C. In some embodiments of the present invention, room temperature refers to 20°C to 30°C.

[0096] In the present invention, when referring to the unit of a data range, if the unit is only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3-5h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0097] All documents mentioned in the present invention are cited as references in this application, just as each document is cited as a reference separately. Unless they conflict with the invention purpose and / or technical solution of this application, the cited documents involved in this invention are cited with all their contents and all their purposes. When the present invention involves cited documents, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the present invention involves cited documents, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement the present invention. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description in this application.

[0098] In the present invention, unless otherwise clearly specified and limited, when a first feature is “above” or “below” a second feature, it can mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. In the present invention, unless otherwise clearly specified and limited, when a first feature is “above” or “below” a second feature, it can mean a relative positional relationship in terms of horizontal heights, or it can simply mean that there is an attachment relationship without limiting the relative positional relationship in terms of horizontal heights. Moreover, when a first feature is “above”, “above” or “above” a second feature, it can mean that the first feature is directly above or obliquely above the second feature, or it can simply mean that the first feature is at a higher level than the second feature. When a first feature is “below”, “below” or “below” a second feature, it can mean that the first feature is directly below or obliquely below the second feature, or it can simply mean that the first feature is at a lower level than the second feature.

[0099] In the present invention, the content of each metal component in the alloy can be expressed in the form of nominal composition. Taking zirconium-niobium alloy as an example, "Zr-2.5Nb" means that the weight percentage of Nb is 2.5%.

[0100] China categorizes industrially pure titanium into four grades based on the amount of impurities it contains: TA1, TA2, TA3, and TA4, with increasing impurity content and decreasing purity. TA1, TA2, TA3, and TA4 correspond roughly to US grades 1 through 4: Gr.1, Gr.2, Gr.3, and Gr.4, respectively. As purity decreases, the strength and hardness of industrially pure titanium increase, while its plasticity, impact toughness, and fatigue resistance decrease. TA3 and TA4 are recommended for high strength, hardness, and wear resistance requirements, while TA1 and TA2 are recommended for better formability.

[0101] As used herein, "pure titanium" may be selected from any suitable commercially pure titanium.

[0102] As used herein, “titanium alloy” may be selected from, but not limited to, TA1ELI, TC4, TC4ELI, TC20, and the like.

[0103] As used herein, "pure zirconium" may be selected from any suitable commercially pure zirconium.

[0104] As used herein, "zirconium alloy" may be selected from, but not limited to, Zr-1Nb, Zr-2.5Nb, and the like.

[0105] The first aspect of the present invention

[0106] In the first aspect of the present invention, a metal composite material is provided, the structure of which can be referred to as Figure 1 The metal composite material includes: a base layer 21, and an intermediate layer 22 and a surface oxide layer 23 sequentially stacked on at least one side of the base layer 21.

[0107] The base layer is made of titanium-based material. Preferably, the base layer is made of titanium-based or titanium alloy-based material.

[0108] The middle layer is made of zirconium-based material. Preferably, the material of the middle layer is zirconium-based or zirconium alloy-based;

[0109] The surface oxide layer contains zirconium oxide.

[0110] In the present invention, "titanium-based," "titanium alloy-based," "zirconium-based," and "zirconium alloy-based" define the characteristic material components contained in the corresponding materials, corresponding to the characteristic material components of titanium (Ti), titanium alloy, zirconium (Zr), and zirconium alloy, respectively, and potentially define the basic properties of the corresponding materials. It should be understood that the defined corresponding materials have the same or similar material properties as the corresponding metal products (pure titanium, titanium alloy, pure zirconium, zirconium alloy), are infinitely miscible, and do not produce intermetallic compound phases. It should also be understood that these material types are non-restrictive in the definition of material components. In addition to the "necessary amount" of characteristic material components, other types of metal components are allowed to be contained as long as they do not affect the basic properties of the material. The "necessary amount" refers to the minimum amount of the corresponding metal required to maintain the properties of the corresponding metal material (e.g., the properties of pure titanium, titanium alloy, pure zirconium, zirconium alloy, etc.) (e.g., the minimum content of titanium, titanium alloy, zirconium, and zirconium alloy). Non-limiting examples of numerical values ​​for the "necessary amount" include 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc., and can be expressed as a percentage by mass. Examples of "other metal components" include niobium (Nb), cobalt (Co), and chromium (Cr).

[0111] The metal composite material provided by the present invention has a base layer, an intermediate layer and a surface oxide layer stacked in sequence (an intermediate layer and a surface oxide layer are provided on at least one side of the base layer), wherein the base layer and the intermediate layer are completely metallurgically bonded, are firmly welded together, have high interface bonding strength, will not fall off, and then firmly bond the surface oxide layer formed in situ through the surface of the intermediate layer away from the base layer side. Further, the metal composite material provided by the present invention is a titanium-zirconium metal composite material, the base layer adopts titanium-based materials (such as titanium-based, titanium alloy-based), with higher strength and hardness and high mechanical safety, and the intermediate layer adopts zirconium-based materials (zirconium-based, zirconium alloy-based). On the one hand, zirconium and titanium have similar physical and chemical properties and can be infinitely soluble in each other, so the intermediate layer can be firmly combined with the base layer, and on the other hand, zirconium can provide a surface that can be self-oxidized to form a dense surface oxide layer containing zirconium oxide, with high surface hardness and good wear resistance. Moreover, the raw material cost of the metal composite material is low, which can significantly reduce the product price, thereby benefiting ordinary patients.

[0112] Titanium and titanium alloys have been widely used in orthopedic implants due to their excellent corrosion resistance, good biocompatibility and low elastic modulus. In joint prostheses, titanium and titanium alloys are mainly used for femoral stems and acetabular cups. However, titanium and titanium alloy materials have low shear strength and poor wear resistance, and are not suitable for joint surface materials, such as femoral condyle and femoral head. The present application utilizes zirconium oxide coating to improve wear resistance, reduce wear when used as a joint prosthesis, and extend the service life of the implant material.

[0113] In some embodiments, the thickness of the base layer is 30 mm to 100 mm. The thickness of the base layer can be any one of the following thicknesses or an interval consisting of any two thicknesses: 30 mm, 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, etc. An example of an interval consisting of any two thicknesses is 40 mm to 100 mm, etc. By controlling the base layer to an appropriate thickness, it is beneficial to better forge the femoral condyle in subsequent processes; if the base layer is too thick, it will cause waste, the preparation of the intermediate piece will be difficult, the temperature control requirements for heating will be high, the equipment requirements will be high, and it will also easily lead to surface cracking and poor bonding of the local interface layer, such as the possibility of voids; if the base layer is too thin, it will not meet the implantation requirements.

[0114] In some embodiments, the material of the base layer can be appropriately selected from existing titanium and titanium alloys, and the selectable range can refer to the Chinese national standard GB / T13810-2017 "Titanium and Titanium Alloy Processing Materials for Surgical Implants" and the like.

[0115] In some embodiments, the material of the substrate layer is industrial pure titanium, (α+β) two-phase titanium alloy, or β-type titanium alloy.

[0116] In some embodiments, the thickness of the intermediate layer is 0.5 mm to 5 mm. The thickness of the intermediate layer can be any one of the following thicknesses, or a range consisting of any two thicknesses: 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, etc. An example of a range consisting of any two thicknesses is 1 mm to 5 mm. The intermediate layer is made of a zirconium-based material (zirconium-based or zirconium alloy-based), which not only allows for a strong bond with the base layer but also provides a surface that can undergo auto-oxidation.

[0117] The average grain size of the intermediate layer is ≤10 μm, preferably ≤5 μm, and more preferably ≤3 μm. A smaller grain size is conducive to obtaining a dense oxide layer through the oxidation process. If the grain size is coarse, more cracks will occur.

[0118] In some embodiments, the material of the intermediate layer can be appropriately selected from existing zirconium and zirconium alloys. The range of options can refer to GB / T 26314-2010 "Zirconium and Zirconium Alloys Grades and Chemical Compositions" and the like.

[0119] In some embodiments, the intermediate layer is made of industrial pure zirconium, (α+β) two-phase zirconium alloy, or β-type zirconium alloy.

[0120] In some embodiments, the connection between the base layer and the intermediate layer is metallurgical bonding, which can be achieved by, for example, a combination of explosion welding and diffusion bonding.

[0121] In some embodiments, the thickness of the surface oxide layer is 3 μm to 25 μm. The thickness of the surface oxide layer can be any one of the following thicknesses or a range consisting of any two thicknesses: 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 25 μm, etc. Examples of the range consisting of any two thicknesses include 5 μm to 10 μm, 3 μm to 20 μm, 4 μm to 20 μm, 5 μm to 20 μm, etc.

[0122] In some embodiments, the surface roughness of the surface oxide layer may be any one of ≤0.2 μm, ≤0.18 μm, ≤0.16 μm, ≤0.15 μm, ≤0.14 μm, ≤0.12 μm, ≤0.1 μm, ≤0.05 μm, etc.

[0123] By controlling the oxidation conditions, the thickness, surface roughness, hardness and other parameters of the surface oxide layer can be adjusted to achieve better wear resistance.

[0124] In some embodiments, the main component of the surface oxide layer is zirconium oxide. It can be understood that the surface oxide layer contains a necessary amount of zirconium oxide, so that the surface oxide layer is endowed with the excellent properties of zirconium oxide.

[0125] In some embodiments, the surface oxide layer is formed by in-situ oxidation of the surface of the intermediate layer away from the substrate layer. During the oxidation process, the surface metal is converted into an oxide layer in situ, the oxide layer has a uniform thickness, and the oxide layer has a strong bonding force with the substrate. The surface oxide layer formed by in-situ oxidation has a dense and uniform structure, which can give the material excellent wear resistance. Furthermore, the zirconium element participates in the in-situ oxidation to form zirconium oxide. Compared with the zirconium oxide coating formed by spraying, the dense zirconium oxide layer formed by in-situ oxidation in the present application has a uniform thickness, a smooth surface, low roughness, high hardness, and strong wear resistance.

[0126] The thickness of the base layer, the thickness of the intermediate layer, the average grain size of the intermediate layer, the thickness of the surface oxide layer, and the surface roughness of the surface oxide layer can be selected independently or in any combination from appropriate features in the aforementioned manner.

[0127] Second aspect of the present invention

[0128] In a second aspect of the present invention, a femoral condyle prosthesis is provided, comprising the metal composite material according to the first aspect of the present invention.

[0129] In some embodiments, the metal composite material of the first aspect of the present invention is provided.

[0130] In some embodiments, the metal composite material of the first aspect of the present invention is molded into a predetermined shape during its preparation process, resulting in a metal composite material that can be used as a femoral condyle prosthesis. This metal composite material, when used as a femoral condyle prosthesis, can effectively reduce wear, aseptic loosening, and the revision rate of joint prostheses. Furthermore, it releases little or no metal ions, minimizing the risk of allergic reactions caused by metal ions. Furthermore, it is low-cost, making it accessible to the general public.

[0131] In some embodiments, the structure of the femoral condyle prosthesis can be seen in Figure 1 The femoral condyle prosthesis includes a base layer 21, and an intermediate layer 22 and a surface oxide layer 23 stacked in sequence on one side of the base layer 21. The definitions of the base layer 21, the intermediate layer 22 and the surface oxide layer 23 can refer to the first aspect of the present invention.

[0132] In some embodiments, an intermediate layer 22 and a surface oxide layer 23 are sequentially stacked on both sides of the base layer 21 .

[0133] In some embodiments, the femoral condyle prosthesis is a titanium-zirconium composite. Compared to cobalt-chromium-molybdenum femoral condyles, this titanium-zirconium composite femoral condyle can reduce wear of the ultra-high molecular weight polyethylene tibial liner and reduce the release of Co, Cr, and Ni metal ions. Compared to zirconium-niobium alloy femoral condyles, this femoral condyle has a dense and uniform oxide layer on its surface, resulting in high surface hardness. Furthermore, the substrate is made of titanium or a titanium alloy, which offers greater strength and hardness, and improved mechanical safety. Due to the low cost of raw materials, this femoral condyle can significantly reduce product prices, thereby benefiting ordinary patients.

[0134] The third aspect of the present invention

[0135] In a third aspect of the present invention, a method for preparing a metal composite material or a femoral condyle prosthesis is provided, which can be used to prepare the metal composite material of the first aspect of the present invention or the femoral condyle prosthesis of the second aspect of the present invention.

[0136] In some embodiments, the preparation method comprises the following steps:

[0137] S100 (explosive composite): explosively composite the base layer blank and the intermediate layer blank to obtain a titanium-zirconium composite blank; further, the base layer blank is made of titanium or titanium alloy, and the intermediate layer blank is made of zirconium or zirconium alloy;

[0138] S200 (rolling composite): hot rolling and annealing the titanium-zirconium composite blank to obtain a titanium-zirconium composite blank having a base titanium layer and an intermediate zirconium layer;

[0139] In some embodiments, the preparation method comprises the following steps:

[0140] S100 (explosive composite): explosively composite the base layer blank and the intermediate layer blank to obtain a titanium-zirconium composite blank; further, the base layer blank is made of titanium or titanium alloy, and the intermediate layer blank is made of zirconium or zirconium alloy;

[0141] S200 (rolling composite): hot rolling and annealing the titanium-zirconium composite blank to obtain a titanium-zirconium composite blank having a base titanium layer and an intermediate zirconium layer; and

[0142] S300 (forging, oxidation): Forging treatment is performed, and then in-situ oxidation is performed on one side of the middle zirconium layer to form a surface oxide layer.

[0143] Further, in some embodiments, step S300 includes the following steps: S320, S340, and S360;

[0144] S320 (surface grain refinement): removing the oxide layer on the surface of the middle zirconium layer of the titanium-zirconium composite blank, performing cold deformation, and refining the grains on the surface of the middle zirconium layer to obtain a composite blank to be forged;

[0145] S340 (forging): forging and annealing the composite blank to produce a titanium-zirconium composite forging having a matrix titanium layer and an intermediate zirconium layer;

[0146] S360 (surface oxidation treatment): The surface roughness of the middle zirconium layer of the titanium-zirconium composite forging is processed to an appropriate degree (such as ≤0.2μm), and then heated under conditions of contact with oxygen to form a surface oxide layer by in-situ oxidation.

[0147] In the preparation method of the metal composite material or femoral condyle prosthesis provided above, the base layer and the intermediate layer can be compounded by explosive compounding, rolling compounding and diffusion bonding compounding methods to form a strong and firm interface bonding force; further, based on the metal surface provided by the intermediate layer, a cold deformation method (such as rolling, ball rolling or shot peening, etc.) is adopted and combined with annealing treatment to make full use of the dynamic and static recrystallization principles to refine the grain size of the titanium-zirconium composite blank surface (the surface on one side of the intermediate zirconium layer), thereby providing a good smooth surface foundation for in-situ oxidation to form a dense oxide layer, and the aforementioned metal composite material and femoral condyle prosthesis can be prepared.

[0148] Step S100 (explosion compounding)

[0149] In step S100, the base layer blank and the intermediate layer blank are explosively composited to produce a titanium-zirconium composite blank;

[0150] Furthermore, the material of the base layer blank is titanium-based or titanium alloy-based, and the material of the intermediate layer blank is zirconium-based or zirconium alloy-based.

[0151] In this application, the method for explosively compounding the base layer blank and the intermediate layer blank can be referred to Figure 3 . Explosively compounding the base layer blank and the intermediate layer blank includes: placing the intermediate layer blank 12 above the base layer blank 11 with a suitable gap (such as 0.5mm to 10mm), placing the explosive 14 on the surface of the intermediate layer blank 12 away from the base layer blank 11, detonating the explosive, and compounding and connecting the base layer blank 11 and the intermediate layer blank 12. The composite material obtained by this explosive compounding has a very high interfacial bonding strength. This is because titanium and zirconium are adjacent elements in the same subgroup, have similar properties, and can be infinitely soluble in each other, so the interface has a high bonding strength after connection. From the perspective of material cost, the cost of titanium and titanium alloys is significantly lower than that of zirconium and zirconium alloys. Therefore, explosive compounding combines the advantages of the two materials without sacrificing the overall mechanical properties of the composite material.

[0152] Explosive cladding, also known as explosive welding, is a metal cladding technology that can join dissimilar metals. This technology uses explosive detonation to create an instantaneous ultra-high pressure, ultra-high speed, and ultra-high temperature impact, creating a metal collision jet that propels one material (cladding) toward another (base) at high speed, forming a new material through cladding.

[0153] In this application, the base layer blank 11 and the intermediate layer blank 12 are used to provide the base layer 21 and the intermediate layer 22 in the metal composite material or the femoral condyle prosthesis, respectively. Therefore, the corresponding raw materials can be appropriately selected according to the base layer and the intermediate layer defined in the first aspect of the present invention.

[0154] In some embodiments, the base layer blank and the intermediate layer blank are each independently a plate material, which can be respectively referred to as a base plate and a cover plate.

[0155] In some embodiments, the substrate may be any one of a rolled plate, a forged plate, an extruded plate, and the like.

[0156] In some embodiments, the base layer blank (e.g., substrate) has a thickness of 30 mm to 100 mm. The base layer blank (e.g., substrate) can have any one of the following thicknesses or a range consisting of any two thicknesses: 30 mm, 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, etc. An example of a range consisting of any two thicknesses is 40 mm to 100 mm.

[0157] In some embodiments, the thickness of the intermediate layer stock material (e.g., the cover plate) is 0.5 mm to 5 mm. The thickness of the intermediate layer stock material (e.g., the cover plate) can be any one of the following thicknesses or a range consisting of any two thicknesses: 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, etc. An example of a range consisting of any two thicknesses is 1 mm to 5 mm.

[0158] In some embodiments, the equiaxed microstructure of the intermediate layer blank (eg, cladding plate) is beneficial for subsequent oxidation to form a dense oxide layer.

[0159] In some embodiments, the average grain size of the intermediate layer stock material (e.g., cladding plate) is ≤10 μm, preferably ≤5 μm, and further preferably ≤3 μm. Controlling the average grain size of the intermediate layer stock material facilitates a strong bond with the base layer stock material and provides suitable reaction conditions for subsequent in-situ oxidation to form a dense surface oxide layer, thereby imparting advantageous characteristics such as uniform thickness, dense structure, and good wear resistance to the surface oxide layer.

[0160] In some embodiments, there are no specific requirements for the microstructure of the matrix layer blank (e.g., substrate), and the matrix can be selected from among equiaxed, bimodal, trimodal, basketweave, and Widmanstatten structures. The matrix microstructure type can be selected based on mechanical performance requirements, meeting the performance requirements of the implant site. Widmanstatten structures are advantageous for achieving high toughness, while basketweave, bimodal, trimodal, and equiaxed structures are advantageous for achieving high strength and toughness.

[0161] In the present invention, the base layer plays a bearing role and needs to meet certain mechanical performance requirements. The intermediate layer forms a strong surface oxide layer on the base layer, which plays a role in reducing wear and can give the artificial joint excellent wear resistance.

[0162] Traditional titanium products have poor wear resistance. A zirconium coating can improve wear resistance. However, surface coatings prepared using traditional physical and chemical precipitation methods are prone to detachment. In this application, a zirconium-containing intermediate layer is firmly metallurgically bonded to a base layer. After forging, one side of the zirconium-containing intermediate layer can be oxidized. The in-situ formed surface oxide layer has good adhesion and is not easily detached.

[0163] In some embodiments, the thickness of the base layer blank is 30 mm to 100 mm; and / or,

[0164] In some embodiments, the thickness of the intermediate layer blank is 0.5 mm to 5 mm; and / or,

[0165] In some embodiments, the average grain size of the intermediate layer blank is ≤10 μm, preferably ≤5 μm, and further preferably ≤3 μm.

[0166] The thickness of the base layer blank, the thickness of the intermediate layer blank, and the average grain size of the intermediate layer blank can be selected independently or in any combination from the appropriate features in the aforementioned manner.

[0167] In some embodiments, in step S100, the intermediate layer blank is placed above the base layer blank with a gap of 0.05 mm to 10 mm, explosives are placed on the surface of the intermediate layer blank away from the base layer blank, and the explosives are detonated to compositely connect the base layer blank and the intermediate layer blank.

[0168] In some embodiments, the placement gap between the intermediate layer blank and the base layer blank can be 0.05mm to 10mm, further can be 0.5mm to 10mm, and can also be selected from any one of the following gaps or any two intervals: 0.05mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.8mm, 2.0mm, 2.2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm, 8.5mm, 9mm, 9.5mm, 10mm, etc.

[0169] S200(rolling composite)

[0170] In step S200 (rolling and cladding), the titanium-zirconium composite blank is hot rolled and annealed to produce a titanium-zirconium composite blank. The titanium-zirconium composite blank comprises a base titanium layer and an intermediate zirconium layer, corresponding to the base layer blank and the intermediate layer blank, respectively. The base titanium layer refers to a titanium-based or titanium alloy-based base layer, and the intermediate zirconium layer refers to a zirconium-based or zirconium alloy-based intermediate layer.

[0171] In some embodiments, in the step of hot rolling the titanium-zirconium composite billet, the rolling temperature is 500° C. to 900° C., and / or the heating time is 0.8 to 1.0 min / mm, and / or the deformation is controlled to be 30% to 90%.

[0172] Those skilled in the art are generally aware that the time required for hot rolling is related to the thickness of the rolled sample; thicker samples require longer rolling times. In the present invention, as described elsewhere, "heating time" for hot rolling is expressed in "min / mm," representing the heating time required per millimeter of the rolled sample. In step S200, the rolled sample is a titanium-zirconium composite billet.

[0173] In some embodiments, the rolling temperature may be 500° C. to 900° C., and may be any one of the following temperatures or a temperature range consisting of any two of the following temperatures: 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., 900° C., etc. Examples of a temperature range consisting of any two of the following temperatures include 600±10° C., 850±10° C., 600±5° C., 850±5° C., etc.

[0174] In some embodiments, in the step of hot rolling the titanium-zirconium composite billet, the heating time is 0.8 to 1.0 min / mm, which can be any one of the following time lengths or a time interval consisting of any two of the following time lengths: 0.8 min / mm, 0.82 min / mm, 0.84 min / mm, 0.85 min / mm, 0.86 min / mm, 0.88 min / mm, 1.0 min / mm, etc.

[0175] In some embodiments, in the step of hot rolling the titanium-zirconium composite billet, the heating time is 0.8-0.82 min / mm, 0.98-1.0 min / mm, etc.

[0176] In some embodiments, the controlled deformation amount is 30% to 90%, which can be any one of the following deformation amounts or an interval consisting of any two deformation amounts: 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc. Examples of the interval consisting of any two deformation amounts include 30% to 70%, 50% ± 2%, etc.

[0177] In some embodiments, the base layer blank is made of pure titanium, the rolling temperature is 600±10°C (further such as 600±5°C), the heating time is 0.8-0.82 min / mm, and the deformation is controlled to be 50%±2%.

[0178] In some embodiments, the base layer blank is made of titanium alloy, the rolling temperature is 850±10°C (further such as 850±5°C), the heating time is 0.98-1.0 min / mm, and the deformation is controlled to be 50%±2%.

[0179] S300 (forging, oxidation): Forging treatment is performed, and then in-situ oxidation is performed on one side of the middle zirconium layer to form a surface oxide layer.

[0180] The forging process in step S300 may be performed using or referring to the parameters of the forging method in step S340 , including but not limited to the forging temperature, heating time for forging, die preheating temperature, annealing method and other parameters.

[0181] The in-situ oxidation in step S300 may be performed using or referring to the parameters of the in-situ oxidation method in step S360, including but not limited to parameters such as surface roughness, oxygen concentration, heating temperature, heating time, and thickness of the surface oxide layer.

[0182] S320 (surface grain refinement)

[0183] In step S320 (surface grain refinement), the oxide layer on the surface of the middle zirconium layer of the titanium-zirconium composite blank is removed, cold deformation is performed, and the grains on the surface of the middle zirconium layer are refined to obtain a composite blank to be forged.

[0184] In some embodiments, the oxide layer on the surface of the middle zirconium layer of the titanium-zirconium composite blank may be removed by a commonly used method in the art, such as sanding.

[0185] In some embodiments, the cold deformation method is selected from any one of rolling cold deformation, ball rolling cold deformation and shot peening cold deformation.

[0186] In some embodiments, the cold deformation conditions are selected from any one of the following:

[0187] The cold deformation method is rolling, in which the pressure is reduced by 0.01mm to 0.05mm each time;

[0188] The ball cold deformation method is adopted, wherein the ball diameter is 0.8mm to 3mm;

[0189] A shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8 mm to 3 mm, the pressure is 0.8 MPa to 5.0 MPa, and the processing time is 0.4 min to 5 min, and can further be 0.5 min to 5 min.

[0190] In some embodiments, the cold deformation condition is selected from any one of the following:

[0191] A rolling cold deformation method was used, wherein each reduction was 0.02±0.001 mm. Experimental studies have shown that using this reduction can achieve the same, similar, or better results as in Examples 1 to 11 below, achieving the surface grain refinement required in this step, forming a lower surface roughness, and imparting excellent wear resistance to the product. For details, see Tables 1 and 4.

[0192] The ball cold deformation method is adopted, wherein the ball diameter is 1±0.05mm;

[0193] The shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8±0.02mm, the pressure is 2±0.1MPa, and the processing time is 0.5±0.02min.

[0194] After a large number of experimental studies and explorations, the inventors of this application found that cold deformation using the ball rolling cold deformation method or shot peening cold deformation method provided by the present invention can also achieve the surface grain refinement required in this step, form a lower surface roughness, and give the product excellent wear resistance.

[0195] In some embodiments, after cold deformation, the grain size of the surface of one side of the intermediate zirconium layer is refined to ≤10 μm, preferably ≤5 μm, and more preferably ≤3 μm.

[0196] In some embodiments, the annealing method after hot rolling is not particularly limited, and conventional annealing methods may be used, such as natural cooling in air, continuous cooling, furnace cooling, water cooling, oil cooling, and the like.

[0197] S340(Forging)

[0198] In step S340 (forging), the composite blank to be forged is forged and annealed to produce a titanium-zirconium composite forging. The titanium-zirconium composite forging has a base titanium layer and an intermediate zirconium layer, which correspond to the base layer blank and the intermediate layer blank, respectively, and also correspond to the base titanium layer and the intermediate zirconium layer of the titanium-zirconium composite blank.

[0199] In some embodiments, in the step of forging the composite blank to be forged, the forging temperature is 450°C to 760°C (further can be 500°C to 750°C), and / or the heating time is 30min to 300min, and / or the mold preheating temperature is ≥190°C (further can be ≥200°C).

[0200] In some embodiments, the forging temperature may be 450°C to 760°C, further 500°C to 750°C, and may be any one of the following temperatures or a temperature range consisting of any two of the following temperatures: 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 760°C, etc. Examples of the temperature range consisting of any two of the following temperatures include 600±10°C, 750±10°C, 600±5°C, 750±5°C, etc.

[0201] In some embodiments, in the step of forging the composite blank to be forged, the heating time is 30 min to 300 min, which can be any one of the following time lengths or a time interval consisting of any two of the following time lengths: 30 min, 45 min, 50 min, 60 min, 80 min, 90 min, 100 min, 120 min, 150 min, 180 min, 200 min, 210 min, 240 min, 250 min, 270 min, 300 min, etc.

[0202] In some embodiments, the mold preheating temperature is ≥190°C, and further can be ≥200°C. Examples of mold preheating temperatures include 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 200±10°C, 200±5°C, and the like. A relatively high mold preheating temperature is more conducive to better forging. During the billet forging process, the mold temperature is preferably close to the billet temperature, while the actual preheating temperature may be much lower than the billet temperature (e.g., 200-300°C lower), which will cause heat to dissipate from the billet, causing the temperature to drop rapidly, leading to cracking.

[0203] In some embodiments, the base layer blank is made of pure titanium, the forging temperature is 600±10°C (further such as 600±5°C), the heating time is 30±5 min, and the mold preheating temperature is 200±10°C (further such as 200±5°C).

[0204] In some embodiments, the base layer blank is made of titanium alloy, the forging temperature is 750±10°C (further such as 750±5°C), the heating time is 60±5 min, and the mold preheating temperature is 250±10°C (further such as 250±5°C).

[0205] In some embodiments, the annealing method after forging is not particularly limited and can be achieved by conventional methods.

[0206] When used to prepare a femoral condyle prosthesis, the mold can be used for forming while forging, and this step can also be called forging forming.

[0207] S360 (surface oxidation treatment)

[0208] In step S360 (surface oxidation treatment), the surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is processed to a certain degree (such as ≤0.2μm, ≤0.1μm, ≤0.05μm), and then heated under conditions of contact with oxygen to form a surface oxide layer by in-situ oxidation.

[0209] In some embodiments, the step of machining the surface roughness of one side of the intermediate zirconium layer of the titanium-zirconium composite forging to a certain degree may include machining, grinding, and polishing. Machining can be used to process the blank into the finished shape. Grinding and polishing can reduce the surface roughness to ≤ 0.2 μm.

[0210] In some embodiments, the volume ratio of oxygen in the contact gas is 10% to 100%, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, etc.

[0211] In some embodiments, in the step of heat treatment under oxygen contact conditions, the heating temperature is 490°C to 760°C, and can further be 500°C to 700°C, and can be any one of the following temperatures or a temperature range consisting of any two temperatures: 490°C, 500°C, 550°C, 600°C, 650°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, etc. Examples of a temperature range consisting of any two temperatures include 650±10°C, 650±5°C, etc.

[0212] In some embodiments, the heating time is 0.45h to 5.5h, and can further be 0.5h to 5h, and can be any one of the following time lengths or a time interval consisting of any two of the following time lengths: 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc.

[0213] Before the surface oxidation reaction is carried out, the surface roughness of the middle zirconium layer side of the titanium-zirconium composite forging needs to be processed to an appropriate range, such as ≤0.2μm, ≤0.15μm, ≤0.1μm, ≤0.05μm, etc.

[0214] In some embodiments, the surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is machined to ≤0.1 μm, the heating temperature is 650±10° C., and the heating time is 3 h±0.1 h.

[0215] In some embodiments, the thickness of the formed surface oxide layer is 3 μm to 25 μm, and further can be 3 μm to 20 μm. The thickness of the surface oxide layer can be any of the following thicknesses or an interval consisting of any two thicknesses: 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 25 μm, etc. An example of an interval consisting of any two thicknesses is 5 μm to 10 μm, etc. See also the definition of the first aspect of the present invention.

[0216] The femoral condyle prosthesis prepared by the above preparation method can not only effectively reduce wear and avoid the release of Co, Ni and Cr metal ions, but also has low cost.

[0217] Conventional technology uses ion spraying to prepare zirconium oxide coatings on titanium and titanium alloy surfaces. However, the coatings produced by this method have poor uniformity and poor adhesion to the substrate. In the present application, during the oxidation process, the surface metal is converted into an oxide layer in situ. The oxide layer has a uniform thickness and strong adhesion to the substrate. Furthermore, a complete metallurgical bond can be achieved between the base layer and the intermediate layer, resulting in a strong bond between the intermediate layer and the surface oxide layer. Therefore, the surface oxide layer is firmly bonded and will not fall off. The surface oxide layer formed by in-situ oxidation has a dense and uniform structure, which can give the material excellent wear resistance.

[0218] In some embodiments, before the surface oxidation reaction is performed, the surface roughness of the middle zirconium layer of the titanium-zirconium composite forging is processed to ≤ 0.2 μm, and / or,

[0219] The thickness of the surface oxide layer formed by in-situ oxidation is 3 μm to 25 μm.

[0220] The thickness of the surface oxide layer and the surface roughness of the surface oxide layer can be selected independently or in any combination from the appropriate features in the aforementioned manner.

[0221] The fourth aspect of the present invention

[0222] In a fourth aspect of the present invention, there is provided an application of the metal composite material of the first aspect of the present invention, or the metal composite material prepared by the preparation method of the third aspect of the present invention.

[0223] The metal composite material can be used to prepare artificial joint prostheses including but not limited to femoral condyle.

[0224] In some embodiments, there is provided use of the metal composite material of the first aspect of the present invention, or the metal composite material prepared by the preparation method of the third aspect of the present invention, in preparing an artificial joint prosthesis.

[0225] In some embodiments, the artificial joint prosthesis comprises a knee prosthesis.

[0226] In some embodiments, the knee prosthesis comprises a femoral condyle prosthesis.

[0227] The fifth aspect of the present invention

[0228] In a fifth aspect of the present invention, there is provided the use of the femoral condyle prosthesis according to the second aspect of the present invention, or the femoral condyle prosthesis prepared by the preparation method according to the third aspect of the present invention, in treating joint injuries.

[0229] In some embodiments, the joint injury comprises a knee injury.

[0230] In some embodiments, the knee injury comprises a femoral condyle injury.

[0231] The sixth aspect of the present invention

[0232] In the sixth aspect of the present invention, an artificial joint friction pair is provided, comprising a first support body and a second support body, wherein the first support body is the femoral condyle prosthesis described in the second aspect of the present invention, and the second support body is a soft joint component, and the friction surface of the joint prosthesis and the friction surface of the second support body cooperate with each other.

[0233] The soft joint component herein can be made of the soft end material of an existing "soft-hard" friction pair. "Soft" and "hard" are relative terms. Preferred soft end materials include UHMWPE and PEEK.

[0234] Some specific examples are provided below.

[0235] The embodiments of the present invention will be described in detail below with reference to the examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. For experimental methods in the following examples where specific conditions are not specified, reference is made to the guidance provided in the present invention, and may also be made according to experimental manuals or conventional conditions in the art, or according to conditions recommended by the manufacturer, or with reference to experimental methods known in the art.

[0236] In the following specific examples, the measured parameters of raw material components may have slight deviations within the range of weighing accuracy unless otherwise specified. For temperature and time parameters, acceptable deviations caused by instrument testing accuracy or operational accuracy are allowed.

[0237] Example

[0238] Examples 1 to 11 were carried out according to the parameters in Table 1.

[0239] Taking Example 1 as an example, a metal composite material sample (which can be used as a femoral condyle prosthesis) is prepared by the following steps.

[0240] (1) Explosive bonding: A 60 mm thick TA3 plate was used as the substrate, and a 3 mm thick Zr-2.5Nb plate was used as the cover plate. Explosives were placed on the cover plate, with a gap of 2 mm between the cover plate and the substrate. After igniting the explosives, the cover plate and the substrate were bonded together. The Zr-2.5Nb (wt%) plate was 3 mm thick, had an equiaxed microstructure, and had an average grain size of 5 μm ( Figure 4 ).

[0241] (2) Rolling and compounding: The slab described in (1) is hot rolled at a rolling temperature of 600° C., a heating time of 48 minutes, and a deformation amount of 50%.

[0242] (3) Refining surface grains: After annealing, the surface oxide scale of the plate described in (2) is removed, and then the plate is rolled, with a reduction of 0.02 mm each time.

[0243] (4) Forging: Cut the plate described in (3) and forge it. The heating temperature before forging is 600°C and the temperature is maintained for forging. The heating time is 30 minutes and the mold preheating temperature is 200°C.

[0244] (5) Surface oxidation treatment: The forging described in (4) was annealed, machined, ground and polished to a surface roughness of 0.0232 μm, and then oxidized in air at an oxidation temperature of 650° C. for 3 h, with an oxide layer thickness of 8.97 μm.

[0245] The other Examples 2 to 12 adopt the same method as Example 1, with the only difference being the process parameters shown in Table 1. The thickness of the surface oxide layer formed in each of Examples 1 to 12 is shown in Table 2.

[0246] Table 1. Example parameters

[0247]

[0248]

[0249] Table 2. Surface oxide layer thickness of different examples

[0250] Example Oxide layer thickness (μm) 1 15.1±0.6 2 17.3±0.3 3 20.1±0.5 4 5.3±0.3 5 8.1±0.1 6 4.0±0.4 7 12.1±0.4 8 5.1±0.7 9 8.1±0.5 10 19.8±0.2 11 4.9±0.7 12 4.5±0.2

[0251] Comparative Example

[0252] Comparative Examples 1 to 17 were carried out according to the parameters in Table 3.

[0253] Comparative Examples 1 to 17 adopt methods substantially the same as those of the aforementioned embodiment, with the only difference being the process parameters shown in Table 3.

[0254] Table 3. Comparative Example Parameters and Results

[0255]

[0256] According to the results of the comparative examples in Table 3, it can be seen that if the preparation parameters are inappropriate (such as inappropriate billet size, inappropriate microstructure of the intermediate layer billet, inappropriate rolling temperature, inappropriate forging temperature, etc.), the surface oxide layer formed will not form or the effect will be poor, such as coarse grains, many microcracks, etc. The surface oxide layer with refined grains, low surface roughness and good wear resistance obtained in the present application is the comprehensive result of the synergistic effect of various preparation parameters.

[0257] Comparative Example 18. Preparation of zirconium oxide coating by conventional PVD method

[0258] A zirconium oxide coating with a thickness of about 6 to 7 μm is deposited on the surface of pure titanium or titanium alloy using a conventional physical vapor deposition method (PVD method).

[0259] Comparative Example 19. Preparation of titanium oxide coating by conventional micro-arc oxidation method

[0260] Femoral condyle was prepared by using Ti-10Zr, Ti-30Zr and Ti-50Zr (mass percentage) alloys, and oxidized by micro-arc oxidation to form a titanium dioxide coating with a thickness of about 6 to 7 μm.

[0261] Comparative Example 20: Changing the material of the intermediate layer blank

[0262] The method is basically the same as that of Example 1, except that the intermediate layer blank is replaced by stainless steel, cobalt-chromium-molybdenum alloy, and nickel-based alloy respectively.

[0263] Comparative Example 21: Commercially available femoral condyle CoCrMo (brand ASTM F75) was used.

[0264] Comparative Example 22: Commercially available femoral condyle ZrNb alloy (brand Zr-2.5Nb) was used.

[0265] Wear resistance

[0266] The metal composite material samples prepared in the aforementioned Examples 1 to 12 and Comparative Examples 1 to 17, the samples prepared in Comparative Examples 18 to 20, the cobalt-chromium-molybdenum (CoCrMo) sample (Comparative Example 21), and the zirconium-niobium alloy sample (Comparative Example 22) were respectively combined with ultra-high molecular weight polyethylene (UHMWPE) samples to form friction pairs and simulate the wear of different joint surface assemblies in vivo on a pin-disc wear machine. A pin with a diameter of 6 mm was prepared with the same material as the soft end, and a disk with a diameter of 50 mm was prepared with a hard material. Both the pin and the disk were immersed in calf serum. The pin was subjected to a vertical load of 60 N and made a reciprocating motion on the disk with a stroke of 20 mm. One reciprocating motion was considered a cycle. The wear of the pin and disk was observed after 500,000 cycles and 5,000,000 cycles, respectively. The wear rate was calculated by weighing the weight change. The results can be seen in Table 4. In Table 4, the example number of the metal composite material sample (femoral condyle sample) and the soft end together represent the friction pair used for testing, for example, "Example 1-UHMWPE" represents the friction pair consisting of the femoral condyle sample prepared in Example 1 (as the hard end) and UHMWPE (as the soft end), and "Comparative Example 1-UHMWPE" represents the friction pair consisting of the femoral condyle sample prepared in Comparative Example 1 (as the hard end) and UHMWPE (as the soft end).

[0267] The metal composite materials (femoral condyle samples) prepared in this application exhibit excellent wear resistance, with a wear rate generally below 7 mg / million after 500,000 cycles and below 5 mg / million after 5,000,000 cycles. Specifically, the samples of Examples 1-12 exhibited a wear rate generally below 6 mg / million after 500,000 cycles and below 4 mg / million after 5,000,000 cycles.

[0268] The wear rates for Comparative Examples 4-17 were significantly higher, with some even exceeding those for CoCrMo / UHMWPE. This is presumably due to the high number of microcracks in the oxide layer. During wear, the oxide layer detaches, exposing the substrate and causing wear of the UHMWPE, which increases the overall wear of the friction pair.

[0269] In Comparative Example 18, a zirconium oxide coating was prepared using a conventional physical vapor deposition method (PVD method). It was found that the coating would fall off after 50 to 100 abrasions.

[0270] Comparative Example 19 used micro-arc oxidation to prepare titanium dioxide coating. The surface morphology was observed by scanning electron microscopy, and porous titanium oxide was found to be formed on the surface. According to the wear performance test, the wear resistance was poor, and the wear amount after 5 million times reached 25.30 mg / million times.

[0271] In Comparative Example 20, after the intermediate layer blank was replaced with stainless steel, cobalt-chromium-molybdenum alloy, and nickel-based alloy, respectively, it was found through testing that no ceramic coating was formed on the surface, and a chemical reaction occurred between the interfaces to form a brittle second phase, resulting in low interface bonding strength. After wear testing, the wear loss after 5 million times reached 31.88 mg / million times.

[0272] Comparative Example 21 uses CoCrMo (grade ASTM F75) and UHMWPE to form a friction pair for wear performance testing. The wear rate reaches 15.43 mg / million cycles after 500,000 times, and the wear rate reaches 13.37 mg / million cycles after 5 million times.

[0273] In Comparative Example 22, ZrNb alloy (grade Zr-2.5Nb) and UHMWPE were used to form a friction pair for wear performance testing. Both ZrNb alloy and UHMWPE showed wear, with the wear rate reaching 21.54 mg / million cycles after 500,000 times. Moreover, the sample was damaged and failed before reaching 5 million times of wear.

[0274] According to Table 4, compared with the CoCrMo / UHMWPE friction pair prepared with traditional CoCrMo (Comparative Example 21), the metal composite material of the embodiment of the present application can effectively reduce wear; the wear test results of the metal composite material of the embodiment of the present application are comparable to the wear rate results of the zirconium niobium alloy / UHMWPE friction pair (Comparative Example 22), and some embodiments have better wear resistance.

[0275] Table 4. Comparison of wear rates of different friction pairs

[0276]

[0277] The technical features of the above-mentioned embodiments and examples can be combined in any appropriate manner. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments and examples are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0278] The above embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in a specific and detailed manner, but they cannot be understood as limiting the scope of protection of the present invention. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and the equivalent forms obtained also fall within the scope of protection of the present invention. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the scope of protection of the claims attached to the present invention. Therefore, the scope of protection of the patent of the present invention shall be based on the contents of the attached claims, and the description and drawings can be used to interpret the contents of the claims.

Claims

1. A metal composite material, characterized in that: The metal composite material comprises: a base layer, and an intermediate layer and a surface oxide layer sequentially stacked on at least one side of the base layer; The material of the base layer is titanium-based or titanium alloy-based; the material of the intermediate layer is zirconium-based or zirconium alloy-based; the surface oxide layer contains zirconium oxide; the thickness of the base layer is 30 mm to 100 mm; the thickness of the intermediate layer is 0.5 mm to 5 mm; the average grain size of the intermediate layer is ≤ 10 μm; the connection between the base layer and the intermediate layer is metallurgical bonding; the thickness of the surface oxide layer is 3 μm to 25 μm; and the surface roughness of the surface oxide layer is ≤ 0.1 μm. The metal composite material is prepared by a method comprising the following steps: Explosively compounding a base layer blank and an intermediate layer blank to obtain a titanium-zirconium composite blank; wherein the base layer blank is made of titanium or titanium alloy, and the intermediate layer blank is made of zirconium or zirconium alloy; Hot rolling and annealing the titanium-zirconium composite blank to obtain a titanium-zirconium composite blank having a base titanium layer and an intermediate zirconium layer; wherein, in the step of hot rolling the titanium-zirconium composite blank, the rolling temperature is 500° C. to 900° C., the heating time is 0.8 to 1.0 min / mm, and the deformation is controlled to be 30% to 90%; The forging process is performed, and then the intermediate zirconium layer is in-situ oxidized to form a surface oxide layer; wherein, the oxide layer on the surface of the intermediate zirconium layer of the titanium-zirconium composite blank is removed, cold deformation is performed, and the surface of the intermediate zirconium layer is grain-refined to obtain a composite blank to be forged; the composite blank to be forged is forged and annealed to obtain a titanium-zirconium composite forging having a matrix titanium layer and an intermediate zirconium layer; the surface roughness of the intermediate zirconium layer of the titanium-zirconium composite forging is processed to ≤ 0.2 μm, and then heat-treated under conditions of contact with oxygen to form a surface oxide layer by in-situ oxidation; in the step of forging the composite blank to be forged, the forging temperature is 450°C ~ 760°C, the heating time is 30 min ~ 300 min, and the mold preheating temperature is ≥ 190°C.

2. The metal composite material according to claim 1, wherein Possess one or more of the following characteristics: (b1) the average grain size of the intermediate layer is ≤ 5 μm; (b2) The thickness of the surface oxide layer is 5 μm to 10 μm; (b3) The surface roughness of the surface oxide layer is ≤ 0.05 μm.

3. The metal composite material according to any one of claims 1 to 2, wherein Possess one or more of the following characteristics: (c1) The material of the substrate layer is industrial pure titanium, α+β two-phase titanium alloy or β-type titanium alloy; (c2) The material of the intermediate layer is industrial pure zirconium, α+β two-phase zirconium alloy or β-type zirconium alloy; (c3) The main component of the surface oxide layer is zirconium oxide; (c4) The surface oxide layer is formed by in-situ oxidation of the surface of the intermediate layer away from the base layer.

4. A femoral condyle prosthesis, characterized in that: The metal composite material comprises the metal composite material according to any one of claims 1 to 3.

5. The method for preparing the metal composite material according to any one of claims 1 to 3, characterized in that: The steps include: Explosively compounding a base layer blank and an intermediate layer blank to obtain a titanium-zirconium composite blank; wherein the base layer blank is made of titanium or titanium alloy, and the intermediate layer blank is made of zirconium or zirconium alloy; Hot rolling and annealing the titanium-zirconium composite blank to obtain a titanium-zirconium composite blank having a base titanium layer and an intermediate zirconium layer; and The forging process is performed, and then one side of the intermediate zirconium layer is in-situ oxidized to form a surface oxide layer.

6. The preparation method according to claim 5, wherein Possess one or more of the following characteristics: (d1) The thickness of the substrate layer blank is 30 mm to 100 mm; (d2) The thickness of the intermediate layer blank is 0.5 mm to 5 mm; (d3) The microstructure of the intermediate layer blank is an equiaxed structure; (d4) the average grain size of the intermediate layer blank is ≤ 10 μm; (d5) The thickness of the surface oxide layer formed by in-situ oxidation is 3 μm to 25 μm.

7. The preparation method according to claim 5, wherein The explosively compounding the base layer blank and the intermediate layer blank comprises: The intermediate layer blank is placed above the base layer blank with a gap of 0.05 mm to 10 mm, explosives are placed on the surface of the intermediate layer blank away from the base layer blank, and the explosives are detonated to compositely connect the base layer blank and the intermediate layer blank.

8. The preparation method according to claim 5, wherein The base layer blank is made of pure titanium, the rolling temperature is 600 ± 10°C, the heating time is 0.8 ~ 0.82min / mm, and the deformation is controlled to be 50% ± 2%; or, The base layer blank is made of titanium alloy, the rolling temperature is 850±10°C, the heating time is 0.98~1.0min / mm, and the deformation is controlled to be 50%±2%.

9. The preparation method according to claim 5, wherein The cold deformation method is selected from any one of rolling cold deformation, ball rolling cold deformation and shot peening cold deformation; The conditions for performing the cold deformation are selected from any one of the following: The rolling cold deformation method is adopted, wherein each time the pressure is reduced by 0.01 mm to 0.05 mm; The ball cold deformation method is adopted, wherein the ball diameter is 0.8 mm to 3 mm; The shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8 mm to 3 mm, the pressure is 0.8 MPa to 5.0 MPa, and the processing time is 0.4 min to 5 min.

10. The preparation method according to claim 9, characterized in that The conditions for performing the cold deformation are selected from any one of the following: The rolling cold deformation method is adopted, wherein each pressing is 0.02 ± 0.001 mm; The ball cold deformation method is adopted, wherein the ball diameter is 1 ± 0.05 mm; The shot peening cold deformation method is adopted, wherein the shot peening diameter is 0.8 ~ 0.82 mm, the pressure is 2 ± 0.1 MPa, and the processing time is 0.5 ± 0.02 min.

11. The preparation method according to claim 9, wherein After the cold deformation, the grain size on one side of the intermediate zirconium layer is refined to ≤ 10 μm.

12. The preparation method according to claim 11, wherein After the cold deformation, the grain size on one side of the intermediate zirconium layer is refined to ≤ 5 μm.

13. The preparation method according to claim 5, characterized in that The base layer blank is made of pure titanium, the forging temperature is 600±10°C, the heating time is 30±5 min, and the mold preheating temperature is 200±10°C; or, The material of the base layer blank is titanium alloy, the forging temperature is 750±10℃, the heating time is 60±5 min, and the mold preheating temperature is 250±10℃.

14. The preparation method according to claim 5, wherein In the step of heating under the condition of contact with oxygen, The volume ratio of oxygen in the contact gas is 10% to 100%; Heating temperature is 490℃ ~ 760℃; The heating time is 0.5 h ~ 5 h.

15. The preparation method according to claim 14, wherein The surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging is processed to ≤ 0.2 μm, and then heat-treated under the condition of contact with oxygen to form a surface oxide layer by in-situ oxidation. The surface roughness of one side of the middle zirconium layer of the titanium-zirconium composite forging was processed to ≤ 0.1 μm, the heating temperature was 650±10°C, and the heating time was 3 h±0.1 h.

16. Use of the metal composite material according to any one of claims 1 to 3 or the metal composite material prepared by the preparation method according to any one of claims 5 to 15 in the preparation of artificial joint prostheses.

17. The use according to claim 16, characterized in that The artificial joint prosthesis includes a knee joint prosthesis; wherein, the knee joint prosthesis includes a femoral condyle prosthesis.

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