Krosaki Harima’s Advanced Ceramics for Ultra Precision Field

Jun Sugawara General manager & Chief engineer Precision ceramics technology group Krosaki Harima Corporation

Ceramics Division Krosaki Harima Corporation

Table of Contents Krosaki Harima’s Advanced Ceramics for Ultra Precision Field 1. Background Company & Division

2. Low thermal expansion Ceramics ➢ NEXCERATM ( Cordierite Ceramics)

3. Application for a Calibration tool

4. Application for a Mirror and Scale

Ceramics Division Krosaki Harima Corporation Background The largest Refractory company in Japan • Shareholders ：Nippon Steel Co. Ltd. 42.9% • Established ： 1918 (has been in existence for 94 years) • Employees ： around 4,200 （Consolidated） • Capital ： Around $71 Mill. • Turnover ： Around $1.3 Bill. (2011)

Advanced Ceramics

as Precision Components Refractory Ceramics Products 3 Ceramics Division Krosaki Harima Corporation

Global Production and Service Network

Krosaki USA Inc. (Crown Point, IN ) KHC Europe Office (Düsseldorf, Amsterdam) Krosaki Magnesita Refractories Krosaki Harima YKR SDKT QSK DHC

AMR Refractarios, S.A. WKS Refractories

IFGL Krosaki Shanghai SRIC Magnesita S.A. TRL Krosaki Partner Refractories KCICA Production Base Sales Company & Office Agencies Consolidated subsidiaries 13 Licensee ( Over see 8, Japan 5) 4 Ceramics Division Krosaki Harima Corporation Our advanced ceramics

N117B

C201

Boron carbide ① Standard High stiffness & hardness BC101 → High regidity Low density

The ceramics are used properly to meet the needs of the customer according to the characteristics such as low cost and high stiffness. Special emphasis of our material development and business are placed on the low thermal expansion ceramics and the high stiffness ceramics. Ceramics Division Krosaki Harima Corporation

Thermal expansion and Young’s modulus

450

400 B4C,SiC 350

300 Al2O3 Sialon 250 200 NEXCERA® 150 Super invar alloy Cast Iron Young's modulus(Gpa) 100 Invar alloy 50 Zerodur Aluminum alloy 0 0.01 0.1 1 10 100 Thermal expansion coefficient α (10-6/K)

Most of advanced ceramics have lower thermal expansion coefficient and higher stiffness compared to metal materials. Especially, Sialon has a lowest value in advanced ceramics equal to invar alloy. NEXCERA has an extremely low thermal expansion coefficient equal to Zerodur, but the young’s modulus are excellent compared to Zerodur.

Ceramics Division Krosaki Harima Corporation Table of Contents Krosaki Harima’s Advanced Ceramics for Ultra Precision Field 1. Background Company & Division

2. Low thermal expansion Ceramics > NEXCERATM ( Cordierite Ceramics)

3. Application for Calibration tools

4. Application for Mirrors and Scales

Ceramics Division Krosaki Harima Corporation

NEXCERATM Charasteristics

NEXCERA has been developed as a cutting-edge material having both an extremely low thermal expansion coefficient and superior mechanical properties.

1. Cordierite (2MgO-2Al2O3-5SiO2) based polycrystalline ceramics 2. Ultra low thermal expansion coefficient at 23℃ -6 α <= 0.03 (x 10 /K) at RT Equal to LTEG’ 3. Light in weight 2.5 g/cm3 Lighter than Aluminum’ Equal to LTEG’

4. High Stiffness 130-140 GPa High Strength 210Mpa 1.5-2 times of LTEG’

5. Pore- Less can be finished for Optical-Mirror surfaces

Ceramics Division Krosaki Harima Corporation 2a . NEXCERATTM

Characteristics Table

Code N113B N117B LTEG New Low Thermal Materials NEXCERA NEXCERA expansion glass

Color Black Black Brown Density g/cm3 2.5 2.55 2.53 Young’s Modulus GPa 130 140 60 - 90 Bending Strength MPa 210 230 ( 100～50 )

Fracture Toughness MPaｍ1/2 1.2 1.2 ( 0.8 ) Hardness HV GPa 88 6.6 Thermal Conductivity W/mK 3.7 4.2 1.46

Thermal Expansion ppm < 0.03 < 0.03 0 ±0.02 Coefficient (at 23℃)

Ceramics Division Krosaki Harima Corporation

Thermal Expansion Property of NEXCERATM

Measuring Method : Laser Interferometer Thermal Expansion Curve 0.010

0.009 L/L (%) 0.008 ⊿

ΔＬ／Ｌ ％ 0.007 Thermal Expansion Coefficient S /K) 0.006 h 6 ri d － nk an 0.005 p 10 Ex

× N113B 0.004

0.003

0.002 Thermal Expansion Ratio Thermal Expansion 0.001 α＝0.01×10-6/Ｋ（at 23℃） 0.000

Thermal Expansion Ratio -60 -40 -20 0 20 40 60 80 100 TemperatureTemparature ℃ (℃) Thermal Expansion Coeff. ( Coeff. Expansion Thermal Temperature (℃) The thermal expansion curve indicates NEXCERA once shrinks with the temperature rising, but it expands further rise of the temperature, drawing a minimum thermal expansion coefficient at around room temperature region.

Ceramics Division Krosaki Harima Corporation Comparison of CTE measurement

×10-6/K at 20℃ NEXCERA KH NMIJ (Japan) PTB (Germany) Samples Krosaki Harima National Metrology Institute Physikalisch-Technische Corporation of Japan / AIST Bundesanstalt (Braunschweig)

Sample A -0.001 -0.0035 ------U（α）＝0.0017（K=2） Sample B 0.021 0.0256 ------U（α）＝0.0025（K=2） Sample C -0.007 ------0.0063 U（α）＝0.0026(K=2) Sample D 0.023 ------0.0255 U（α）＝0.0039(K=2)

The table indicates that CTE data measured in KH are in good agreement with the results of national metrology Institutes.

Ceramics Division Krosaki Harima Corporation

Advantages of NEXCERATM Long-term dimensional stability of NEXCERATM Akira Takahashi Meas. Sci. Technology 23(2012) 035001

NEXCERATM 13 months Standard Scale (550mm)

6 months Position deviation ±4.6nm(2σ) per 550mm in length during 13 months

less than uncertainty of measuring system

Zerodur Standard Scale (300mm) 4 months 8 months Shrink 90nm 13 months per 300mm in length 16 months during 13 months

Ceramics Division Krosaki Harima Corporation Dimensional Stability Measurement by NMIJ

National Metrology Institute of Japan (NMIJ)

We have been measuring the length change of NEXCERATM blocks with linking optical flats by an interferometric method cooperating with NMIJ.

観測部Measuring Laser安定化レーザ of 3 wave lengths

ブロックゲージ面Block gauge surface Reference 参照ミラー ブロックゲージGauge Block Mirror b レーザ光導入部 a 干渉縞の ズレFringe shift Length長さ L

Fringe干渉縞画像 image Laser beam entrance entrance beam Laser ベースプレート にリンギング Air空気屈折率、熱膨張補正等 refractive index system Linking & thermal expansion correction of NMIJ < Measuring Principle >

◆Cooperation with NMIJ of AIST

Ceramics Division Krosaki Harima Corporation

Result of Dimensional Stability

NEXCERATM Gauge Block (200mm)

100 80 Data of NMIJ (Japan) 60 40 20 0 -20 -40

Length change (nm) Data of PTB -60 (Germany) -80 -100 0 6 12 18 24 30 Time (month) NEXCERATM has a higher dimensional stability compare to Zero expansion glasses.

Ceramics Division Krosaki Harima Corporation Table of Contents Krosaki Harima’s Advanced Ceramics for Ultra Precision Field 1. Background Company & Division

2. Low thermal expansion Ceramics > NEXCERATM ( Cordierite Ceramics)

3. Application for Calibration tools

4. Application for Mirrors and Scales

5. Sialon Ceramics

Ceramics Division Krosaki Harima Corporation

Applications of NEXCERATM

High dimensional stability for long-term passage ==> Used as calibration tools and primary standards. Hole Plate for calibration of CMM (Coordination Measuring Machine)

CMM is calibrated by measuring holes which positions are accurately defined in advance by a public institute of Metrology.

Cooperated with AIST ( AIST : National Institute of Advanced Industrial Science and Technology)

Ceramics Division Krosaki Harima Corporation NEXCERA Calibration Tools

Expert model of Hole Plate Normal model of Hole Plate

410 x 410mm 610 x 610mm 410 x 410mm 610 x 610mm Custom-made model of Hole Plate

410 x 410

Ceramics Division Krosaki Harima Corporation

NEXCERA Calibration Tools

Daily Checkup Master of CMM NEXCERA + TiN-Coated Ball 200 x 200

350 x 350 x 200mm

NEXCERA + CFRP 300 x 300 Ceramics Division Krosaki Harima Corporation NEXCERATM Step Gauge

Step Gauge 350mm Step Gauge 500mm & 1000mm

Step Gauge 550mm

Ceramics Division Krosaki Harima Corporation

NEXCERATM Ball Bars

New ESCALON HA 1 m beam with 51 balls by Trapet Precision Engineering

Ball Bar for CMM 980mm φ１inch Dimension Master KIT by TRESA Co. Ball Bar 500mm φ15/16

350 x 350 mm

Ceramics Division Krosaki Harima Corporation Gauges for non-contact CMM

Sphere Standards Ball bars 500, 250, 125mm with matte surface φ1 inch φ 1＆φ4 inch

made of NEXCERATM

made of NEXCERATM

Step cylinder φ30 x 27 Gauge for X-ray CT

Ceramics Division Krosaki Harima Corporation

Ball Bars of other materials

Ball bars (CFRP) φ1 & φ2 inch x 600mm Target bar 1000mm made of Ball bar NEXCERATM (CFRP) 1500mm

Ball bar (Sialon) 300mm Cubic bar

(CFRP+ Al2O3)

Ceramics Division Krosaki Harima Corporation Gauges

Plate Step Gauge 600mm ＮＥＸＣＥＲＡ Gear Pitch Master made of NEXCERATM

Hole Bar 600 & 800mm ＮＥＸＣＥＲＡ

Ceramics Division Krosaki Harima Corporation

NEXCERATM Gauge Block

NEXCERA Gauge Block

NEXCERA gauge blocks have already come onto the market.

Ceramics Division Krosaki Harima Corporation NEXCERA Hole Plate Hole Plate for calibration of CMM mirror surface

< Specifications > diameter : φ20 mm roundness : <1 µm roughness Ra : <0.05 µm cylindricity : <2 µm 410 X 410mm 610 X 610mm

・The high-precision machinability of NEXCERA can lead to the achievement of the specifications • Hole Positions have been defined by NMIJ with uncertainty (k=2) of 0.35µm

Ceramics Division Krosaki Harima Corporation

Hole Accuracies of a Hole Plate

Roundness 0.77～1.07μm

Cylindricity 1.89μm

Straightness 0.88μm

Ceramics Division Krosaki Harima Corporation Uncertainty of Hole Positions

Calibration Certificate by NMIJ

NEXCERA Hole Plate

Uncertainty (k=2 , 95%) = 0.35μm

Ceramics Division Krosaki Harima Corporation

Example of Measurement Result

[Krosaki Harima] XY-Plane YZ-Plane XZ-Plane

Zeiss PRISMO

800 700 700 700 600 600 600 500 500 500 400 400 400

300

Y [mm] Y 300 Z [mm] Z

300 [mm]Z

200 200 200

100 100 100

0 0 0 0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700 -100 -100 -100 X [mm] X [mm] Y [mm]

校正値 ZX面内誤差20000倍拡大 校正値 XY面内誤差20000倍拡大 校正値 YZ面内誤差20000倍拡大 Ｘ-axis Error 2.48μm／m Ｙ-axis Error 7.99μm／m Ｘ-axis Error 2.3μm／m Ｙ-axis Error 8.84μm／m Ｚ-axis Error 3.32μm／m Ｚ-axis Error 3.3μm／m Squareness 5.74μrad Squareness 0.16μrad Squareness 12.25μrad The error tendency of CMM can be recognized easily.

Ceramics Division Krosaki Harima Corporation Example of Measurement Result

[A Company] Squareness XZ 0.4μm Scale error Y 1.2μm/350mm

XY

Figure 1 XZ-axis Measurement XZ

Squareness XZ 6.8μm Scale error X 0.2μm/350mm

Ceramics Division Krosaki Harima Corporation

Example of Measurement Result

[B company]

Evaluation of Calibration Leiz PMM654 for CMM using NEXCERA Before Calibration After Calibration [C company]

Comparison between NEXCERATM Hole Plate and Steel Ball Plate

Mitutoyo LEGEX707

Ceramics Division Krosaki Harima Corporation Advantage of NEXCERA Step-Gauge Thermal deformation Analysis of Step-Gauge, 500mm in length

Surface temperature : 20℃～30℃

Up side 30℃

∆Τ=10℃ Down side 20℃

STEEL NEXCERATM

Max. displacement ：25.5μm Max. displacement : 0.1μm CTE11.7×10-6/K 207GPa CTE0.05×10-6 /K 130GPa

Ceramics Division Krosaki Harima Corporation

Advantage of NEXCERA Step-Gauge

NEXCERA Step-gauge is brought into an inspection room after 40℃ heat treatment.

m) ±0.1μm μ )

The length change saturates to be ℃ less than±0.1µm within 30 minutes. Measuring length change ( Surface temperature ( Time ( Hr )

NEXCERA Calibration tool does not require a time of temperature-constant operation. => You can reduce a loss of time in a calibration of CMM.

Ceramics Division Krosaki Harima Corporation Table of Contents Krosaki Harima’s Advanced Ceramics for Ultra Precision Field 1. Background Company & Division

2. Low thermal expansion Ceramics > NEXCERATM ( Cordierite Ceramics)

3. Application for a Calibration tool

4. Application for a Mirror and Scale

Ceramics Division Krosaki Harima Corporation

4-1 Polishing property of N117B

Strong points of NEXCERA in polishing process

1. The pore-less microstructure => which reduces a defect by pores

2. Homogeneous structure of one crystal phase => which reduces a step on polished surface because of no difference of grains hardness

3. Can be polished by oxide abrasive = > which reduces scratches on polished surface because of its chemical effect

Ceramics Division Krosaki Harima Corporation Polishing by oxide abrasive ● Comparison of rough polishing

by oxide abrasive (SiOX) Ra 6nm Rmax 100nm Ra 2nm Rmax 30nm

Cordierite of other company NEXCERATM N117B

Ceramics Division Krosaki Harima Corporation

NEXCERA (N117B) Mirror application

Φ150×30t

Aluminum + SiO2 Coating on NEXCERA Reflectivity 90 % 90% Reflectivity

Average Roughness Ra 0.31nm 550 700 Wave length (nm)

NEXCERA’s strong points for polishing have achieved an extremely smooth surface with Ra of 0.31 nm and flatness of less than λ/10.

Ceramics Division Krosaki Harima Corporation Trial manufactures of NEXCERATM

A trial sample of NEXCERA’s Air Slider NEXCERA Linear Scale 200 x 35 x 5 mm

NEXCERA Frameless Mirror

49 x 49 mm λ/10 24.4 x 24.4 mm λ/10 Dielectric multilayer coating

Mirror substrate (140 x 55 x 8 ) for a Surveying instrument Ceramics Division Krosaki Harima Corporation

Manufacturing Process Overview

Raw materials ⇒ Slurry Mixing ⇒ Dried as granule

Pressing ⇒ Chalk-like Block

Green ⇒ Near-Net Shape (by cutting tools)

Sintering ⇒ Shrink 20% in length

Machining ⇒ Grinding,

Inspection

Ceramics Division Krosaki Harima Corporation Green Machining Process

Before sintering, a pressed Chalk-like block of NEXCERATM is easily machined by Cutting Tools as same as a steel material.

Ribbed Mirror Substrate φ750 x 180 mm Rib thickness 3mm Rib depth 160mm

Ceramics Division Krosaki Harima Corporation

NEXCERA Bonding Technology

Self SEM micrograph of bonding area Ｎ113B Lid plate Lid

Bonding interface

Ribbed Body Rib A box type bonding sample

Ultrasonic microscope image Comparison of flexural strength at the bonding face between bonding interface and bulk portion

Ceramics Division Krosaki Harima Corporation Lightweight Mirror

Using the green machining method and bonding Ultrasonic microscope image technology, a light weight Mirror is manufactured around the bonding interface as shown here.

Φ340 Ribbed body ( Rib thickness 3mmt )

Bonded Ribbed Mirror φ340x70 Bonding

φ340 Top Plate (4mm thickness)

Ceramics Division Krosaki Harima Corporation

4-2 Lightweight ribbed Mirror

Flatness < λ/10 55 nm

Φ340x70mmt 5.4kg

Material density =2.55g/cm3 Apparent density = 0.85g/cm3

Ceramics Division Krosaki Harima Corporation Lightweight Mirror Φ340 x 70t Coated ribbed Mirror

Dielectric multilayer coating Aluminum + SiOX coating

2 types of coating for NEXCERA ribbed mirror with λ/10 flatness

Ceramics Division Krosaki Harima Corporation

Flatness of Lightweight Mirror

J. Sugawara Proc. ASPE(2010) 50, 404 Zygo GPI XP/D 12” ( Krosaki Harima )

Ultimate horizontal flatness Interferometer ( developed by National Metrology Institute of Japan ) Supported on three points of outer end Flatness PV= 45nm, < λ/10

Size: φ340 x 70t

Ceramics Division Krosaki Harima Corporation Flatness Stability of the ribbed Mirror

Flatness change of φ340 x 70 Mirror in heat cycles Flatness 58nm

Before heat cycles

Heat Cycle (RT==> -20℃ 11hr ==> +60℃ 11hr ==> RT) 4 times

Flatness 60nm

NEXCERA Mirror can maintain its ultra precision flatness after 4 heat cycles.

After heat cycles

Ceramics Division Krosaki Harima Corporation

Big ribbed Mirror substrate

NEXCERA Big ribbed body φ 640mm x 150mmH rib thickness 3mmt Weight : around 22kg

Ceramics Division Krosaki Harima Corporation Bonding of a big ribbed mirror Ultrasonic microscope image around the joining interface Top plate

Ribbed body

Joined big ribbed body φ 640 x 150mmH Rib thickness of 3mm

➢ φ 780 x 150mm ribbed Mirror is being manufactured now.

Ceramics Division Krosaki Harima Corporation

Thank you for your kind attention!

Mt. Fuji NEXCERATM

Ceramics Division Krosaki Harima Corporation