Polymer Testing 70 (2018) 526–532

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Optimization of the preparation process of biodegradable masterbatches and T

characterization of their rheological and application properties
Chen-yao Chena, Jin Gua, Yun-xuan Wenga,b,∗, Zhi-gang Huanga,b, Dan Qiuc, Shuang-xi Shaoc
a
School of Material and Mechanical Engineering, Beijing Technology and Business University, Beijing, 100048, China
b
Plastic Beijing Municipal Key Laboratory of Health and Safety Quality Evaluation Technology, Beijing, 100048, China
c
Fenghua Institute, Ningbo University of Technology, China

A R T I C LE I N FO A B S T R A C T

Keywords: Using glycerin as a plasticizer, polylactic acid (PLA) and titanium dioxide (TiO2) were blended and granulated
Dyeing force using a twin-screw extruder to obtain a biodegradable white color masterbatch. The rheological properties of the
Masterbatch masterbatch were characterized by a torque rheometer and a melt flow rate (MFR) tester. The dyeing force of the
Opacifying ability sample was characterized by measuring its whiteness index, lightness index, and yellowness index using a color
Polylactic acid
meter, while the opacifying ability of the sample was characterized by measuring its light transmittance with a
Regression equation
Response surface methodology
haze meter. Temperature sensors were set up in each zone of the extruder screws to measure their temperatures
in real time. By using quadratic orthogonal rotation combination design, and in conjunction with a response
surface methodology (RSM), the effects of processing conditions, such as screw shear speed, processing tem-
perature, and glycerin content, on the opacifying ability of white PLA masterbatch were studied. In addition,
Design-Expert software was used to simulate the relationship between various processing conditions and the
opacifying ability of white PLA masterbatch. The experimental results showed that, when the glycerin content
was 1%, the whiteness index of the masterbatch was highest and its color was brightest. When the glycerin
content was 3.22%, the light transmittance of the masterbatch was lowest and its opacifying ability was
strongest. This paper was the first to use response surface methodology to study optimization of the preparation
process for biodegradable masterbatches.

1. Introduction biodegradable masterbatches can be talc, silica, calcium carbonate,

Due to the intensification of white pollution and the shortage of
global petroleum resources, biodegradable plastics, such as polylactic
acid (PLA), poly (butyleneadipate-co-terephthalate) (PBAT), are in-
creasingly used in packaging, daily necessities, and medical applica-
tions [1,2]. In the processing of these products, color masterbatches are
often used for coloration. However, the vast majority of color mas-
terbatches in today's market are prepared using conventional polymers,
such as LLDPE and LDPE [3], as carriers. Because color masterbatches
based on these traditional polymers are not biodegradable, products
made from these masterbatches are also not biodegradable. Therefore,
in order to ensure the biodegradability of final products, color mas-
terbatches and the carriers used in them must be biodegradable. The
carrier polymer of biodegradable color masterbatches can be PLA,
polyhydroxyalkanoates (PHA), and polybutylene succinate (PBS).
Among these biodegradable materials, PLA has become a hotspot of
development and research in recent years [4]. The filler of
starch or cellulose [5], and the dispersant can be glycerin, corn oil or
cleanse oil [6].
White color masterbatches are often used to color injection-molded
products such as knives, forks, and spoons. The white color of these
products is mostly produced by the solid pigment titanium dioxide
(TiO2). TiO2 is a nontoxic, light, high gloss material with a high re-
fractive index and a high scattering rate [7,8]. Due to its high refractive
index and excellent opacifying ability, TiO2 is superior to other white
pigments and is widely used in white color masterbatches. Opacifying
ability or opacity is an important indicator of the dyeing performance of
white color masterbatches because it represents the performance of the
pigment in terms of light absorption, scattering and reflection. Opacity
also reflects the ability of the coating to cover the surface color of the
substrate [9]. With an identical pigment addition, the pigment with
better opacifying ability will produce lighter and thinner plastic pro-
ducts with the same level of whiteness. When the mass fraction of TiO2
in the carrier is higher than 30%, the viscosity of the polymer system

∗
Corresponding author. School of Material and Mechanical Engineering, Beijing Technology and Business University, Beijing, 100048, China.
E-mail address: wyxuan@th.btbu.edu.cn (Y.-x. Weng).

https://doi.org/10.1016/j.polymertesting.2018.08.011
Received 30 May 2018; Received in revised form 22 July 2018; Accepted 11 August 2018
Available online 11 August 2018
0142-9418/ © 2018 Published by Elsevier Ltd.
C.-y. Chen et al.
rapidly increases, which reduces the processability of the material [10]
and requires the use of a plasticizer to adjust the viscosity of the system.
Sarazin et al. [11] used glycerin as a plasticizer for PLA/TPS composites
and found that the effect of plasticization was significant. Because of
the significant impact of the process parameters on the properties of the
composite [12], the type of plasticizer, toner content, screw shear rate,
and processing temperature all influence color masterbatch processing
and coloring performance. Therefore, in order to optimize the effects of
various processing conditions on the use performance of biodegradable
masterbatches, it is particularly important to find a method that can
optimize their preparation process.
Using polylactic acid as the carrier for color masterbatches, TiO2 as
the pigment toner and glycerin as the plasticizer, an optimized method
for the preparation of biodegradable masterbatches with high opaci-
fying ability was developed. The biodegradable resin, plasticizer, and
pigment were placed into a twin-screw extruder for granulation. In
addition, temperature sensors were set up in each zone of the extruder
screws to automatically collect temperatures and other process para-
meters during processing. Furthermore, response surface methodology
(RSM) was used in conjunction with a three-variable quadratic re-
gression equation and orthogonal rotation experiments to analyze the
preparation processes and study the factors affecting the opacifying
ability of the biodegradable masterbatch during extrusion granulation.
RSM is an optimization method combining experimental design
with statistics [13]. It includes numerous methods, such as experi-
mental design, modeling, testing, model suitability, and searching for
the best combination of conditions. Through regression fitting and re-
sponse surface analysis, the response value at the level of each factor
can be easily calculated [14]. RSM is widely used in the preparation of
composite materials and optimization of process variables [15–17], but
its use in masterbatch preparation has not been reported.
2. Experimental
2.1. Materials
PLA (4032D, NatureWorks, USA): vitrification temperature of
55–60 °C, melt index of 7 g/10 min, and peak melting temperature of
155–170 °C;
TiO2 (Shanghai Sinopharm Group): relative density of approxi-
mately 4.0;
Glycerin (AR, Shanghai Sinopharm Group): boiling point 290 °C.
2.2. Principal equipment used
Twin-screw extrusion granulator, DT-20, Screw diameter: 20 mm,
L/D: 44, Nanjing Dingtian Machinery Manufacturing Co., Ltd.
Twin-screw film blower, XSS-300, Shanghai Kechuang Rubber and
Plastic Machinery Equipment Co., Ltd.
Torque rheometer, XSS-300, Shanghai Kechuang Rubber and Plastic
Machinery Equipment Co., Ltd.
Electric thermostatic blast drying oven, DHG-9245A, Shanghai
Yiheng Technology Co., Ltd.;
High speed mixer, SHR-10A, Suzhou Shengguang Plastic Machinery
Co., Ltd.;
Melt flow rate (MFR) tester, XNR-400, Jinjian Detection Instrument
Co., Ltd.;
Digital haze meter, NDH-20D, Feng Cheng Power Equipment Co.,
Ltd.;
Automatic color meter, SC-80C, Beijing Kangguang Instrument Co.,
Ltd.
2.3. Sample preparation
2.3.1. Masterbatch preparation
The masterbatch used for testing consisted of three parts: colorant,
527
Polymer Testing 70 (2018) 526–532
Table 1
Process formulations of the masterbatches.
PLA (Wt%) GI (Wt%) TiO2 (Wt%)
70 0 30
70 1 30
70 3 30
70 5 30
70 7 30
carrier, and plasticizer. The carrier was PLA, the colorant was titanium
dioxide, and the plasticizer was glycerin. The specific formulations are
listed in Table 1.
PLA and TiO2 were placed into a high-speed mixer and mixed at
100 °C for 20 min, followed by the addition of glycerin. After even
mixing, the mixture was placed into a twin-screw extruder to produce
granules. For the twin screws, the temperature from the inlet to the
screw head was 120–155 °C, and the screw movement frequency was
30 Hz.
2.3.2. Preparation of thin films
PLA resin was premixed with the masterbatch described in section
2.3.1 (the content of TiO2 in the pigmented resin was 1%) and put into
the extruder/film blower. The temperatures for the three stages of film
blowing were 165 °C, 175 °C, and 180 °C.
2.3.3. Preparation of sample plates
PLA resin was premixed with the masterbatch described in section
2.3.1 (the content of TiO2 in the pigmented resin was 1%) and put into
the torque rheometer. After further mixing, the mixture was pressed
into plates. The temperature of the torque rheometer was set to 170 °C,
175 °C, or 180 °C. The rotation speed was 60 rpm, and the processing
time was 8 min. The press temperature was 190 °C.
2.3.4. Design of RSM based on opacifying ability
(1) Design of experiments based on a CCD [18,19] model.
The experimental design was based on a two-level factorial design
plus the extreme points and the center point. Usually, the experimental
table was coded and then converted into actual operating values. In
general, the values were 0, ± 1, and ± α, where ± 1 were the cubic
points and were also called the corner points. There were a total of 2k
corner points. The value of 0 was the center point, and α was the axial
point, whose value was given by the formula α= F (1/4) , where F was the
number of experiments for the factorial design. F= 2k , and k was the
number of factors.
In this experiment, a combination design of ternary quadratic re-
gression and orthogonal rotation was used to obtain the following va-
lues: k = 3, F = 8, and α = 1.68. Based on these values, a group of 20
experiments was designed, of which the number of factorial experi-
ments was 8 and the number of star points was 6, while 6 center point
repetitions were performed to ensure uniform precision.
Three factors, i.e., glycerin content (A), twin-screw frequency (B),
and maximum temperature of twin screw processing (C), were selected
as independent variables, and 5 levels were assigned for each factor and
coded as 0, ± 1, and ± 1.68, respectively. The light transmittance of
the masterbatch was used as the response value to design a 3-factor, 5-
level test. The specific experimental factors and level design are shown
in Table 2.
(2) According to the experimental conditions specified in Table 3, the
masterbatch was prepared by twin-screw extrusion and granula-
tion.
(3) Using the masterbatch prepared in Table 3, films and sample plates
were prepared according to 1.3.2 and 1.3.3.
C.-y. Chen et al. Polymer Testing 70 (2018) 526–532

Table 2 (lgTstandard )/ Dstandard = (lgT )/ D

Experimental factors and levels to test the process optimization of the mas-
terbatch based on opacifying ability. where: Tstandard - light transmittance of the film with the standard
thickness, unit: %;
Factor Code value

−1.68 −1 0 +1 +1.68 T - the measured value of the light transmittance of the film;
Dstandard - the standard thickness of the film (0.02 mm);
A: Glycerin content 1% 2.2% 4% 5.8% 7% D – the measured thickness of the film, unit: mm
B: Screw frequency (Hz) 25 26 27.5 29 30
C: Temperature (°C) 130 134 140 146 150
2.4.3. Test of rheological performance
A torque rheometer was used to measure 50 g of the masterbatch
Table 3 sample at a temperature of 150 °C and a rotation speed of 60 rpm. The
Experimental table for the combination of ternary quadratic regression and test was continued for 8 min to measure the rheological properties of
orthogonal rotation. the masterbatch.
No. A: Glycerin content B: Screw frequency C: Temperature
2.4.4. Melt index
% Hz °C
An XNR-400 melt flow rate meter was used to measure the melt
1 2.22 26.01 134.05 index. In brief, the meter was warmed up to 190 °C, after which ap-
2 5.78 26.01 134.05 proximately 5 g of the test material was put into the tester and kept
3 2.22 28.99 134.05 warm for 1 min. After the resin was completely melted, the amount of
4 5.78 28.99 134.05
resin flowing out of the tester in 30 s was measured under a force of
5 2.22 26.01 145.95
6 5.78 26.01 145.95
2160 g. A total of 5 measurements were averaged, and this value was
7 2.22 28.99 145.95 used to calculate the amount of resin flowing out of the tester in 10 min,
8 5.78 28.99 145.95 which was considered as the melt index of the sample.
9 1.00 27.50 140.00
10 7.00 27.50 140.00
11 4.00 25.00 140.00 3. Results and discussion
12 4.00 30.00 140.00
13 4.00 27.50 130.00 3.1. The effect of glycerin content on the coloring properties of PLA/TiO2
14 4.00 27.50 150.00
masterbatch
15 4.00 27.50 140.00
16 4.00 27.50 140.00
17 4.00 27.50 140.00 Table 4 shows the dyeing force of masterbatches with varying gly-
18 4.00 27.50 140.00 cerin content. Colored PLA plate are shown in Fig. 1.
19 4.00 27.50 140.00 The dyeing force of masterbatch on plastics can be characterized by
20 4.00 27.50 140.00
the whiteness index of the masterbatch coloring plate. The higher the
whiteness(W), the stronger the coloration. The lightness index(L) in-
2.4. Characterization and material properties testing dicates the brightness of the template, and its value is related to the
degree of light reflection from the sample plate. The higher the light-
2.4.1. Dyeing force testing ness, the brighter the sample and the higher the degree of light re-
The whiteness index, lightness index, and yellowness index of the flection. As shown in Table 4, the whiteness and lightness of the mas-
sample plates produced by masterbatch injection were measured using terbatch increased first and then decreased at the content of glycerin
a color meter. The color values were represented by the CIE1964 uni- increased, while the yellowness of the masterbatch decreased first and
form color space system of L*, a* and b* [20]. According to the CIE then increased. When the content of glycerin was 1%, the whiteness of
1964 standard color system, the dyeing force of TiO2 on plastics can be the masterbatch was 5.79 higher than that of the masterbatch con-
characterized by the whiteness index of the masterbatch coloring plate. taining no glycerin, while the lightness of the masterbatch increased by
The higher the whiteness (W), the stronger the coloration. In addition, 1.28, indicating that when the glycerin content was 1%, the dyeing
lightness (L) indicates the brightness of the sample plate, and its value is force of masterbatch was best.
related to the degree of light reflection from the sample plate. The Opacifying ability is an important application property of a mas-
higher the lightness, the brighter the sample and the higher the degree terbatch, and light transmittance is directly related to opacifying
of light reflection. If value a is positive, the color of the sample plate is ability. When the film thickness is fixed, the ability of the pigment
reddish, otherwise the color of the sample plate is greenish. If value b is particles to block and absorb light is directly related to the opacifying
positive, the color of the sample plate is yellowish, otherwise the color ability of the film [21]. PLA film colored by masterbatch are shown in
of the sample plate is bluish. Finally, yellowness (Y) is the yellow index Fig. 2. As shown in Table 5, the light transmittance of the masterbatch
of the sample plate. was decreased to a certain extent after the addition of glycerin. This
indicate that glycerol is not only a plasticizer in the PLA/TiO2 system,
but also increases the compatibility between PLA and TiO2, so that the
2.4.2. Opacifying ability testing
Three pieces approximately 50 mm in size were randomly chosen Table 4
and cut from the film. The thickness of each sample was then measured Dyeing force of masterbatches with varying glycerin content.
at three locations using a film thickness gauge, and the average value
L∗ a∗ b∗ W (whiteness) Y (yellowness)
was calculated. Subsequently, the light transmittance of each sample
was also measured at three locations using a digital haze meter and Pure PLA 65.21 0.31 4.26 25.27 16.87
averaged. The measured light transmittance was then converted into PLA/TiO2 83.15 −0.16 5.43 46.40 17.47
the light transmittance of a film with the standard thickness of PLA/TiO2/GI-1% 84.43 −0.41 4.66 52.19 15.81
PLA/TiO2/GI-3% 80.96 0.07 6.60 36.55 19.83
0.02 mm. Finally, the measured light transmittance of all three samples
PLA/TiO2/GI- 5% 71.61 0.69 6.73 21.48 21.76
was averaged to obtain the light transmittance result of the experiment. PLA/TiO2/GI-7% 80.12 0.17 8.33 28.20 22.93
The conversion formula for standard transmittance is as follows:

528
C.-y. Chen et al. Polymer Testing 70 (2018) 526–532

Fig. 1. Colored PLA plate: a) PLA/TiO2; b) PLA/TiO2/GI-1%; c) PLA/TiO2/GI-3%; d) PLA/TiO2/GI- 5%; d) PLA/TiO2/GI-7%.

Table 6
Experimental design and results of masterbatch process optimization based on
opacifying ability.
No. A: Glycerin B: Screw C: Temperature Y: Light
content frequency transmittance

% Hz °C %

1 2.22 26.01 134.05 93.60

2 5.78 26.01 134.05 92.70
3 2.22 28.99 134.05 91.20
4 5.78 28.99 134.05 93.10
5 2.22 26.01 145.95 93.60
6 5.78 26.01 145.95 92.70
7 2.22 28.99 145.95 90.90
8 5.78 28.99 145.95 92.60
Fig. 2. Colored PLA film: a) PLA/TiO2; b) PLA/TiO2/GI-1%; c) PLA/TiO2/GI- 9 1.00 27.50 140.00 92.20
3%; d) PLA/TiO2/GI- 5%; d) PLA/TiO2/GI-7%. 10 7.00 27.50 140.00 92.70
11 4.00 25.00 140.00 92.90
12 4.00 30.00 140.00 90.30
Table 5
13 4.00 27.50 130.00 93.10
Light transmittance of masterbatches with varying glycerin content. 14 4.00 27.50 150.00 92.50
T% (light transmittance) 15 4.00 27.50 140.00 90.20
16 4.00 27.50 140.00 90.00
PLA/TiO2 92.27 17 4.00 27.50 140.00 90.20
PLA/TiO2/GI-1% 90.82 18 4.00 27.50 140.00 90.10
PLA/TiO2/GI-3% 91.52 19 4.00 27.50 140.00 90.00
PLA/TiO2/GI- 5% 86.61 20 4.00 27.50 140.00 89.80
PLA/TiO2/GI- 7% 90.92

TiO2 was better dispersed in the PLA carrier, therefore, the addition of
glycerin enhanced the opacifying ability of white PLA masterbatch, and
the opacifying ability was greatest when the glycerin content was 5%.
However, there was no regular pattern in the change of light trans-
mittance values at different glycerin contents, indicating that the gly-
cerin content was not the main factor affecting the opacifying ability of
PLA/TiO2 masterbatch. Therefore, RSM was used to explore the factors
affecting the opacifying ability of PLA/TiO2 masterbatch.
3.2. Optimization of the PLA/TiO2/GI masterbatch extrusion process using
RSM based on opacifying ability
Table 6 shows the experimental design and results of masterbatch
process optimization based on opacifying ability. Regression analysis
was performed for the data shown in Table 6 using Design-Expert 8.05
software. The results of the regression analysis are shown in Table 7.
The results of the analysis of variance shown in Table 7 indicate that
the P value of the regression model was < 0.0001, showing that the
model was highly significant, and the differences between different
treatments were also significant. The value of R2 was 0.9837, and the
corrected value was 0.9540, indicating that the model accounted for
95.4% of the change in the response. The lack of fit had a P value
of > 0.05, indicating that there was no significant difference in terms of
lack of fit, and the model was adequately fitted to the experiments with
minimal experimental error. Linear items A and B, quadratic items A2,
B2 and C2, and cross-term AB each exerted an extremely significant
influence on the test results, and their significance level reached 0.01.
Linear item C exerted a significant influence on the test results, and its
significance level reached 0.05. Cross-terms AC and BC showed no
obvious effect. According to the regression coefficients of the linear
items, the influence exerted by each factor on the test results was
ranked as follows (strongest to weakest): B-screw frequency > A-gly-
cerin content > C-temperature.
After removing insignificant terms, the regression equation between
each factor and the indicator is:
Y= 844.0585 − 8.765 × A− 14.215 × B− 7.621 × C+ 0.2546 × AB
+ 0.2754 × A2 + 0.2605 × B2 + 0.0283 × C 2 (1)
where: Y is the light transmittance;

529
C.-y. Chen et al. Polymer Testing 70 (2018) 526–532

Table 7
Variance analysis of the experimental results.
Source of variance Sum of squares Degree of freedom Mean square F value P value Significance

Model 36.26 9 4.03 128.38 < 0.0001 **

A-mixing ratio 0.51 1 0.51 16.27 0.0024 **
B-Screw frequency 6.16 1 6.16 196.33 < 0.0001 **
C- Temperature 0.24 1 0.24 7.64 0.0200 *
AB 3.65 1 3.65 116.16 < 0.0001 **
AC 5.0E-003 1 5.0E-003 0.16 0.6982 –
BC 0.080 1 0.08 2.55 0.1414 –
A2 11.06 1 11.06 352.59 < 0.0001 **
B2 4.78 1 4.78 152.21 < 0.0001 **
C2 14.41 1 14.41 459.21 < 0.0001 **
Residual error 0.31 10 0.031
Lack of fit 0.20 5 0.040 1.73 0.2813 –
Pure error 0.12 5 0.023
Total difference 36.57 19

Note: ** significance level reached 0.01; * significant level reached 0.05; - not significant.

A, B, C are the actual values of the three experimental factors.

Various factors of masterbatch processing were analyzed by RSM.

The response surfaces and isolines corresponding to the effects of gly-
cerin content and screw frequency on light transmittance are shown in
Figs. 3 and 4, respectively.
As indicated by the response surface in Fig. 1, the value of light
transmittance decreased first and then increased as factors A and B were
changed. In Fig. 2, the shape of the isolines was an ellipse [22] with its
center at the minimum value of light transmittance on the response
surface, indicating that the glycerin content (A) and screw frequency
(B) exerted significant effects on the light transmittance of the mas-
terbatch. These results are consistent with the results of the regression
analysis.
Using the regression equation (1) in conjunction with Design-Expert
software, the predicted optimal processing conditions were as follows:
glycerin content of 3.22%, screw frequency of 28.76 Hz and tempera-
Fig. 4. Isolines corresponding to the effects of glycerin content and screw fre-
ture of 140.61 °C. Under these conditions, the coordination between
quency on light transmittance.
glycerin, screw shearing and processing temperature was better. The
interaction of various conditions makes the blending effect of system
optimal, representing as the light transmittance of the film made from Table 8
the masterbatch reached 89.72%, and the light transmittance of the Comparison of optimal experimental results and predicted values.
masterbatch was lowest and its opacifying ability was strongest. The Optimization Index Experimental Experimental Predicted Error
predicted processing conditions were verified by experiments (Table 8). Condition Value Value
As shown in Table 8, the light transmittance value in the experi-
Light transmittance Glycerin content: 90.0% 89.72% 0.31%
mental verification was 90.0%, while its predicted value was 89.72%.
3.22%
Therefore, the predicted value of masterbatch light transmittance ob- Frequency: 89.85% 0.14%
tained by this optimization method was consistent with the experi- 28.76 Hz
mental value. Temperature: 89.86% 0.15%
140.61 °C

In summary, the screw frequency, i.e., the rotational speed of the

Fig. 3. Response surface corresponding to the effects of glycerin content and
screw frequency on light transmittance.
screws, was the primary factor influencing the opacifying ability of
PLA/TiO2 masterbatch. In particular, a higher screw frequency pro-
duces a stronger shearing force and better dispersion of the pigment
[23], which increases the opacifying ability of the corresponding mas-
terbatch. In addition, the regression equation obtained from the ex-
periment was suitable for simulating the process of twin-screw extru-
sion, while masterbatch light transmittance was predicted by inputting
the corresponding experimental factors.
Table 9 shows the dyeing strength of PLA/TiO2/GI masterbatch
under the optimal conditions of the extrusion process (glycerin content:
3.22%, screw frequency: 28.76 Hz, temperature: 140.61 °C).
Although the masterbatch with 5% glycerin content had the best
opacifying ability, the whiteness and lightness of this masterbatch was
significantly decreased, which resulted in a lower dyeing force in
comparison with other masterbatches. As shown in Table 9, under

530
C.-y. Chen et al. Polymer Testing 70 (2018) 526–532

Table 9 As shown in Table 10, after the addition of TiO2, the melting index
Color data of PLA/TiO2/GI masterbatch prepared using the extrusion process of the masterbatch with no glycerin was low, and the flowability of the
under optimal conditions. mixture was poor. After the addition of glycerin, the melt index of the
L∗ a∗ b∗ W (whiteness) Y (yellowness) masterbatch increased. When the glycerin content was 3.22%, the melt
flow of the masterbatch was too dilute and its melt index could not be
PLA/TiO2/GI-1% 84.43 −0.41 4.66 52.19 15.81 measured. Therefore, glycerin can improve the melt fluidity of a mas-
PLA/TiO2/GI- 5% 71.61 0.69 6.73 21.48 21.76
terbatch.
PLA/TiO2/GI-3.22% 80.42 0.05 5.81 39.88 18.61

4. Conclusion

(1) In this study, the process formulation of PLA/TiO2 masterbatch was

analyzed using RSM. Within the range of process conditions, each
process condition was continuously analyzed for all conditional
points, so that the trend, mode and efficacy of their influence on the
opacifying ability of the masterbatch were investigated. As a result,
the optimal process conditions were obtained. In this way, the in-
fluence exerted by the processing conditions of PLA/TiO2 mas-
terbatch on its opacifying ability was quickly and comprehensively
analyzed using a small number of experiments. Therefore, it is
feasible to use RSM, ternary quadratic regression, and orthogonal
rotation experiments to optimize the preparation process of a bio-
degradable masterbatch.
(2) The processing process of white PLA masterbatch was analyzed and
optimized using RSM. The experimental analysis showed that the
screw frequency was the main factor affecting the opacifying ability
of a masterbatch. The glycerin content and screw frequency inter-
actively affected the light transmittance of the masterbatch, and
Fig. 5. Rheological curves of masterbatches with varying glycerin content. their effects were significant. The best opacifying ability was
achieved when the glycerin content was 3.22%. In addition,
through simulation, a regression equation was obtained for twin-
Table 10
screw processing of a masterbatch that could be used to predict the
Melt indexes of masterbatches with varying glycerin content.
opacifying ability of a produced masterbatch.
GI/% 0 1 3.22 (3) Compared to the masterbatch with a glycerin content of 5%, the
MF/[g·(10 min)–1] 3.96 7.2 –
whiteness and lightness of PLA/TiO2 masterbatch with 3.22% gly-
cerin content was increased, indicating that the decrease in dyeing
force was not significant, while the best opacifying ability was
optimal processing conditions, the whiteness and lightness of the maintained, and a balance was thus reached between dyeing force
masterbatch were higher than those of the masterbatch prepared with and opacifying ability. The rheological properties of the mas-
5% glycerin content. Therefore, if the dyeing force of the masterbatch is terbatch during its processing were tested at glycerin contents of 0,
not reduced excessively when its opacifying ability is increased, the 1% and 3.22%. It was found that the addition of glycerin improved
dyeing force and opacifying ability of the PLA/TiO2 masterbatch can be the processing performance of white PLA.
balanced. (4) PLA white masterbatch was prepared by adding glycerin into the
PLA/TiO2 system. When the glycerin content was 1%, the dyeing
force of the white masterbatch was the highest. When the glycerin
3.3. Rheological properties of PLA/TiO2/GI masterbatch during its content was 5%, the opacifying ability of the white masterbatch
processing was best, but its dyeing force dropped markedly.

In addition to the properties of whiteness and opacifying ability, the Acknowledgments

rheological properties of masterbatches during processing are also im-
portant. In this study, 3 different masterbatches, i.e., the masterbatch
with the highest degree of whiteness (with 1% glycerin content), the
masterbatch with the best optimal conditions (glycerin content 3.22%),
and the masterbatch containing no glycerin, were selected for torque
rheometer tests to analyze their processing performance. The torque
rheological curves of the tested masterbatches are shown in Fig. 5.
As shown in Fig. 3, as the glycerin content increased, the maximum
torque and balance torque of the masterbatch continuously decreased,
suggesting that the addition of glycerin reduced the viscosity of the
system and improved the processing performance of the masterbatch.
At the same time, the equilibration time of the masterbatch decreased
after the addition of glycerin, while TiO2 wetting was enhanced. As the
equilibrium time was reduced, the affinity and wettability of the
medium (mixture of carrier resin PLA and glycerin) to the pigment
increased, and the system quickly reached dispersive equilibrium be-
tween aggregation and fragmentation [24].
The melt indexes of the tested masterbatches are shown in Table 10.
The authors gratefully acknowledge the financial support from the
National Science Fund (Project No. 51773005, 51473006, 51173005)
and the Project Program of Fenghua Institute of Science and
Technology of Ningbo University of Technology (Project No. FHI-
017102), and The Project of PXM2018_014213_000033 of BTBU.
Appendix A. Supplementary data
Supplementary data related to this article can be found at https://
doi.org/10.1016/j.polymertesting.2018.08.011.
References
[1] I. Armentano, N. Bitinis, E. Fortunati, S. Mattioli, N. Rescignano, R. Verdejo,
M.A. Lopez-Manchado, J.M. Kenny, Multifunctional nanostructured PLA materials
for packaging and tissue engineering, Prog. Polym. Sci. 38 (2013) 1720–1747.
[2] I. Armentano, E. Fortunati, N. Burgos, F. Dominici, F. Luzi, S. Fiori, A. Jiménez,

531
C.-y. Chen et al.
K. Yoon, J. Ahn, S. Kang, J.M. Kenny, Processing and characterization of plasticized
PLA/PHB blends for biodegradable multiphase systems, Express Polym. Lett. 9
(2015).
[3] X.U. Ying, H. Qiao, W.U. Li-Feng, Performance of color masterbatch with LLDPE/
LDPE, Plastics 4 (2008).
[4] Y.N. Wang, Y.X. Weng, L. Wang, Characterization of interfacial compatibility of
polylactic acid and bamboo flour (PLA/BF) in biocomposites, Polym. Test. 36
(2014).
[5] Narayan R, Balakrishnan S, Kubik D A, et al. Biodegradable Polymer Masterbatch,
and a Composition Derived Therefrom Having Improved Physical Properties: US,
US8008373 Patent. (2011).
[6] Ding S. A Fully-biodegradable Plastic Masterbatch and its Preparation Process: Ep,
EP1659149 Patent. (2006).
[7] K. Ohenoja, M. Illikainen, Jouko Niinimäki, Effect of operational parameters and
stress energies on the particle size distribution of TiO 2 pigment in stirred media
milling, Powder Technol. 234 (2013) 91–96, https://doi.org/10.1016/j.powtec.
2012.09.038.
[8] M. Huldén, E. Sjöblom, Adsorption of some common surfactants and polymers on
TiO2-pigments, Prog. Colloid Polym. Sci. 82 (1990) 28.
[9] J.C. Auger, R.G. Barrera, B. Stout, Scattering efficiency of clusters composed by
aggregated spheres, J. Quant. Spectrosc. Radiat. Transfer 79 (2003) 2.
[10] C. Lei, D. Chen, R. Huang, et al., Time‐dependent rheological behavior of low‐-
density polyethylene white color masterbatches under dynamic stress field, J. Appl.
Polym. Sci. 85 (2010) 14.
[11] P. Sarazin, G. Li, W.J. Orts, et al., Binary and ternary blends of polylactide, poly-
caprolactone and thermoplastic starch[J], Polymer 49 (2008) 2.
[12] L.M. Sánchez, Dinámica relacional y comunicacional y perfiles de pérdidas perso-
nales en la fase pre clínica de casos de Alzheimer no genético de instalación tem-
prana, Polym. Test. 30 (2003) 5.
532
Polymer Testing 70 (2018) 526–532
[13] M.A. Bezerra, R.E. Santelli, E.P. Oliveira, et al., Response surface methodology
(RSM) as a tool for optimization in analytical chemistry, Talanta 76 (2008) 5.
[14] P. Colonna, J.L. Doublier, J.P. Melcion, F.D. Monredon, C. Mercier, Extrusion
cooking and drum drying of wheat starch. I. Physical and macromolecular mod-
ifications, Cereal Chem. 61 (1984) 6.
[15] B. Maridass, B.R. Gupta, Process optimization of devulcanization of waste rubber
powder from syringe stoppers by twin screw extruder using response surface
methodology, Polym. Compos. 29 (2010) 12.
[16] Y. Li, J. Peng, W. Lui, et al., Effects of glycerin and ethylene–acrylic acid on com-
position optimization of PVOH/starch‐blended biodegradable resin using response
surface methodology, J. Appl. Polym. Sci. 114 (2010) 5.
[17] Y. Zare, H. Garmabi, F. Sharif, Optimization of mechanical properties of PP/
Nanoclay/CaCO3 ternary nanocomposite using response surface methodology, J.
Appl. Polym. Sci. 122 (2011) 5.
[18] C. Reyesmoreno, C. Romerourías, J. Miláncarrillo, et al., Optimization of the solid
state fermentation process to obtain tempeh from hardened chickpeas (Cicer ar-
ietinum L.), Plant Foods Hum. Nutr. 55 (2000) 3.
[19] G. Ylimaki, Z.J. Hawrysh, R.T. Hardin, et al., Response surface methodology in the
development of rice flour yeast breads: sensory evaluation, J. Food Sci. 56 (2010) 3.
[20] K. Ohsawa, M. Yamaguchi, Multiprimary display optimized for CIE1931 and
CIE1964 color matching functions, Proc. SPIE-Int. Soc. Opt. Eng. 4421 (2001) 939.
[21] K. Tanaka, Transfer of semicrystalline polymers sliding against a smooth steel
surface, Wear 75 (1982) 1.
[22] G.E.P. Box, J.S. Hunter, W.G. Hunter, Statistics for Experimenters : an Introduction
to Design, Data Analysis, and Model Building 73 Wiley, 1978, p. 10.
[23] Gerard K, Robbins A L. Dispersion of pigments in ethylene polymers: US,
US3257351 Patent,. 3257,351 (1966).
[24] X. Liu, T. Wang, L.C. Chow, et al., Effects of inorganic fillers on the thermal and
mechanical properties of poly(lactic acid), Int. J. Polym. Sci. 2014 (2014).