CN102503546B - Antioxidant impregnating agent of graphite die used for hot-pressing sintering of diamond tool and preparation method and processing method thereof - Google Patents
Antioxidant impregnating agent of graphite die used for hot-pressing sintering of diamond tool and preparation method and processing method thereof Download PDFInfo
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Abstract
The invention discloses an antioxidant impregnating agent of graphite dies used for hot-pressing sintering of diamond tools and preparation method and processing method of the antioxidant impregnating agent of graphite dies. The antioxidant impregnating agent is made from compound phosphates, high temperature-resistant curing agents, compression-resistant reinforcing agents, pH regulators and water. The method comprises the following steps of: firstly adding water into compound phosphates and heating and mixing to dissolve completely to obtain a homogenous transparent liquid; then adding hightemperature-resistant curing agents and compression-resistant reinforcing agents to the transparent liquid and heating and mixing until homogenous; and finally adding pH regulators to adjust the pH value of the liquid mixture to 1 to 3, to obtain the solution of antioxidant impregnating agent. The solution of antioxidant impregnating agent, prepared by the invention, is applied to antioxidant treatment of a graphite die by impregnation; and the related performances of the graphite die are tested after treatment. The graphite die treated by the antioxidant impregnating agent substantially retains electrical properties of graphite, has an electrical resistivity of not more than 20 omega mm<2>/m, and is substantially not be oxidized at a temperature below 800 DEG C. The porosity is reduced by 50% and the compression strength is greatly increased.
Description
Technical field
The present invention relates to a kind of anti-oxidant soaker, particularly relate to the anti-oxidant soaker of graphite jig and compound method and treatment process for a kind of thermal pressing sintering diamond tool.
Background technology
The thermal pressing sintering diamond tool graphite jig is being undertaken the dual function of Heating element and mould support in the diamond tool manufacturing processed, and the quality good or not of graphite jig directly has influence on dimensional precision, face shaping of diamond tool etc.The sintering process of hot pressed gold diamond tool requires: temperature reaches 1000 ℃ ± 2 ℃, and forming pressure is 16～50MPa, and the heat-insulation pressure keeping time is 15～30min, and environment is antivacuum state.Under this working condition, requirement has electroconductibility, higher resistivity, enough physical strength, antioxidant property and longer work-ing life preferably as the graphite jig of moulding and Heating element, with this, guarantees dimensional precision, excellent properties and the longer work-ing life of hot pressed gold diamond tool.
At present, domestic high temperature hot pressing diamond tool graphite jig, generally select common graphite or high purity graphite to process, through constantly type selecting, development and improvement, its main technical parameters can meet the requirement of its hot-pressing sintering technique basically, but compare with current international most advanced level, also have larger gap.
Europe, the United States, day etc. developed country hot pressed gold diamond tool graphite jig, be mainly the graphite material of ultra-fine grain structure, high purity and high graphitization degree, require its median size to be less than 15 μ m, even, below 10 μ m, medium pore size is less than 2 μ m.The graphite jig of the high graphitization degree made from the carbon raw of ultra-fine grain, have that void content is little, compact structure, surface smoothness is high, resistance to compression, High anti bending strength, resistivity is high, oxidation-resistance is these characteristics by force, can guarantee thus dimensional precision, surface smoothness and the grinding performance of hot pressed gold diamond tool.
Because the raw-material super fine powder technology difficulty of carbon element is very big, at present, only have the developed countries such as Europe, the United States, day can produce the graphite jig of this ultra-fine grain structure, the carbon element particle of domestic production, median size can only reach 37～45 μ m, indivedual manufacturers can reach 25 μ m, but can't produce in batches.Simultaneously, the high purity graphite of domestic production, its purity is also far below abroad, and graphite jig short texture, the particle produced thus are thicker, and mold surface finish is low, void content is high, and antioxidant property and ultimate compression strength are relatively low.Therefore, current graphite jig is the following problem of ubiquity in use: (1) die surface oxidation rate is too fast, due to oxidation corrosion, cause that die surface pore and surfaceness increase, outward appearance and dimensional precision reduce, not only affect graphite jig work-ing life, and affect the diamond tool working accuracy.(2) mould is in reusing process, and due to the oxidation corrosion strength decreased, usually in hot pressing, fracture appears in mould, and this not only causes the huge waste of graphite, has increased the diamond tool manufacturing cost simultaneously, has also brought the hidden danger on the production safety.(3) mould conduction, heat conductivility descend, and affect inner quality and the stability thereof of diamond tool.Therefore, in the high temperature hot pressing process, in order to ensure stability and the production security of diamond tool quality, have to limit the access times of graphite jig.At present, domestic graphite jig access times, at 5～8 times, are only 1/4th of external product access times, and this not only causes the huge waste of graphite material, has increased the manufacturing cost of diamond tool simultaneously.On domestic market, the hyperfine structure graphite jig is mainly to rely on import, and price is very high, is 4～5 times of domestic common graphite mould quotation.Therefore, manufacture diamond tool for high temperature hot pressing and carry out anti-oxidant monographic study with graphite jig, select that a kind of technique is simple, cost is low, be easy to the antioxidation treatment technology of suitability for industrialized production, have very important significance.
In recent years, Chinese scholars has been carried out large quantity research to the graphite anti-oxidation tech, has researched and developed multiple reduction graphite material oxidation consumption new technology, such as: antioxidation surface coating method, solution dipping method, self-healing and charcoal pottery composite algorithm etc.In air, the anti-oxidant problem of graphite material below 1600 ℃ solves substantially, but considers from over-all properties and the purposes of graphite material, and still have unsolved technical problem, various anti-oxidation treatment methods also have certain defect and limitation.Top coat method cost value is high, and the difference of thermal expansion coefficients between coating and graphite matrix is large, in the high temperature hot pressing process, easily comes off or cracks, and forms the diffusion admittance of oxygen, can reduce the antioxidant property of graphite jig; Self-healing and charcoal pottery composite algorithm, by being added on the ceramic particle oxidation in the graphite material matrix, form ceramic membrane on the graphite material surface, make the surface of graphite material there are some ceramic material properties, although improved oxidation-resistance and the ultimate compression strength of graphite, but can cause the decline of graphite material electroconductibility, self lubricity reduction etc., manufacture diamond tool for hot pressed sintering and be restricted with the graphite jig antioxidation treatment; Solution dipping method is to have porousness for graphite material; select preparation Special Anti oxidation soaker solution, by certain treatment process, antioxidant is sealed to the pore of graphite material; and form one deck protection against oxidation layer on surface, stop the oxidation corrosion of oxidizing gas to graphite.Solution dipping method is less to the properties influence of graphite material, has substantially kept the self-characteristic of graphite material after processing, and shortcoming is that antioxidant effect is not so good as coating, self-healing and charcoal pottery composite algorithm.
Summary of the invention
The object of the invention is to overcome the defect that current high temperature hot pressing diamond tool exists with graphite jig, provide that a kind of technique is simple, cost is low, be applicable to the antioxidation treatment technology of thermal pressing sintering diamond tool with the pyrographite mould, the technical problem to be solved in the present invention is to provide the anti-oxidant soaker of graphite jig and compound method and treatment process for a kind of thermal pressing sintering diamond tool.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides the anti-oxidant soaker of graphite jig for a kind of thermal pressing sintering diamond tool, described anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and water, described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 15～45%, 0.5～6%, 0.2～4%, 0.1～2% and the water of surplus, and each composition weight percentage sum is 100%.
According to the anti-oxidant soaker of graphite jig for above-mentioned thermal pressing sintering diamond tool, described composite phosphate is to take aluminium dihydrogen phosphate as main, adds any one or two kinds of in zinc phosphate and ammonium hydrogen phosphate;
Described high temperature resistant solidifying agent is alkaline metal fluoride cpd;
Described resistance to compression toughener be in nitride, carbide and oxide compound any or any two or three kinds; Perhaps described resistance to compression toughener is to take nitride as main, adds any one or two kinds of in carbide and oxide compound;
Described pH adjusting agent is industrial phosphoric acid.(industrial phosphoric acid generally adopts the phosphoric acid that phosphoric acid that mass percentage concentration is 65% or mass percentage concentration are 85%).
According to the anti-oxidant soaker of graphite jig for above-mentioned thermal pressing sintering diamond tool, described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, the mass ratio of add-on is 3～1:1; Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and ammonium hydrogen phosphate, the mass ratio of add-on is 3～1:1; Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate and ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, ammonium hydrogen phosphate three, the mass ratio of add-on is 3:1:1～1:1:1;
Described alkaline metal fluoride cpd be in Sodium Fluoride, Potassium monofluoride and Calcium Fluoride (Fluorspan) any or any two;
Described nitride is boron nitride or silicon nitride; Described carbide is charing boron or carborundum; Described oxide compound is boron trioxide or silicon-dioxide.
According to the anti-oxidant soaker of graphite jig for above-mentioned thermal pressing sintering diamond tool, described resistance to compression toughener is to take nitride as main, adds carbide, and during the two mixing of nitride and carbide, the shared weight percentage of nitride is 50～75%;
Described resistance to compression toughener is to take nitride as main, adds oxide compound, and during the two mixing of nitride and oxide compound, the shared weight percentage of nitride is 50～75%;
Described resistance to compression toughener is to take nitride as main, add carbide and oxide compound, when nitride, carbide and oxide compound three mix, the shared weight percentage of nitride is 50～75%, the two weight percentage accounted for altogether of carbide and oxide compound is 25～50%, when carbide and oxide compound are 25～50% blend according to the weight percentage accounted for altogether, blending ratio is arbitrary proportion.
According to the anti-oxidant soaker of graphite jig for above-mentioned thermal pressing sintering diamond tool, when described alkaline metal fluoride cpd is any two in Sodium Fluoride, Potassium monofluoride and Calcium Fluoride (Fluorspan), the mass ratio between two kinds of fluorochemicals is 1:1.
A kind of compound method of above-mentioned anti-oxidant soaker, described compound method comprises the following steps:
A, according to the proportioning ratio of above-mentioned anti-oxidant soaker, prepare various raw materials, at first add water in composite phosphate, under the condition constantly stirred, heated, being heated to 65～80 ℃ fully dissolves, dissolve 0.5～1.5h under 65～80 ℃ of conditions, obtain homogeneous transparent liquid after fully dissolving, gained homogeneous transparent liquid is placed for a long time without crystalline polamer;
Add high temperature resistant solidifying agent and resistance to compression toughener in b, the homogeneous transparent liquid that obtains at step a, continue heated and stirred even, during heated and stirred, temperature is controlled at 60～75 ℃, and the heated and stirred time is 0.5～1.0h;
Add pH adjusting agent in c, last liquid after step b stirs, the pH value to 1 of adjusting mixing liquid～3, obtaining uniform and stable translucent suspension after adjusting is anti-oxidant soaker solution.
According to the compound method of above-mentioned anti-oxidant soaker, in the described anti-oxidant soaker solution of step c with P
2o
5meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Described anti-oxidant soaker solution 25 ℃, be coated with under the condition of-4 glasss its Nian Du<=30s.
A kind of method of utilizing above-mentioned anti-oxidant soaker to process graphite jig the treating method comprises following steps:
A, at first graphite jig base sample is carried out to pre-treatment, described pre-treatment for being cleaned successively, dry, calcination;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a, the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.1～0.8MPa, and dipping temperature is 25～65 ℃, vacuum tightness is-0.015MPa that dipping time is 1.5～5.0h; Described anti-oxidant soaker solution is to utilize above-mentioned anti-oxidant soaker proportioning ratio formulated, and compound method is to adopt above-mentioned compound method;
C, thermal treatment: the graphite jig after step b dip treating is cured, and solidification value is warming up to 900 ℃ by room temperature, is incubated 15～20 min after being warming up to 900 ℃; Adopt after solidifying that stove is cold is lowered the temperature, be cooled to room temperature.
Process the method for graphite jig according to the above-mentioned anti-oxidant soaker that utilizes, described in step a, clean is to adopt organic solvent industrial spirit or distilled water to be soaked, being about to graphite jig base sample is immersed in organic solvent or distilled water, soak time is 1.0～1.5h, after cleaning, removes in the graphite jig micropore and surperficial greasy dirt dust;
During described drying, drying temperature is 120～150 ℃, is dried to constant weight;
Described calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination, controlling calcination temperature is 600～700 ℃, calcination time is 30～40min., be cooled to room temperature after calcination, remove the organism of graphite surface after calcination, then adopt pressurized air to purge the graphite jig surface, remove top layer discrete particle and dust, expose unoxidized graphite surface.
Process the method for graphite jig according to the above-mentioned anti-oxidant soaker that utilizes, described in step c, by room temperature, be warming up to 900 ℃, its heat-up rate is 4～6 ℃/min; The described room temperature that is cooled to, temperature fall time is 10～15h.
The present invention adopts solution dipping method antioxidation treatment technology, with graphite jig, a kind of anti-oxidant impregnant composition is disclosed for the thermal pressing sintering diamond tool manufacture, with this composition, graphite jig is carried out to antioxidation treatment, graphite jig after antioxidation treatment, the basic electrology characteristic that keeps graphite material self, meeting fully in thermal pressing sintering diamond tool manufacture process requirement situation, improving oxidation-resistance and the ultimate compression strength of graphite jig, extending the work-ing life of graphite jig.
positive beneficial effect of the present invention:
1, utilize the anti-oxidant soaker solution of the present invention, under certain processing requirement, thermal pressing sintering diamond tool is carried out to antioxidation treatment with graphite jig, the graphite jig after processing, substantially the electrology characteristic that has kept graphite material self, resistivity is not more than 20 Ω mm
2/ m, void content has reduced by 50%
,in not oxidation substantially below 800 ℃, ultimate compression strength obviously improves
.the anti-oxidant soaker of the present invention also can be used for the anti-oxidant dip treating of various graphite materials, and its antioxidation treatment effect is better than similar products at home and abroad.
2, the present invention adopts the anti-oxidant soaker of different proportionings, its graphite jig is carried out to dip treating, after processing, its graphite jig is tested, and compare with the graphite jig detection data after utilizing existing soaker to process, with this, the impact of soaker of heterogeneity on oxidation-resistance and the ultimate compression strength of graphite jig is described, test result refers to table 1.
The impact of table 1 heterogeneity soaker on graphite jig oxidation-resistance and ultimate compression strength
Indicate: in technical solution of the present invention 1, the proportioning of anti-oxidant soaker forms and refers to embodiment 1, compound method and refer to embodiment 9, the dip treating method of graphite jig is referred to embodiment 13; In technical solution of the present invention 2, the proportioning of anti-oxidant soaker forms and to refer to embodiment 2, compound method and refer to embodiment 9, the dip treating method of graphite jig is referred to embodiment 13; In technical solution of the present invention 3, the proportioning of anti-oxidant soaker forms and to refer to embodiment 3, compound method and refer to embodiment 9, the dip treating method of graphite jig is referred to embodiment 13.
3,, from above-mentioned table 1 test-results, adopt the solution dipping method treatment technology, and utilize the composition of the anti-oxidant soaker of the present invention, graphite jig is carried out to anti-oxidant dip treating, graphite jig after processing, antioxidant property is better, and ultimate compression strength is significantly improved.
4, utilize technical solution of the present invention to carry out anti-oxidant dip treating to graphite jig, the graphite jig sample after dip treating is carried out to correlation detection, its resistivity is not more than 20 Ω mm
2/ m, void content has reduced by 50%, and graphite jig is in diamond high speed, ultra-thin parting tool Application in manufacture, respond well, meets the hot-pressing sintering technique requirement fully; Sintering temperature is in the time of 600～900 ℃, and mean life processed front the use 5～8 times by graphite jig, after the anti-oxidant dip treating of the present invention, uses 16～20 times.
5, from the anti-oxidant dipping experiment of table 1 and product practical application, the anti-oxidant soaker of the present invention is a kind of oxidation-resistant material of excellent property, this soaker can be for the anti-oxidant dip treating process of various graphite materials, be specially adapted to the anti-oxidant dip treating of thermal pressing sintering diamond tool with graphite jig, graphite jig after processing, basic graphite material self electrology characteristic that keeps, antioxidant property is good, ultimate compression strength obviously improves, and its antioxidation treatment effect is better than similar products at home and abroad.
four, embodiment:
Following examples only, in order to further illustrate the present invention, do not limit content of the present invention.
Embodiment 1:
The anti-oxidant soaker of graphite jig for a kind of thermal pressing sintering diamond tool, described anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and water, described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 30%, 3%, 2%, 0.8% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate and ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, ammonium hydrogen phosphate three, the mass ratio of add-on is 3:1:1;
Described high temperature resistant solidifying agent is Sodium Fluoride; Described resistance to compression toughener is boron nitride; Described pH adjusting agent is the industrial phosphoric acid that mass percentage concentration is 85%.
Embodiment 2: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 20%, 2.5%, 1.5%, 1.2% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, the mass ratio of add-on is 3:1; Described high temperature resistant solidifying agent is Potassium monofluoride; Described resistance to compression toughener is charing boron.
Embodiment 3: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 40%, 5%, 1%, 0.3% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and ammonium hydrogen phosphate, the mass ratio of add-on is 3:1; Described high temperature resistant solidifying agent is Calcium Fluoride (Fluorspan); Described resistance to compression toughener is boron trioxide.
Embodiment 4: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 45%, 2%, 3%, 0.2% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate and ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, ammonium hydrogen phosphate three, the mass ratio of add-on is 2:1:1; The mixture that described high temperature resistant solidifying agent is Sodium Fluoride and Potassium monofluoride, the mixing quality of the two is than being 1:1; The mixture that described resistance to compression toughener is silicon nitride and carborundum, when the two mixes, the shared weight percentage of silicon nitride is 70%.
Embodiment 5: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 15%, 0.5%, 0.2%, 2% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate and ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, ammonium hydrogen phosphate three, the mass ratio of add-on is 1:1:1; The mixture that described high temperature resistant solidifying agent is Sodium Fluoride and Calcium Fluoride (Fluorspan), the mixing quality of the two is than being 1:1; The mixture that described resistance to compression toughener is silicon nitride and silicon-dioxide, when the two mixes, the shared weight percentage of silicon nitride is 75%.
Embodiment 6: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 25%, 1.5%, 1.2%, 0.5% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, the mass ratio of add-on is 2:1; Described high temperature resistant solidifying agent is Sodium Fluoride; The mixture that described resistance to compression toughener is boron nitride and charing boron, when the two mixes, the shared weight percentage of boron nitride is 65%.
Embodiment 7: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 35%, 4.5%, 3.5%, 0.5% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, the mass ratio of add-on is 1:1; Described high temperature resistant solidifying agent is Sodium Fluoride; The mixture that described resistance to compression toughener is boron nitride and boron trioxide, when the two mixes, the shared weight percentage of boron nitride is 60%.
Embodiment 8: substantially the same manner as Example 1, difference is:
Described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 42%, 6%, 4%, 0.6% and the water of surplus, and each composition weight percentage sum is 100%.
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds ammonium hydrogen phosphate, and between aluminium dihydrogen phosphate and ammonium hydrogen phosphate, the mass ratio of add-on is 2:1; Described high temperature resistant solidifying agent is Calcium Fluoride (Fluorspan); The mixture that described resistance to compression toughener is boron nitride and charing boron, boron trioxide three, when the three mixes, boron nitride, charing boron and the shared weight percentage of boron trioxide are respectively 55%, 30% and 15%.
Embodiment 9:
A kind of compound method of anti-oxidant soaker, the detailed step of described compound method is as follows:
A, according to the proportioning ratio of anti-oxidant dipping described in embodiment 1, prepare various raw materials, at first add water in composite phosphate, under the condition constantly stirred, heated, being heated to 70 ℃ fully dissolves, dissolve 1h under 70 ℃ of conditions, obtain homogeneous transparent liquid after fully dissolving, gained homogeneous transparent liquid is placed for a long time without crystalline polamer;
Add high temperature resistant solidifying agent and resistance to compression toughener in b, the homogeneous transparent liquid that obtains at step a, continue heated and stirred even, during heated and stirred, temperature is controlled at 70 ℃, and the heated and stirred time is 1.0h;
Add pH adjusting agent in c, last liquid after step b stirs, regulate the pH value to 1 of mixing liquid～3, obtain uniform and stable translucent suspension after adjusting and be anti-oxidant soaker solution (in anti-oxidant soaker solution with P
2o
5meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Described anti-oxidant soaker solution 25 ℃, be coated with under the condition of-4 glasss its Nian Du<=30s).
Embodiment 10: substantially the same manner as Example 9, difference is:
In step a: the proportioning ratio according to anti-oxidant dipping described in embodiment 2 is prepared various raw materials, is heated to 80 ℃ and fully dissolves, and under 80 ℃ of conditions, dissolves 0.5h;
In step b: during heated and stirred, temperature is controlled at 75 ℃, and the heated and stirred time is 0.5h.
Embodiment 11: substantially the same manner as Example 9, difference is:
In step a: the proportioning ratio according to anti-oxidant dipping described in embodiment 3 is prepared various raw materials, is heated to 65 ℃ and fully dissolves, and under 65 ℃ of conditions, dissolves 1.5h;
In step b: during heated and stirred, temperature is controlled at 60 ℃, and the heated and stirred time is 1.0h.
Embodiment 12: substantially the same manner as Example 9, difference is:
In step a: the proportioning ratio according to anti-oxidant dipping described in embodiment 6 is prepared various raw materials, is heated to 75 ℃ and fully dissolves, and under 75 ℃ of conditions, dissolves 1.0h;
In step b: during heated and stirred, temperature is controlled at 65 ℃, and the heated and stirred time is 1.0h.
Embodiment 13:
A kind of method of utilizing anti-oxidant soaker to process graphite jig of the present invention the treating method comprises following steps:
A, at first graphite jig base sample is carried out to pre-treatment, described pre-treatment for being cleaned successively, dry, calcination;
Described cleaning is to adopt industrial spirit or distilled water to be soaked, and is about to graphite jig base sample and is immersed in organic solvent or distilled water, and soak time is 1.0～1.5h, after cleaning, removes in the graphite jig micropore and surperficial greasy dirt dust;
During described drying, drying temperature is 130 ℃, is dried to constant weight;
Described calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination, controlling calcination temperature is 650 ℃, calcination time is 35min, be cooled to room temperature after calcination, remove the organism of graphite surface after calcination, then adopt pressurized air to purge the graphite jig surface, remove top layer discrete particle and dust, expose unoxidized graphite surface;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a, the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.5MPa, and dipping temperature is 45 ℃, and vacuum tightness is-0.015MPa that dipping time is 3.0h; Described anti-oxidant soaker solution is to utilize the described anti-oxidant soaker proportioning ratio of embodiment 1 formulated, and compound method is the compound method that adopts embodiment 9;
C, thermal treatment: the graphite jig after step b dip treating is cured, and solidification value is warming up to 900 ℃ (its heat-up rate is 4～6 ℃/min) by room temperature, is incubated 15～20 min after being warming up to 900 ℃; Adopt after solidifying that stove is cold is lowered the temperature, be cooled to room temperature (temperature fall time is 10～15h).
Graphite jig after dip treating is tested.
Embodiment 14: substantially the same manner as Example 13, difference is:
Step a: during described drying, drying temperature is 120 ℃; Controlling calcination temperature is 600 ℃, and calcination time is 40min;
Step b: the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.8MPa, and dipping temperature is 25 ℃, and vacuum tightness is-0.015MPa that dipping time is 4.0h; Described anti-oxidant soaker solution is to utilize the described anti-oxidant soaker proportioning ratio of embodiment 2 formulated, and compound method is the compound method that adopts embodiment 9.
Embodiment 15: substantially the same manner as Example 13, difference is:
Step a: during described drying, drying temperature is 150 ℃; Controlling calcination temperature is 700 ℃, and calcination time is 30min;
Step b: the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.3MPa, and dipping temperature is 60 ℃, and vacuum tightness is-0.015MPa that dipping time is 2.0h; Described anti-oxidant soaker solution is to utilize the described anti-oxidant soaker proportioning ratio of embodiment 3 formulated, and compound method is the compound method that adopts embodiment 9.
Claims (1)
1. the anti-oxidant soaker of graphite jig for a thermal pressing sintering diamond tool, it is characterized in that: described anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and water, described composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH adjusting agent and the shared weight percentage of water are respectively 15～45%, 0.5～6%, 0.2～4%, 0.1～2% and the water of surplus, and each composition weight percentage sum is 100%;
Described composite phosphate is to take aluminium dihydrogen phosphate as main, adds zinc phosphate, and between aluminium dihydrogen phosphate and zinc phosphate, the mass ratio of add-on is 3～1:1; Or described composite phosphate is to take aluminium dihydrogen phosphate as main, add ammonium hydrogen phosphate, between aluminium dihydrogen phosphate and ammonium hydrogen phosphate, the mass ratio of add-on is 3～1:1; Or described composite phosphate is to take aluminium dihydrogen phosphate as main, add zinc phosphate and ammonium hydrogen phosphate, between aluminium dihydrogen phosphate and zinc phosphate, ammonium hydrogen phosphate three, the mass ratio of add-on is 3:1:1～1:1:1;
Described high temperature resistant solidifying agent be in Sodium Fluoride, Potassium monofluoride and Calcium Fluoride (Fluorspan) any or any two;
Described resistance to compression toughener is to take nitride as main, adds carbide, and during the two mixing of nitride and carbide, the shared weight percentage of nitride is 50～75%; Or described resistance to compression toughener is to take nitride as main, add oxide compound, nitride and oxide compound the two while mixing, the shared weight percentage of nitride is 50～75%; Or described resistance to compression toughener is to take nitride as main, add carbide and oxide compound, when nitride, carbide and oxide compound three mix, the shared weight percentage of nitride is 50～75%, the two weight percentage accounted for altogether of carbide and oxide compound is 25～50%, when carbide and oxide compound are 25～50% blend according to the weight percentage accounted for altogether, blending ratio is arbitrary proportion;
Described pH adjusting agent is industrial phosphoric acid.
2. the anti-oxidant soaker of graphite jig for thermal pressing sintering diamond tool according to claim 1 is characterized in that: when described high temperature resistant solidifying agent is any two in Sodium Fluoride, Potassium monofluoride and Calcium Fluoride (Fluorspan), the mass ratio between two kinds of fluorochemicals is 1:1.
3. the compound method of an anti-oxidant soaker claimed in claim 1, is characterized in that, described compound method comprises the following steps:
A, according to the proportioning ratio of the described anti-oxidant soaker of claim 1, prepare various raw materials, at first add water in composite phosphate, under the condition constantly stirred, heated, being heated to 65～80 ℃ fully dissolves, dissolve 0.5～1.5h under 65～80 ℃ of conditions, obtain homogeneous transparent liquid after fully dissolving, gained homogeneous transparent liquid is placed for a long time without crystalline polamer;
Add high temperature resistant solidifying agent and resistance to compression toughener in b, the homogeneous transparent liquid that obtains at step a, continue heated and stirred even, during heated and stirred, temperature is controlled at 60～75 ℃, and the heated and stirred time is 0.5～1.0h;
Add pH adjusting agent in c, last liquid after step b stirs, the pH value to 1 of adjusting mixing liquid～3, obtaining uniform and stable translucent suspension after adjusting is anti-oxidant soaker solution.
4. the compound method of anti-oxidant soaker according to claim 3 is characterized in that: in the described anti-oxidant soaker solution of step c with P
2o
5meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Described anti-oxidant soaker solution 25 ℃, be coated with under the condition of-4 glasss its Nian Du<=30s.
5. one kind is utilized anti-oxidant soaker claimed in claim 1 to process the method for graphite jig, it is characterized in that, the treating method comprises following steps:
A, at first graphite jig base sample is carried out to pre-treatment, described pre-treatment for being cleaned successively, dry, calcination;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a, the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.1～0.8MPa, and dipping temperature is 25～65 ℃, vacuum tightness is-0.015MPa that dipping time is 1.5～5.0h; Described anti-oxidant soaker solution is to utilize the proportioning ratio of the described anti-oxidant soaker of claim 1 formulated, and compound method is to adopt compound method claimed in claim 3;
C, thermal treatment: the graphite jig after step b dip treating is cured, and solidification value is warming up to 900 ℃ by room temperature, is incubated 15～20 min after being warming up to 900 ℃; Adopt after solidifying that stove is cold is lowered the temperature, be cooled to room temperature.
6. the method for utilizing anti-oxidant soaker to process graphite jig according to claim 5, it is characterized in that, described in step a, clean is to adopt organic solvent industrial spirit or distilled water to be soaked, being about to graphite jig base sample is immersed in organic solvent or distilled water, soak time is 1.0～1.5h, after cleaning, removes in the graphite jig micropore and surperficial greasy dirt dust;
During described drying, drying temperature is 120～150 ℃, is dried to constant weight;
Described calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination, controlling calcination temperature is 600～700 ℃, calcination time is 30～40min, be cooled to room temperature after calcination, remove the organism of graphite surface after calcination, then adopt pressurized air to purge the graphite jig surface, remove top layer discrete particle and dust, expose unoxidized graphite surface.
7. the method for utilizing anti-oxidant soaker to process graphite jig according to claim 5, it is characterized in that: be warming up to 900 ℃ by room temperature described in step c, its heat-up rate is 4～6 ℃/min; The described room temperature that is cooled to, temperature fall time is 10～15h.
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| CN 201110314580 CN102503546B (en) | 2011-10-17 | 2011-10-17 | Antioxidant impregnating agent of graphite die used for hot-pressing sintering of diamond tool and preparation method and processing method thereof |
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| CN102910909B (en) * | 2012-10-19 | 2014-03-05 | 辽宁辽洛科技发展有限公司 | Graphite carbon cover and antioxidation dipping treatment method thereof |
| CN104163657A (en) * | 2014-07-21 | 2014-11-26 | 中国矿业大学(北京) | Graphite mould antioxidant impregnation liquid, preparation method and application method thereof |
| CN104528710A (en) * | 2015-01-22 | 2015-04-22 | 南通华耐特石墨设备有限公司 | Generation method of impermeable graphite |
| CN104891480A (en) * | 2015-05-28 | 2015-09-09 | 中国科学院山西煤炭化学研究所 | Preparation method for antioxidative graphite material |
| CN106396380A (en) * | 2016-08-26 | 2017-02-15 | 温书强 | High pressure resistant Jun porcelain ware, and preparation method thereof |
| CN106977231A (en) * | 2017-03-31 | 2017-07-25 | 华东理工大学 | A kind of processing method of new raising carbon material antioxygenic property |
| CN108997028A (en) * | 2018-08-08 | 2018-12-14 | 深圳市科达利实业股份有限公司 | Graphite mold surface anti-oxidation treatment method |
| CN109020624B (en) * | 2018-08-30 | 2020-12-18 | 河南省化工研究所有限责任公司 | Preparation method of high-temperature-resistant graphite mold in air atmosphere |
| CN109437173A (en) * | 2018-11-05 | 2019-03-08 | 上海弘枫实业有限公司 | A kind of preparation process of fire-resistant oxidation resistant graphite |
| CN112645682B (en) * | 2020-12-29 | 2022-06-24 | 滨州双峰石墨密封材料有限公司 | Antioxidant, high-temperature antioxidant flexible graphite plate preparation process and graphite plate |
| CN115636689B (en) * | 2022-09-09 | 2023-09-19 | 华能国际电力股份有限公司 | Oxidation resistance dipping treatment method and oxidation resistance production line of graphite sealing piece for thermal power generating unit |
| CN115784779B (en) * | 2022-12-02 | 2023-10-20 | 中色正锐(山东)铜业有限公司 | Graphite corrosion inhibitor and preparation method and application thereof |
| CN116063103B (en) * | 2023-03-06 | 2023-07-21 | 江西宁和达新材料有限公司 | Preparation method of antioxidant graphite gasket |
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